Formulations for use with intermediate transfer members in indirect printing systems and printing processes therewith

Abstract

The present disclosure relates to a formulation for use with an intermediate transfer member of an indirect printing system and a printing method using the same. The present disclosure further relates to an intermediate transfer member having a release layer surface coated with the formulation of the present invention. The present disclosure also relates to a printing substrate, a printed product and a printed pattern produced using the formulation of the present invention, and a kit including the formulation.

Description

[Technical Field]

[0001] This disclosure relates to indirect printing processes and systems, and more particularly to compositions suitable for processing intermediate transfer members. [Background technology]

[0002] The following is a list of references that may be relevant to the subject matter of this disclosure: [1] U.S. Patent No. 9,428,663 describes an indirect printing apparatus employing a sacrificial coating on an intermediate transfer member. [2] U.S. Patent Application No. 2015 / 0361288 describes a sacrificial coating composition for an indirect printing process. [3] U.S. Patent Application No. 10, i 081, 175 describes an auxiliary liquid set, an image recording method and an image recording apparatus. [4] International Publication No. WO 2014 / 021840 describes optically transparent fluid compositions formulated for application onto printed materials.

[0003] The following patent applications / publications to the present applicant [5]–

[33] provide potentially relevant background material and are incorporated herein by reference in their entirety: [5] WO 2017 / 208246 (Publication of PCT / IL2017 / 050616 filed on 1 June 2017); [6] WO / 2019 / 111223 (Publication of PCT / IB2018 / 059761 filed on December 7, 2018); [7]PCT application no. PCT / IB2019 / 055288; [8] WO / 2017 / 009722 (Publication of PCT / IB2016 / 053049 filed on 25 May 2016); [9] WO / 2016 / 166690 (Publication of PCT / IB2016 / 052120 filed on April 4, 2016);

[10] WO / 2016 / 151462 (Publication of PCT / IB2016 / 051560 filed on 20 March 2016);

[11] WO / 2016 / 113698 (Publication of PCT / IB2016 / 050170 filed on 14 January 2016);

[12] WO / 2015 / 110988 (Publication of PCT / IB2015 / 050501 filed on 22 January 2015);

[13] WO / 2015 / 036812 (Publication of PCT / IB2013 / 002571 filed on 12 September 2013);

[14] WO / 2015 / 036864 (Publication of PCT / IB2014 / 002366 filed on 11 September 2014);

[15] WO / 2015 / 036865 (Publication of PCT / IB2014 / 002395 filed on 11 September 2014);

[16] WO / 2015 / 036906 (Publication of PCT / IB2014 / 064277 filed on 12 September 2014);

[17] WO / 2013 / 136220 (Publication of PCT / IB2013 / 051719 filed on March 5, 2013);

[18] WO / 2013 / 132419 (Publication of PCT / IB2013 / 051717 filed on March 5, 2013);

[19] WO / 2013 / 132424 (Publication of PCT / IB2013 / 051727 filed on March 5, 2013);

[20] WO / 2013 / 132420 (Publication of PCT / IB2013 / 051718 filed on 5 March 2013);

[21] WO / 2013 / 132439 (Publication of PCT / IB2013 / 051755 filed on 5 March 2013);

[22] WO / 2013 / 132438 (Publication of PCT / IB2013 / 051751 filed on March 5, 2013);

[23] WO / 2013 / 132418 (Publication of PCT / IB2013 / 051716 filed on March 5, 2013);

[24] WO / 2013 / 132356 (Publication of PCT / IB2013 / 050245 filed on 10 January 2013);

[25] WO / 2013 / 132345 (Publication of PCT / IB2013 / 000840 filed on 5 March 2013);

[26] WO / 2013 / 132339 (Publication of PCT / IB2013 / 000757 filed on 5 March 2013);

[27] WO / 2013 / 132343 (Publication of PCT / IB2013 / 000822 filed on March 5, 2013);

[28] WO / 2013 / 132340 (Publication of PCT / IB2013 / 000782 filed on 5 March 2013);

[29] WO / 2013 / 132432 (Publication of PCT / IB2013 / 051743 filed on March 5, 2013);

[30] WO / 2019 / 012456 (Publication of PCT / IB2018 / 055126 filed on 11 July 2018);

[31] U.S. Patent No. 9,229,664;

[32] WO 2013 / 132424 (publication of PCT / IB2013 / 051727 filed on 5 March 2013); and

[33] WO 2017 / 208152 (Publication of PCT / IB2017 / 053177 filed on 30 May 2017).

[0004] The acceptance of the foregoing references in this specification does not imply that they are related in any way to the patentability of the subject matter of this disclosure. [Overview of the project] [Problems that the invention aims to solve]

[0005] The inventors of this invention have developed an aqueous formulation for use with an intermediate transfer member (ITM) in an indirect printing system. [Means for solving the problem]

[0006] As further disclosed herein, aqueous formulations of the present invention can offer one or more of the following advantages: improved solubility at room temperature, good hydration on ITM, improved ink image quality, good ink wetting and ink diffusion properties, improved wet image quality and / or improved image transfer with aqueous inks, improved transfer to substrate media without drying peeling during printing, improved shelf life, and improved processing in indirect printing machines. Sometimes, to achieve one or more of the aforementioned advantages, formulations according to the present invention may contain at least one modified polysaccharide as disclosed herein.

[0007] Furthermore, when the aqueous formulations of the present invention are used as ITM-treated formulations in the printing processes disclosed herein, high-quality ink images and print patterns / printed products with improved mechanical properties, such as improved abrasion resistance. To achieve improved mechanical properties, formulations according to the present invention may further include at least one particulate material as disclosed herein.

[0008] In this invention, the release surface of the intermediate transfer member is pre-treated (e.g., coated) with an aqueous formulation according to the invention before the ink image is applied thereto. The aqueous formulation (also referred to herein as the aqueous treatment formulation) is applied to the surface of the ITM to form a thin wetting treatment layer, which is optionally subjected to a drying process on the ITM release surface, leaving a thin dried treatment film on the ITM release surface. Subsequently, droplets of aqueous ink are applied to the thin dried treatment film (e.g., by an inkjet method) to form an ink image thereon. Note that the ink droplets may be continuous or discontinuous. Note further that the ink droplets may cover all or part of the thin dried treatment film (in the latter case, there will be areas on the dried treatment film where no ink is applied). The formed ink image is then subjected to a drying process, leaving an ink residue on the dried treatment film. The dried ink image is then transferred together with the thin dried treatment film from the ITM surface to the final printing substrate (e.g., foil-based, paper-based, or plastic-based).

[0009] Therefore, a thin treatment layer according to the present disclosure is present on the upper surface region of the final printed substrate. Being the uppermost layer, the thin treatment layer enables beneficial adjustment of image surface properties, such as coefficient of friction, mechanical strength, etc., and thus functions as a protective layer for the ink image surface.

[0010] As further disclosed in the present application, the printed image resulting from the present invention exhibits improved durability, for example, from the viewpoints of abrasion resistance and / or coefficient of friction. The improvement is considered to be achieved due to the presence of specific components in the aqueous treatment formulation. Specifically, the aqueous treatment formulation according to the present invention contains specific thermoplastic and / or thermosetting particle materials, which provide the resulting printed product (i.e., the substrate on which the ink image is adhered together with the thin dried treatment film) with improved mechanical properties (such as improved abrasion resistance and / or improved coefficient of friction) compared to a printed product manufactured without said particle materials. The improved mechanical properties of the printed product are seen in both the regions on the image where the ink is present and the regions where the ink is not present (i.e., the regions where only the thin dried treatment film is present).

[0011] It has been found that the aforementioned specific particle materials can coexist beneficially with various components of the aqueous treatment formulation, the properties of various components of the indirect printing system according to the present invention (e.g., ITM, ink formulation), and printing conditions (e.g., temperature, operating speed).

[0012] Additives such as wax particles or a binder are well known in the art as ink additives that improve the rub resistance of an ink image formed using the ink. The additives are specific to the ink being used, and adding it to each ink in the printing process is necessary to achieve the rub resistance of the printed ink. In contrast to ink additives well known in the art, thermoplastic and / or thermosetting particulate materials are present in the aqueous treatment formulation according to the present invention. There is no ink present in the aqueous treatment formulation. In the printing process according to the present invention, a thin dried treatment film is first formed (the thermoplastic and / or thermosetting particulate materials are present in the thin dried treatment film). The ink is then deposited on the thin dried treatment film. The dried treatment film thus provides improved image durability for a wide variety of inks. Specifically, as demonstrated hereinafter in this specification, the improved durability of the ink images of the present invention is achieved with a wide range of inks, rather than being limited to specific inks. Accordingly, the improved durability achieved in accordance with the present invention can be considered universal for all inks without showing any impairment to print quality, color gamut, etc.

[0013] Thanks to the nature of the indirect printing method utilizing the aqueous formulation according to the present invention, the need for a rub-resistant (or other resistant) ink additive can be eliminated. However, it should be noted that the ink formulations according to the present invention may or may not contain a rub-resistant or other mechanically improving additive. For this purpose, if such an additive (e.g., well known in the art) is present in the ink formulation, the improvement in the mechanical properties of the resulting ink image can be either additive (the sum of the improvements resulting from the ink additive and from the aqueous treatment formulation according to the present invention) or synergistic (exceeding the sum of the improvements resulting from the ink additive and from the aqueous treatment formulation according to the present invention).

[0014] It should be further noted that the improved mechanical properties of the image of the printed product resulting from the present invention are shown in both the areas of the image containing ink and the areas without ink. The areas without ink originate from areas on the treated ITM where no ink adheres and therefore only the treated layer is transferred during transfer to the substrate. Such areas exhibit improved durability, such as an improved coefficient of friction.

[0015] Coating compositions such as varnishes or lacquers are well known in the art for providing improved mechanical properties to printed images. These coating compositions are occasionally applied directly onto printed images to provide a protective coating layer. Such protective coating layers are known for their relatively high thickness (e.g., a layer thickness exceeding 1 micron). In contrast to such direct printing processes, the aqueous treatment formulations according to the present invention form a thin layer (on a nanometer scale) on the ITM. Apart from beneficially providing improved durability to the resulting printed product, the use of aqueous treatment formulations in the process according to the present invention also provides improved transfer from the ITM to the final substrate surface by ensuring contact. Furthermore, the thin treatment layer generated from the aqueous treatment formulations according to the present invention also affects the surface of the ITM (e.g., blanket), thus enabling beneficial lateral distribution of ink droplets on the ITM, and thus providing improved print quality, among other things, to the resulting ink image. Furthermore, the thin layer formed by the aqueous treatment formulation according to the present invention also provides protection for the ITM surface from contamination, degradation, and mechanical damage, and can also function as a disposal coating transferred from the ITM surface to the final substrate surface, ensuring that the ITM surface remains fresh after each transfer. Therefore, using the aqueous formulation according to the present invention eliminates the need for applying a varnish / protective layer.

[0016] Accordingly, in one aspect thereof, the present invention provides an aqueous (treated) formulation for use with an intermediate transfer member of a printing system, the formulation is At least one water-soluble polymer [e.g., cellulose ether, e.g., methylcellulose and hydroxypropyl methylcellulose (HPMC), and at least one modified polysaccharide], At least one water-containing carrier liquid, and Optionally, one or more of the following: (a) at least one water-retaining agent (water absorbent), (b) at least one surfactant (e.g., nonionic surfactant, silicone surfactant), and (c) at least one wetting agent, e.g., polyethyleneimine (PEI). Includes, The aforementioned formulation optionally further comprises at least one particle material selected from (i) at least one thermoplastic polymer particle material, (ii) at least one thermosetting polymer particle material, or (iii) a combination thereof.

[0017] In one further embodiment, the present invention provides an aqueous (treated) formulation for use with an intermediate transfer member in a printing system, the formulation being: At least one modified polysaccharide such as cellulose ether, e.g., methylcellulose and hydroxypropylmethylcellulose (HPMC), At least one water-containing carrier liquid, (i) at least one thermoplastic polymer particle material, (ii) at least one thermosetting polymer particle material, or (iii) a combination thereof, and at least one particle material selected from these, Optionally, one or more of the following: (a) at least one water-retaining agent (water absorbent), (b) at least one surfactant (e.g., nonionic surfactant, silicone surfactant), and (c) at least one wetting agent, e.g., polyethyleneimine (PEI). Includes.

[0018] In another embodiment, the present invention provides an aqueous (treated) formulation for use with an intermediate transfer member in a printing system, the aqueous formulation is At least one modified polysaccharide [e.g., cellulose ethers such as methylcellulose and hydroxypropyl methylcellulose (HPMC)], At least one wetting agent (e.g., PEI), At least one absorbent, At least one surfactant (e.g., a nonionic surfactant, a silicone surfactant), At least one water-containing carrier liquid Includes, The aforementioned formulation optionally further comprises at least one particle material selected from (i) at least one thermoplastic polymer particle material, (ii) at least one thermosetting polymer particle material, or (iii) a combination thereof.

[0019] Furthermore, in another embodiment, the present invention provides an aqueous (treated) formulation for use with an intermediate transfer member in a printing system, the formulation is a. At least one modified polysaccharide [e.g., cellulose ether such as methylcellulose and hydroxypropyl methylcellulose (HPMC)] having solubility in at least 1.5%, or at least 2%, or at least 3%, or at least 4%, or at least 5%, or at least 7%, or at least 8%, or at least 10% by weight of water or aqueous treatment formulation at 25°C, and at least one of the following properties: i. Gelation temperature measured at a 2% weight concentration in water or aqueous-treated formulation, at least 50°C, or at least 55°C, or at least 57°C, or at least 60°C, or at least 62°C, or at least 65°C, or at least 68°C, or at least 70°C, or at least 75°C, and optionally, up to 120°C, up to 110°C, up to 105°C, or between 60 and 120°C, or between 60 and 110°C, or between 60 and 100°C, or between 65 and 110°C, or between 65 and 105°C, or between 65 and 100°C, or between 70 and 110°C, or between 70 and 100°C, or between 75 and 110°C, or between 75 and 100°C, or between 80 and 100°C. ii. The viscosity at mPa·s, measured at a 2% weight concentration in water at 25°C, is within the range of a maximum of 11, a maximum of 10, a maximum of 9, a maximum of 8, a maximum of 7, a maximum of 6, a maximum of 5, a maximum of 4, and optionally, at least 0.5 or at least 1 or at least 2, or within the range of 0.5 to 10, 1 to 8, 2 to 8, 2 to 5, or 2 to 4. Having at least one modified polysaccharide, b.Water c. Optionally, at least one, two, or all three of the following: at least one water absorbent, at least one surfactant (e.g., a nonionic surfactant, a silicone surfactant), and at least one wetting agent [e.g., polyethyleneimine (PEI)]. Includes, The aforementioned formulation optionally further comprises at least one particle material selected from (i) at least one thermoplastic polymer particle material, (ii) at least one thermosetting polymer particle material, or (iii) a combination thereof.

[0020] In another embodiment, the present invention provides an aqueous (treated) formulation for use with an intermediate transfer member in a printing system, the formulation is (a) At 25°C, at least 1.5%, or at least 2%, or at least 3%, or at least 4%, or at least 5%, or at least 7%, or at least 8%, or at least 10% by weight of water or aqueous treatment formulation, at least one modified polysaccharide (e.g., cellulose ether such as methylcellulose and HPMC), (b) at least one wetting agent, for example, PEI, and (c) A carrier liquid containing water, wherein the water constitutes at least 50%, at least 55%, at least 60%, or at least 65% by weight of the aqueous (treated) formulation. (d) Optionally, at least one, at least two, or all of the following: water absorbent, nonionic surfactant, and silicone surfactant Includes, The aforementioned formulation optionally further comprises at least one particle material selected from (i) at least one thermoplastic polymer particle material, (ii) at least one thermosetting polymer particle material, or (iii) a combination thereof.

[0021] In another embodiment, the present invention provides an aqueous (treated) formulation for use with an intermediate transfer member in a printing system, the aqueous formulation is At least one water-soluble polymer (optionally, at least one modified polysaccharide, e.g., cellulose ether such as methylcellulose and HPMC), (i) a cationic emulsion of at least one oxidized polyethylene wax particle material, (ii) a dispersion and / or emulsion of at least one coating wax particle material, and (iii) a dispersion and / or emulsion of at least one thermosetting polymer particle material, and Water-containing carrier liquid Includes.

[0022] In another embodiment, the present invention provides an aqueous (treated) formulation for use with an intermediate transfer member in a printing system, the aqueous formulation is At least one water-soluble polymer (optionally, at least one modified polysaccharide, e.g., cellulose ether such as methylcellulose and HPMC), At least one oxidized polyethylene wax particle material and at least one cationic emulsion, A carrier liquid containing water, and Optionally, one or more of the following: (a) at least one surfactant, (b) at least one water-retaining agent, and (c) at least one wetting agent. Includes.

[0023] In one further embodiment, the present invention provides an aqueous (treated) formulation for use with an intermediate transfer member in a printing system, the aqueous formulation is At least one water-soluble polymer (optionally, at least one modified polysaccharide, e.g., cellulose ether such as methylcellulose and HPMC), At least one dispersion or emulsion of at least one coating wax particle material, A carrier liquid containing water, and Optionally, one or more of the following: (a) at least one surfactant, (b) at least one water-retaining agent, and (c) at least one wetting agent. Includes.

[0024] In one further embodiment, the present invention provides an aqueous (treated) formulation for use with an intermediate transfer member in a printing system, the aqueous formulation is At least one water-soluble polymer (optionally, at least one modified polysaccharide, e.g., cellulose ether such as methylcellulose and HPMC), At least one dispersion or emulsion of at least one thermosetting polymer particulate material, A carrier liquid containing water, and Optionally, one or more of the following: (a) at least one surfactant, (b) at least one water-retaining agent, and (c) at least one wetting agent. Includes.

[0025] In one further embodiment, the present invention provides an aqueous (treated) formulation for use with an intermediate transfer member in a printing system, the aqueous formulation is At least one water-soluble polymer (optionally, at least one modified polysaccharide, e.g., cellulose ether such as methylcellulose and HPMC), (i) at least one oxidized polyethylene wax particle material, (ii) at least one coating wax particle material, (iii) at least one thermosetting polymer particle material, or (iv) any combination thereof, at least one particle material selected from these, A carrier liquid containing water, and Optionally, one or more of the following: (a) at least one surfactant, (b) at least one water-retaining agent, and (c) at least one wetting agent. Includes.

[0026] Furthermore, in another embodiment, the present invention provides an aqueous (treated) formulation for use with an intermediate transfer member of a printing system, the aqueous formulation is At least one water-soluble polymer (optionally, at least one modified polysaccharide, e.g., cellulose ether such as methylcellulose and HPMC), (i) at least one coating wax particle material, (ii) at least one thermosetting polymer particle material, or (iii) any combination thereof, at least one particle material selected from these, A carrier liquid containing water, and Optionally, one or more of the following: (a) at least one surfactant, (b) at least one water-retaining agent, and (c) at least one wetting agent. Includes.

[0027] In one further embodiment, the present invention provides an aqueous (treated) formulation for use with an intermediate transfer member in a printing system, the aqueous formulation is At least one water-soluble polymer (optionally, at least one modified polysaccharide, e.g., cellulose ether such as methylcellulose and HPMC), At least one coating wax particle material, and Optionally, one or more of the following: (a) at least one surfactant, (b) at least one water-retaining agent, and (c) at least one wetting agent. Includes.

[0028] In one further embodiment, the present invention provides an aqueous (treated) formulation for use with an intermediate transfer member in a printing system, the aqueous formulation is At least one water-soluble polymer (optionally, at least one modified polysaccharide, e.g., cellulose ether such as methylcellulose and HPMC), At least one thermosetting polymer particle material, A carrier liquid containing water, and Optionally, one or more of the following: (a) at least one surfactant, at least one hygrometer, and (c) at least one wetting agent. Includes.

[0029] In another embodiment, the present invention provides an aqueous formulation for use with an intermediate transfer member of a printing system, the aqueous formulation is At least one water-soluble polymer (optionally, the at least one water-soluble polymer is at least one modified polysaccharide, such as methylcellulose and cellulose ethers such as HPMC), At least one surfactant (which may optionally be a first nonionic surfactant having at least 7% solubility in water at 25°C, and / or optionally a second nonionic, silicone-containing surfactant having at least 1% solubility in water at 25°C), (i) at least one thermoplastic polymer particulate material (optionally in the form of an emulsion or dispersion), (ii) at least one thermosetting polymer particulate material (optionally in the form of an emulsion or dispersion), or (iii) a combination thereof, at least one particulate material selected from these, A carrier liquid containing water, optionally comprising at least about 55% by weight of an aqueous formulation, and Optionally, one or more of the following: (a) at least one water-retaining agent, and (b) at least one wetting agent, e.g., PEI. Includes.

[0030] In another embodiment, the present invention provides an aqueous (treated) formulation for use with an intermediate transfer member in a printing system, the aqueous formulation is At least 1.5% by weight of at least one water-soluble polymer having a solubility in water of at least 5% at 25°C (optionally, the at least one water-soluble polymer is at least one modified polysaccharide, e.g., cellulose ether such as methylcellulose and HPMC), A first nonionic surfactant having a solubility in water of at least 5% by weight and at least 7% at 25°C, A second nonionic, silicone-containing surfactant having solubility in at least 1% water at 25°C, (i) at least one thermoplastic polymer particle material, (ii) at least one thermosetting polymer particle material, or (iii) a combination thereof, at least one particle material selected from these, A carrier liquid containing water, wherein the water constitutes at least about 55% by weight of the aqueous formulation, and Optionally, one or more of the following: (a) at least one water-retaining agent, and (b) at least one wetting agent, e.g., polyethyleneimine (PEI). Includes.

[0031] In one further embodiment, the present invention provides an aqueous (treated) formulation for use with an intermediate transfer member in a printing system, the aqueous formulation is At least 1.5% by weight of at least one water-soluble polymer having a solubility in water of at least 5% at 25°C (optionally, the at least one water-soluble polymer is at least one modified polysaccharide, e.g., cellulose ether such as methylcellulose and HPMC), A first nonionic surfactant having a solubility in water of at least 5% by weight and at least 7% at 25°C, A second nonionic, silicone-containing surfactant having solubility in at least 1% water at 25°C, At least one thermoplastic polymer particle material, A carrier liquid containing water, wherein the water constitutes at least about 55% by weight of the aqueous formulation, and Optionally, one or more of the following: (a) at least one water-retaining agent, and (b) at least one wetting agent, e.g., PEI. Includes.

[0032] In one further embodiment, the present invention provides an aqueous (treated) formulation for use with an intermediate transfer member in a printing system, the aqueous formulation is At least 1.5% by weight of at least one water-soluble polymer having a solubility in water of at least 5% at 25°C (optionally, the at least one water-soluble polymer is at least one modified polysaccharide, e.g., cellulose ether such as methylcellulose and HPMC), A first nonionic surfactant having a solubility in water of at least 5% by weight and at least 7% at 25°C, A second nonionic, silicone-containing surfactant having solubility in at least 1% water at 25°C, At least one thermosetting polymer particle material, A carrier liquid containing water, wherein the water constitutes at least about 55% by weight of the aqueous formulation, and Optionally, one or more of the following: (a) at least one water-retaining agent, and (b) at least one wetting agent, e.g., PEI. Includes.

[0033] Furthermore, in one further embodiment, the present invention provides an aqueous (treated) formulation for use with an intermediate transfer member of a printing system, the aqueous formulation is At least 1.5% by weight of at least one water-soluble polymer having a solubility in water of at least 5% at 25°C (optionally, the at least one water-soluble polymer is at least one modified polysaccharide, e.g., cellulose ether such as methylcellulose and HPMC), A first nonionic surfactant having a solubility in water of at least 5% by weight and at least 7% at 25°C, A second nonionic, silicone-containing surfactant having solubility in at least 1% water at 25°C, (i) a dispersion and / or emulsion of at least one thermoplastic polymer particulate material, (ii) a dispersion and / or emulsion of at least one thermosetting polymer particulate material, or (iii) a combination thereof, at least one dispersion and / or emulsion selected from these, A carrier liquid containing water, wherein the water constitutes at least about 55% by weight of the aqueous formulation, and Optionally, one or more of the following: (a) at least one water-retaining agent, and (b) at least one wetting agent, e.g., PEI. Includes.

[0034] In another embodiment, the present invention provides an aqueous (treated) formulation for use with an intermediate transfer member in a printing system, the aqueous formulation is At least 1.5% by weight of at least one water-soluble polymer having a solubility in water of at least 5% at 25°C (optionally, the at least one water-soluble polymer is at least one modified polysaccharide, e.g., cellulose ether such as methylcellulose and HPMC), A first nonionic surfactant having a solubility in water of at least 5% by weight and at least 7% at 25°C, A second nonionic, silicone-containing surfactant having solubility in at least 1% water at 25°C, Emulsion and / or dispersion of at least one thermoplastic polymer particulate material, A carrier liquid containing water, wherein the water constitutes at least about 55% by weight of the aqueous formulation, and Optionally, one or more of the following: (a) at least one water-retaining agent, and (b) at least one wetting agent, e.g., PEI. Includes.

[0035] In one further embodiment, the present invention provides an aqueous (treated) formulation for use with an intermediate transfer member in a printing system, the aqueous formulation is At least 1.5% by weight of at least one water-soluble polymer having a solubility in water of at least 5% at 25°C (optionally, the at least one water-soluble polymer is at least one modified polysaccharide, e.g., cellulose ether such as methylcellulose and HPMC), A first nonionic surfactant having a solubility in water of at least 5% by weight and at least 7% at 25°C, A second nonionic, silicone-containing surfactant having solubility in at least 1% water at 25°C, A dispersion and / or emulsion of at least one thermosetting polymer particle material, A carrier liquid containing water, wherein the water constitutes at least about 55% by weight of the aqueous formulation, and Optionally, one or more of the following: (a) at least one water-retaining agent, and (b) at least one wetting agent, e.g., PEI. Includes.

[0036] In some embodiments, the particulate material according to the present invention is provided in the form of an emulsion.

[0037] In some embodiments, the particulate material according to the present invention is provided in the form of a dispersion.

[0038] In another embodiment, the present invention provides a method for indirect printing, a. To provide an intermediate transfer member (ITM) including a release layer surface. b. To provide an aqueous (treated) formulation in accordance with the present invention. c. Apply an aqueous (treated) compound to the surface of the ITM release layer, and optionally form a wet (treated) layer thereon with a maximum thickness of approximately 1.0 μm (e.g., maximum 0.8 μm, maximum 0.5 μm, maximum 0.4 μm, maximum 0.3 μm) (e.g., uniform thickness). d. Optionally, the wet (treated) layer is subjected to a drying process to form a dried (treated) thin film layer on the surface of the ITM peel layer from the wet (treated) layer, wherein the dried thin film layer optionally has a thickness of at least about 20 nm and a maximum of about 200 nm (for example, a maximum of 200 nm, 190 nm, 180 nm, 170 nm, 160 nm, 150 nm, 140 nm, 130 nm, 120 nm, 110 nm, 100 nm, 90 nm, 80 nm, 70 nm, 60 nm, 50 nm, and optionally, at least 20 nm or at least 30 nm). e. Deposition of droplets of aqueous ink onto a dried (treated) thin film to form an ink image on the surface of the ITM release layer. f. Drying the ink image to leave ink image residue on the surface of the ITM release layer, and g. Transferring ink image residue (e.g., together with the dried thin film layer) onto the printing substrate by pressurized contact between the ITM and the printing substrate. Includes.

[0039] In one further embodiment, the present invention provides a method for indirect printing, a. To provide an intermediate transfer member including a release layer surface. b. To provide an aqueous formulation, wherein the aqueous formulation is At least one water-soluble polymer (optionally, at least one modified polysaccharide, e.g., cellulose ether such as methylcellulose and HPMC), (i) at least one thermoplastic polymer particulate material (optionally provided in the form of an emulsion and / or dispersion), (ii) at least one thermosetting polymer particulate material (optionally provided in the form of an emulsion and / or dispersion), or (iii) a combination thereof, at least one particulate material selected from these, A carrier liquid containing water, and Optionally, one or more of (iv) at least one surfactant, (v) at least one water-retaining agent, and (vi) at least one wetting agent, Including, c. Apply an aqueous formulation to the surface of the ITM release layer, and optionally form a wet (treated) layer thereon having a maximum thickness of approximately 1.0 μm (for example, a maximum of 0.8 μm, 0.5 μm, 0.4 μm, or 0.3 μm) (for example, a uniform thickness). d. Optionally, the wet (treated) layer is subjected to a drying process to form a dried (treated) thin film layer on the surface of the ITM peel layer from the wet (treated) layer, wherein the dried thin film layer optionally has a thickness of at least about 20 nm and a maximum of about 200 nm (for example, a maximum of 200 nm, 190 nm, 180 nm, 170 nm, 160 nm, 150 nm, 140 nm, 130 nm, 120 nm, 110 nm, 100 nm, 90 nm, 80 nm, 70 nm, 60 nm, 50 nm, and optionally, at least 20 nm or at least 30 nm). e. Deposition of droplets of aqueous ink onto a dried (treated) thin film to form an ink image on the surface of the ITM release layer. f. Drying the ink image to leave ink image residue on the surface of the ITM release layer, and g. Transferring ink image residue (e.g., together with the dried thin film layer) onto the printing substrate by pressurized contact between the ITM and the printing substrate. Includes.

[0040] In yet another embodiment, the present invention provides a method for indirect printing onto a substrate, the method being To provide an intermediate transfer member, To provide aqueous treatment formulations substantially as disclosed above and below in this specification, A water-based treatment compound is applied to the image-receiving surface of the ITM to form a wet treatment layer. Optionally, the wet treatment layer is dried at least partially to form at least a partially dried treatment layer. Forming a wet ink image by ejecting water-based ink droplets onto a partially dried processing layer. To form a partially dried ink image thin film by at least partially drying a wet ink image on an aqueous treatment layer, The partially dried ink image thin film is transferred to the printing substrate by pressurized contact between the surface of the ITM and the printing substrate. Includes.

[0041] In one further embodiment, the present invention provides a system for printing, the system is a. Intermediate transfer member including the surface of the release layer, b. Aqueous formulations according to the present invention, c. A processing station for applying an aqueous formulation to the ITM surface and forming a wet (treated) layer thereon, optionally having a maximum thickness of approximately 1.0 μm (e.g., maximum 0.8 μm, maximum 0.5 μm, maximum 0.4 μm, maximum 0.3 μm). d. An image forming station for forming an ink image on an ITM by depositing droplets of aqueous ink onto the ITM surface after a wet (treated) layer has dried to become a dry (treated) thin film, such that droplets of aqueous ink are coated onto a dry thin film, wherein the dry thin film layer optionally has a thickness of at least about 20 nm and a maximum of about 200 nm (for example, a maximum of 200 nm, 190 nm, 180 nm, 170 nm, 160 nm, 150 nm, 140 nm, 130 nm, 120 nm, 110 nm, 100 nm, 90 nm, 80 nm, 70 nm, 60 nm, 50 nm, and optionally at least 20 nm or at least 30 nm), and e. Transfer station for transferring ink images from ITM to a substrate (e.g., together with a dried thin film layer) Includes.

[0042] In yet another embodiment, the present invention provides a system for indirect printing, the system is i. Intermediate transfer member, for example, one including a silicone-based release layer surface, ii. Containers containing aqueous (treated) formulations substantially as disclosed herein, iii. A processing station for applying an aqueous (treatment) compound to the surface of the silicone-based release layer of ITM and forming a wet treatment layer thereon. iv. Optional drying stations for drying aqueous-treated formulations, v. At least one inkjet nozzle positioned in close proximity to the intermediate transfer member and configured to eject ink droplets onto the aqueous treatment mixture formed on the intermediate transfer member, vi. An ink processing station configured to at least partially dry the ink on an aqueous processing mixture formed on an intermediate transfer member to produce an ink image residue, and vii. Ink image residue transfer mechanism for transferring ink image residue to a printing substrate by pressurized contact between ITM and the printing substrate. Includes.

[0043] Furthermore, in one further embodiment, the present invention provides a printing system, a. An intermediate transfer member (ITM) including a flexible endless belt mounted on multiple guide rollers, b. An image forming station configured to form an ink image on the surface of an ITM, wherein first and second guide rollers are positioned upstream and downstream of the image forming station to define an upper run and a lower run passing through the image forming station. c. A printing station through which the lower run of the ITM passes, located downstream of the image forming station, and configured to transfer an ink image from the surface of the ITM to a substrate, and d. A processing station located downstream of the printing station and upstream of the image forming station, for forming a uniform thin layer of liquid formulation on the ITM surface in its lower run, comprising: e. A coating apparatus for coating ITM with an aqueous (treated) formulation according to the present invention, and f. A coating thickness adjustment assembly for removing excess liquid to leave only a desired uniform wet thin layer of a formulation, wherein the layer optionally has a maximum thickness of approximately 1.0 μm (e.g., up to 0.8 μm, up to 0.5 μm, up to 0.4 μm, up to 0.3 μm), and the coating thickness adjustment assembly includes a rounded tip facing the ITM surface in the lower run. Includes.

[0044] In another embodiment, the present invention provides a system for printing, the system is a. Intermediate transfer member including the surface of the release layer, b. Aqueous formulation, and this aqueous formulation is At least one water-soluble polymer (optionally, at least one modified polysaccharide, e.g., cellulose ether such as methylcellulose and HPMC), (i) at least one thermoplastic polymer particulate material (optionally provided in the form of an emulsion and / or dispersion), (ii) at least one thermosetting polymer particulate material (optionally provided in the form of an emulsion and / or dispersion), or (iii) a combination thereof, at least one particulate material selected from these, A carrier liquid containing water, and Optionally, one or more of (iv) at least one surfactant, (v) at least one water-retaining agent, and (vi) at least one wetting agent, Including, c. A processing station for applying an aqueous formulation to the ITM surface and forming a wet (treated) layer thereon, optionally having a maximum thickness of approximately 1.0 μm (e.g., maximum 0.8 μm, maximum 0.5 μm, maximum 0.4 μm, maximum 0.3 μm). d. An image forming station for forming an ink image on an ITM by depositing droplets of aqueous ink onto the ITM surface after a wet (treated) layer has dried to become a dry (treated) thin film, such that droplets of aqueous ink are coated onto a dry thin film, wherein the dry thin film layer optionally has a thickness of at least about 20 nm and a maximum of about 200 nm (for example, a maximum of 200 nm, 190 nm, 180 nm, 170 nm, 160 nm, 150 nm, 140 nm, 130 nm, 120 nm, 110 nm, 100 nm, 90 nm, 80 nm, 70 nm, 60 nm, 50 nm, and optionally at least 20 nm or at least 30 nm), and e. Transfer station for transferring ink images from ITM to a substrate (e.g., together with a dried thin film layer) Includes.

[0045] In yet another embodiment, the present invention provides a system for printing, the system is a. An intermediate transfer member including a flexible endless belt mounted on multiple guide rollers, b. An image forming station configured to form an ink image on the surface of an ITM, wherein first and second guide rollers are positioned upstream and downstream of the image forming station to define an upper run and a lower run passing through the image forming station. c. A printing station through which the lower run of the ITM passes, located downstream of the image forming station, and configured to transfer an ink image from the surface of the ITM to a substrate, and d. A processing station located downstream of the printing station and upstream of the image forming station, for forming a uniform thin layer of liquid formulation on the ITM surface in its lower run, comprising: e. A coating apparatus for coating ITM with an aqueous (treated) compound, wherein the aqueous (treated) compound is At least one water-soluble polymer (optionally, at least one modified polysaccharide, e.g., cellulose ether such as methylcellulose and HPMC), (i) at least one thermoplastic polymer particulate material (optionally provided in the form of an emulsion and / or dispersion), (ii) at least one thermosetting polymer particulate material (optionally provided in the form of an emulsion and / or dispersion), or (iii) a combination thereof, at least one particulate material selected from these, A carrier liquid containing water, and Optionally, one or more of (iv) at least one surfactant, (v) at least one water-retaining agent, and (vi) at least one wetting agent, Including, and f. A coating thickness adjustment assembly for removing excess liquid to leave only a desired uniform wet thin layer of a formulation, wherein the layer optionally has a maximum thickness of approximately 1.0 μm (e.g., up to 0.8 μm, up to 0.5 μm, up to 0.4 μm, up to 0.3 μm), and the coating thickness adjustment assembly includes a rounded tip facing the ITM surface in the lower run. Includes.

[0046] In one further embodiment, the present invention provides a method for improving at least one mechanical property (e.g., abrasion resistance, scratch resistance, coefficient of friction, surface tackiness, etc.) of a printed ink image (on a substrate), the method being: a. To provide an intermediate transfer member including a release layer surface. b. To provide an aqueous formulation in accordance with the present invention, wherein the formulation comprises at least one particulate material as disclosed herein. c. Apply an aqueous formulation to the surface of the ITM release layer, and optionally form a wet (treated) layer thereon having a maximum thickness of approximately 1.0 μm (for example, a maximum of 0.8 μm, 0.5 μm, 0.4 μm, or 0.3 μm) (for example, a uniform thickness). d. Optionally, the wet (treated) layer of (c) is subjected to a drying process to form a dried (treated) thin film layer on the surface of the ITM peel layer from the wet (treated) layer, wherein the dried thin film layer optionally has a thickness of at least about 20 nm and up to 200 nm (e.g., up to 200 nm, 190 nm, 180 nm, 170 nm, 160 nm, 150 nm, 140 nm, 130 nm, 120 nm, 110 nm, 100 nm, 90 nm, 80 nm, 70 nm, 60 nm, 50 nm, and optionally at least 20 nm or at least 30 nm). e. Deposition of droplets of aqueous ink onto a optionally dried (treated) thin film to form an ink image on the surface of the ITM release layer. f. Drying the ink image to leave ink image residue on the surface of the ITM release layer, and g. Transferring ink image residue (e.g., together with the dried thin film layer) onto the printing substrate by pressurized contact between the ITM and the printing substrate. Includes, This generates a printed ink image on a substrate, and the printed ink image has at least one improved mechanical property compared to an ink image generated using the aqueous formulation, but without particulate material.

[0047] In one further embodiment, the present invention provides a method for improving at least one mechanical property (e.g., abrasion resistance, scratch resistance, coefficient of friction, surface tackiness, etc.) of a printed ink image (on a substrate), the method being: a. To provide an intermediate transfer member including a release layer surface. b. To provide an aqueous formulation, the aqueous formulation is At least one water-soluble polymer (optionally, at least one modified polysaccharide, e.g., cellulose ether such as methylcellulose and HPMC), A carrier liquid containing water, and Optionally, one or more of the following: (i) at least one surfactant, (ii) at least one water-retaining agent, and (iii) at least one wetting agent. Including, c. Add to the aqueous formulation of (b) (i) an emulsion and / or dispersion of at least one thermoplastic polymer particulate material, and (ii) one or more dispersions and / or emulsions of at least one thermosetting polymer particulate material. d. The formulation produced in (c) is applied to the surface of the ITM release layer, and a wet (treated) layer having a thickness of approximately 1.0 μm (for example, a maximum of 0.8 μm, 0.5 μm, 0.4 μm, or 0.3 μm) (for example, a uniform thickness) is formed thereon. e. Optionally, the wet (treated) layer of (d) is subjected to a drying process to form a dried (treated) thin film layer on the surface of the ITM peel layer from the wet (treated) layer, wherein the dried thin film layer optionally has a thickness of at least about 20 nm and up to 200 nm (e.g., up to 200 nm, 190 nm, 180 nm, 170 nm, 160 nm, 150 nm, 140 nm, 130 nm, 120 nm, 110 nm, 100 nm, 90 nm, 80 nm, 70 nm, 60 nm, 50 nm, and optionally at least 20 nm or at least 30 nm). f. Deposition of droplets of aqueous ink onto a optionally dried (treated) thin film to form an ink image on the surface of the ITM release layer. g. Drying the ink image to leave ink image residue on the surface of the ITM release layer, and h. Transferring ink image residue (e.g., together with the dried thin film layer) onto the printing substrate by pressurized contact between the ITM and the printing substrate. Includes, This generates a printed ink image on a substrate, the printed ink image having at least one improved mechanical property compared to an ink image generated without adding the emulsion or dispersion of (c) to the aqueous formulation of (b).

[0048] Furthermore, in one further embodiment, the present invention provides a method for improving at least one mechanical property (e.g., abrasion resistance, scratch resistance, coefficient of friction, surface tackiness, etc.) of a printed ink image (on a substrate), the method being: a. To provide an intermediate transfer member including a release layer surface. b. To provide an aqueous formulation, the aqueous formulation is At least one water-soluble polymer (optionally, at least one modified polysaccharide, e.g., cellulose ether such as methylcellulose and HPMC), A carrier liquid containing water, and Optionally, one or more of the following: (i) at least one surfactant, (ii) at least one water-retaining agent, and (iii) at least one wetting agent. Including, c. Add to the aqueous formulation of (b) one or more of the following: (i) a cationic emulsion of at least one oxidized polyethylene wax particle material, (ii) a dispersion and / or emulsion of at least one coating wax particle material, and (iii) a dispersion and / or emulsion of at least one thermosetting polymer particle material. d. The formulation produced in (c) is applied to the surface of the ITM release layer, and a wet (treated) layer having a thickness of approximately 1.0 μm (for example, a maximum of 0.8 μm, 0.5 μm, 0.4 μm, or 0.3 μm) (for example, a uniform thickness) is formed thereon. e. Optionally, the wet (treated) layer of (d) is subjected to a drying process to form a dried (treated) thin film layer on the surface of the ITM peel layer from the wet (treated) layer, wherein the dried thin film layer optionally has a thickness of at least about 20 nm and up to 200 nm (e.g., up to 200 nm, 190 nm, 180 nm, 170 nm, 160 nm, 150 nm, 140 nm, 130 nm, 120 nm, 110 nm, 100 nm, 90 nm, 80 nm, 70 nm, 60 nm, 50 nm, and optionally at least 20 nm or at least 30 nm). f. Deposition of droplets of aqueous ink onto a optionally dried (treated) thin film to form an ink image on the surface of the ITM release layer. g. Drying the ink image to leave ink image residue on the surface of the ITM release layer, and h. Transferring ink image residue (e.g., together with the dried thin film layer) onto the printing substrate by pressurized contact between the ITM and the printing substrate. Includes, This generates a printed ink image on a substrate, the printed ink image having at least one improved mechanical property compared to an ink image generated without adding the emulsion or dispersion of (c) to the aqueous formulation of (b).

[0049] In another embodiment, the present invention provides a method for improving at least one mechanical property of a printed ink image (on a substrate), the method being a. To provide an intermediate transfer member including a release layer surface. b. To provide an aqueous formulation, the aqueous formulation is At least one water-soluble polymer (optionally, at least one modified polysaccharide, e.g., cellulose ether such as methylcellulose and HPMC), A carrier liquid containing water, and Optionally, one or more of the following: (i) at least one surfactant, (ii) at least one water-retaining agent, and (iii) at least one wetting agent. Including, c. Adding to the aqueous formulation of (b) at least one particle material selected from (i) at least one oxidized polyethylene wax particle material (optionally provided in the form of a cationic emulsion), (ii) at least one coating wax particle material (optionally provided in the form of an emulsion and / or dispersion), (iii) at least one thermosetting polymer particle material (optionally provided in the form of an emulsion and / or dispersion), (iv) or any combination thereof, d. The formulation produced in (c) is applied to the surface of the ITM release layer, and a wet (treated) layer having a thickness of approximately 1.0 μm (for example, a maximum of 0.8 μm, 0.5 μm, 0.4 μm, or 0.3 μm) (for example, a uniform thickness) is formed thereon. e. Optionally, the wet (treated) layer of (d) is subjected to a drying process to form a dried (treated) thin film layer on the surface of the ITM peel layer from the wet (treated) layer, wherein the dried thin film layer optionally has a thickness of at least about 20 nm and up to 200 nm (e.g., up to 200 nm, 190 nm, 180 nm, 170 nm, 160 nm, 150 nm, 140 nm, 130 nm, 120 nm, 110 nm, 100 nm, 90 nm, 80 nm, 70 nm, 60 nm, 50 nm, and optionally at least 20 nm or at least 30 nm). f. Deposition of droplets of aqueous ink onto a optionally dried (treated) thin film to form an ink image on the surface of the ITM release layer. g. Drying the ink image to leave ink image residue on the surface of the ITM release layer, and h. Transferring ink image residue (e.g., together with the dried thin film layer) onto the printing substrate by pressurized contact between the ITM and the printing substrate. Includes, This generates a printed ink image on a substrate, the printed ink image having at least one improved mechanical property compared to an ink image generated without adding the particulate material of (c) to the aqueous formulation of (b).

[0050] In one further embodiment, the present invention provides a method for improving at least one mechanical property of a printed ink image (on a substrate), the method being a. To provide an intermediate transfer member including a release layer surface. b. To provide an aqueous formulation, the aqueous formulation is At least 1.5% by weight of at least one water-soluble polymer having a solubility in water of at least 5% at 25°C (optionally, the at least one water-soluble polymer is at least one modified polysaccharide, e.g., cellulose ether such as methylcellulose and HPMC), A first nonionic surfactant having a solubility in water of at least 5% by weight and at least 7% at 25°C, A second nonionic, silicone-containing surfactant having solubility in at least 1% water at 25°C, A carrier liquid containing water, wherein the water constitutes at least about 55% by weight of the aqueous formulation, and Optionally, one or more of the following: (i) at least one water-retaining agent, and (ii) at least one wetting agent, e.g., PEI. Including, c. Adding to the aqueous formulation of (b) at least one particle material selected from (i) at least one thermoplastic polymer particle material (optionally provided in the form of an emulsion and / or dispersion), (ii) at least one thermosetting polymer particle material (optionally provided in the form of an emulsion and / or dispersion), or (iii) a combination thereof, d. The formulation produced in (c) is applied to the surface of the ITM release layer, and a wet (treated) layer having a thickness of approximately 1.0 μm (for example, a maximum of 0.8 μm, 0.5 μm, 0.4 μm, or 0.3 μm) (for example, a uniform thickness) is formed thereon. e. Optionally, the wet (treated) layer of (d) is subjected to a drying process to form a dried (treated) thin film layer on the surface of the ITM peel layer from the wet (treated) layer, wherein the dried thin film layer optionally has a thickness of at least about 20 nm and up to 200 nm (e.g., up to 200 nm, 190 nm, 180 nm, 170 nm, 160 nm, 150 nm, 140 nm, 130 nm, 120 nm, 110 nm, 100 nm, 90 nm, 80 nm, 70 nm, 60 nm, 50 nm, and optionally at least 20 nm or at least 30 nm). f. Deposition of droplets of aqueous ink onto a optionally dried (treated) thin film to form an ink image on the surface of the ITM release layer. g. Drying the ink image to leave ink image residue on the surface of the ITM release layer, and h. Transferring ink image residue (e.g., together with the dried thin film layer) onto the printing substrate by pressurized contact between the ITM and the printing substrate. Includes, This generates a printed ink image on a substrate, the printed ink image having at least one improved mechanical property compared to an ink image generated without adding the particulate material of (c) to the aqueous formulation of (b).

[0051] In one further embodiment, the present invention provides a kit for printing in an indirect printing system, the kit is a. Intermediate transfer member including the surface of the release layer, and b. Aqueous treatment formulation according to the present invention Includes.

[0052] Furthermore, in one further embodiment, the present invention provides a kit for printing in an indirect printing system, the kit is a. Intermediate transfer member including the surface of the release layer, b. Aqueous (treated) formulations, At least one water-soluble polymer (optionally, at least one modified polysaccharide, e.g., cellulose ether such as methylcellulose and HPMC), (i) a cationic emulsion of at least one oxidized polyethylene wax particle material, (ii) a dispersion and / or emulsion of at least one coating wax particle material, and (iii) one or more dispersions and / or emulsions of at least one thermosetting polymer particle material. A carrier liquid containing water, and Optionally, one or more of the following: (iv) at least one surfactant, (v) at least one water-retaining agent, and (vi) at least one wetting agent. Aqueous (treated) formulations containing Includes.

[0053] In another embodiment, the present invention provides a kit for printing in an indirect printing system, the kit is a. Intermediate transfer member including the surface of the release layer, b. Aqueous treated compound, At least one water-soluble polymer (optionally, at least one modified polysaccharide, e.g., cellulose ether such as methylcellulose and HPMC), A carrier liquid containing water, and Optionally, one or more of the following: (i) at least one surfactant, (ii) at least one water-retaining agent, and (iii) at least one wetting agent. Aqueous treatment formulations including, c. One or more of the following: (i) a cationic emulsion of at least one oxidized polyethylene wax particle material, (ii) a dispersion and / or emulsion of at least one coating wax particle material, and (iii) a dispersion and / or emulsion of at least one thermosetting polymer particle material. Includes.

[0054] In one further embodiment, the present invention provides a kit for printing in an indirect printing system, the kit is a. Intermediate transfer member including the surface of the release layer, b. Aqueous (treated) formulations, At least 1.5% by weight of at least one water-soluble polymer having a solubility in water of at least 5% at 25°C (optionally, the water-soluble polymer is at least one modified polysaccharide, such as cellulose ethers like methylcellulose and HPMC), A first nonionic surfactant having a solubility in water of at least 5% by weight and at least 7% at 25°C, A second nonionic, silicone-containing surfactant having solubility in at least 1% water at 25°C, (i) a dispersion and / or emulsion of at least one thermoplastic polymer particulate material, and (ii) one or more dispersions and / or emulsions of at least one thermosetting polymer particulate material A carrier liquid containing water, wherein the water constitutes at least about 55% by weight of the aqueous formulation, and Optionally, one or more of the following: (iii) at least one water-retaining agent, and (iv) at least one wetting agent, e.g., polyethyleneimine. Aqueous (treated) formulations containing Includes.

[0055] In one further embodiment, the present invention provides a kit for printing in an indirect printing system, the kit is a. Intermediate transfer member including the surface of the release layer, b. Aqueous treated compound, At least 1.5% by weight of at least one water-soluble polymer having a solubility in water of at least 5% at 25°C (optionally, the water-soluble polymer is at least one modified polysaccharide, such as cellulose ethers like methylcellulose and HPMC), A first nonionic surfactant having a solubility in water of at least 5% by weight and at least 7% at 25°C, A second nonionic, silicone-containing surfactant having solubility in at least 1% water at 25°C, A carrier liquid containing water, wherein the water constitutes at least about 55% by weight of the aqueous formulation, and Optionally, one or more of the following: (i) at least one water-retaining agent, and (ii) at least one wetting agent (e.g., PEI). Aqueous (treated) formulations including, c. (i) a dispersion and / or emulsion of at least one thermoplastic polymer particulate material, and (ii) one or more dispersions and / or emulsions of at least one thermosetting polymer particulate material Includes.

[0056] Furthermore, in one further embodiment, the present invention provides a kit for printing in an indirect printing system, the kit is a. Intermediate transfer member including the surface of the release layer, b. Aqueous (treated) formulations, At least one water-soluble polymer (optionally, at least one modified polysaccharide, e.g., cellulose ether such as methylcellulose and HPMC), (i) a dispersion and / or emulsion of at least one thermoplastic polymer particulate material, and (ii) one or more dispersions and / or emulsions of at least one thermosetting polymer particulate material A carrier liquid containing water, and Optionally, one or more of the following: (iii) at least one surfactant, (iv) at least one water-retaining agent, and (v) at least one wetting agent. Aqueous treated compound containing Includes.

[0057] In one further embodiment, the present invention provides a kit for printing in an indirect printing system, the kit is a. Intermediate transfer member including the surface of the release layer, b. Aqueous treated compound, At least one water-soluble polymer (optionally, at least one modified polysaccharide, e.g., cellulose ether such as methylcellulose and HPMC), A carrier liquid containing water, and Optionally, one or more of the following: (i) at least one surfactant, (ii) at least one water-retaining agent, and (iii) at least one wetting agent. Aqueous treatment formulations including, c. (i) a dispersion and / or emulsion of at least one thermoplastic polymer particulate material, and (ii) one or more dispersions and / or emulsions of at least one thermosetting polymer particulate material. Includes.

[0058] In one further embodiment, the present invention is (i) Substrates (e.g., uncoated fiber printing substrates, commodity-coated fiber printing substrates, and plastic printing substrates), (ii) One or more ink dots firmly attached to at least one area of ​​the surface of the substrate (for example, forming an ink image on the substrate, the image may be continuous) We provide printed products, including The one or more ink dots and the at least one region of the surface of the substrate are covered with a substantially dry thin film layer (e.g., a continuous thin film) having a thickness of at least about 20 nm and up to about 200 nm (e.g., up to 200 nm, 190 nm, 180 nm, 170 nm, 160 nm, 150 nm, 140 nm, 130 nm, 120 nm, 110 nm, 100 nm, 90 nm, 80 nm, 70 nm, 60 nm, 50 nm, and optionally at least 20 nm or at least 30 nm), wherein the substantially dry thin film layer comprises one or more of (i) at least one thermoplastic polymer particle material, e.g., as disclosed herein, and (ii) at least one thermosetting polymer particle material, e.g., as disclosed herein, and the substantially dry thin film layer optionally further comprises at least one water-soluble polymer (optionally at least one modified polysaccharide, e.g., as disclosed herein).

[0059] In one further embodiment, the present invention is (i) Substrates (e.g., uncoated fiber printing substrates, product-coated fiber printing substrates, and plastic printing substrates), (ii) One or more ink dots that are continuous and can form an ink thin film on the substrate, or which may be spaced apart from each other. Including providing a printable pattern on a substrate, The one or more ink dots are firmly attached to at least one area on the surface of the substrate. The pattern is formed within a defined boundary within the substrate, and the regions surrounding or separating one or more ink dots and the continuous or spaced dots are optionally at least about 20 nm and up to about 200 nm (e.g., up to 200 nm, 190 nm, 180 nm, 170 nm, 160 nm, 150 nm, 140 nm, 130 nm, 120 nm, 110 nm, 100 nm, 90 nm, 80 nm, 70 nm, 60 nm, 50 nm, and optionally at least The material is covered with a substantially dry thin film layer having a thickness of 20 nm or at least 30 nm, wherein the substantially dry thin film layer comprises one or more of (i) at least one thermoplastic polymer particle material, e.g., as disclosed herein, and (ii) at least one thermosetting polymer particle material, e.g., as disclosed herein, and the substantially dry thin film layer optionally further comprises at least one water-soluble polymer (optionally, at least one modified polysaccharide, as disclosed herein).

[0060] In one further embodiment, the present invention provides a printed product / pattern prepared according to the method of the present invention.

[0061] In one further embodiment, the present invention provides an intermediate transfer member including a release layer surface, the surface of which is covered with a substantially dry (treated) continuous thin film as disclosed and illustrated herein.

[0062] The present invention further discloses methods, systems, ITMs, and printing substrates as defined and illustrated herein.

[0063] To better understand the subject matter disclosed herein and to illustrate how it can be put into practice, embodiments are described herein, with reference to the accompanying drawings, only as non-limiting examples. [Brief explanation of the drawing]

[0064] [Figure 1] This is a flowchart of an indirect printing process according to several embodiments of the present invention. [Figure 2A] This is a flowchart of an indirect printing process according to several embodiments of the present invention. [Figure 2B-1] This diagram schematically illustrates a process in which an aqueous treatment formulation and an aqueous ink are applied to an ITM, and the resulting ink image thin film is transferred from the ITM surface to a printing substrate, according to several embodiments of the present invention. [Figure 2B-2] This diagram schematically illustrates a process in which an aqueous treatment formulation and an aqueous ink are applied to an ITM, and the resulting ink image thin film is transferred from the ITM surface to a printing substrate, according to several embodiments of the present invention. [Figure 2B-3] This diagram schematically illustrates a process in which an aqueous treatment compound and an aqueous ink are applied to an ITM, and the resulting ink image thin film is transferred from the ITM surface to a printing substrate, according to several embodiments of the present invention. [Figure 2B-4] This diagram schematically illustrates a process in which an aqueous treatment formulation and an aqueous ink are applied to an ITM, and the resulting ink image thin film is transferred from the ITM surface to a printing substrate, according to several embodiments of the present invention. [Figure 2B-5] This diagram schematically illustrates a process in which an aqueous treatment compound and an aqueous ink are applied to an ITM, and the resulting ink image thin film is transferred from the ITM surface to a printing substrate, according to several embodiments of the present invention. [Figure 2C] This is a flowchart of an indirect printing process according to several embodiments of the present invention. [Figure 3] shows an indirect printing process according to several embodiments of the present invention. [Figure 4A] This is a flowchart of an indirect printing process according to several embodiments of the present invention. [Figure 4B] This is a flowchart of an indirect printing process according to several embodiments of the present invention. [Figure 4C] This is a flowchart of an indirect printing process according to several embodiments of the present invention. [Figure 5] This is a flowchart of an indirect printing process according to several embodiments of the present invention. [Figure 6] This is a photograph of the tip of the dried polyvinyl alcohol (PVA)-based treated formulation described in Comparative Example 8B, which has a thickness of at least 150 to 200 micrometers. [Figure 7A] These are photographs of PVA and HPMC-based treated formulations coated on a silicone blanket, respectively. [Figure 7B] These are photographs of PVA and HPMC-based treated formulations coated on a silicone blanket, respectively. [Figure 8A] This is a photograph of an image obtained from the PVA-treated formulation in formulation 8A. [Figure 8B] This is a photograph of an image produced from the HPMC-treated formulation in formulation 9. [Figure 9A] This is a photograph of an image obtained from the PVA-treated formulation in formulation 8A. [Figure 9B] This is a photograph of an image produced from the HPMC-treated formulation in formulation 9. [Figure 10] This is a photograph of an exemplary image resulting from the use of the processed formulation in Example 11. [Figure 11] This shows the abrasion resistance observed in aqueous treatment formulations containing thermoplastic particle material according to several embodiments of the present invention. [Figure 12A] This shows the abrasion resistance observed in aqueous treatment formulations containing thermosetting particle material according to several embodiments of the present invention. [Figure 12B] This shows the abrasion resistance observed in aqueous treatment formulations containing thermosetting particle material according to several embodiments of the present invention. [Figure 13A] shows the printed surface of paper printed according to some embodiments of the present invention. [Figure 13B] Shows the printed surface of paper printed according to some embodiments of the present invention. [Figure 13C] Shows the printed surface of paper printed according to some embodiments of the present invention. [Figure 13D] shows the printed surface of paper printed according to some embodiments of the present invention. [Figure 14A] shows a printed pattern on the surface of a substrate according to several embodiments of the present invention. [Figure 14B] shows a printed pattern on the surface of a substrate according to several embodiments of the present invention. [Figure 15] shows the relative thicknesses of ink dots and dried thin films according to several embodiments of the present invention. [Modes for carrying out the invention]

[0065] In one aspect of this invention, the present invention provides an aqueous (treated) formulation for use with an intermediate transfer member in a printing system, the formulation being: At least one water-soluble polymer, At least one water-containing carrier liquid, and Optionally, one or more of the following: (a) at least one water-retaining agent (water absorbent), (b) at least one surfactant (e.g., nonionic surfactant, silicone surfactant), and (c) at least one wetting agent, e.g., polyethyleneimine (PEI). Includes, The aforementioned formulation optionally further comprises at least one particle material selected from (i) at least one thermoplastic polymer particle material, (ii) at least one thermosetting polymer particle material, or (iii) a combination thereof.

[0066] Various embodiments are described here in relation to the aforementioned aspects. It should be noted that one or more of these embodiments may be applicable to one or more aspects of the present invention disclosed in this specification. It should be further noted that one or more embodiments described in relation to aqueous (processed) formulations of the present invention may also be applicable to other aspects of the present invention described in this specification, such as methods, systems, processes, products, print patterns, print substrates, ITMs and kits.

[0067] In some embodiments according to the present invention, the water-soluble polymer is at least one modified polysaccharide, such as methylcellulose and cellulose ethers such as HPMC, as disclosed herein.

[0068] In some embodiments according to the present invention, the aqueous treatment formulation is a. At least one modified polysaccharide having, optionally, solubility by weight in at least 1.5%, or at least 2%, or at least 3%, or at least 4%, or at least 5%, or at least 7%, or at least 8%, or at least 10% of water or aqueous treatment formulations at 25°C, and optionally at least one of the following properties: i. Gelation temperature measured at a 2% weight concentration in water or aqueous-treated formulation, at least 50°C, or at least 55°C, or at least 57°C, or at least 60°C, or at least 62°C, or at least 65°C, or at least 68°C, or at least 70°C, or at least 75°C, and optionally, up to 120°C, up to 110°C, up to 105°C, or between 60 and 120°C, or between 60 and 110°C, or between 60 and 100°C, or between 65 and 110°C, or between 65 and 105°C, or between 65 and 100°C, or between 70 and 110°C, or between 70 and 100°C, or between 75 and 110°C, or between 75 and 100°C, or between 80 and 100°C. ii. The viscosity at mPa·s, measured at a 2% weight concentration in water at 25°C, is within the range of a maximum of 11, a maximum of 10, a maximum of 9, a maximum of 8, a maximum of 7, a maximum of 6, a maximum of 5, a maximum of 4, and optionally, at least 0.5 or at least 1 or at least 2, or within the range of 0.5 to 10, 1 to 8, 2 to 8, 2 to 5, or 2 to 4. Having at least one modified polysaccharide, b. Water, and c. Optionally, one or more of the following: at least one water absorbent, at least one surfactant, and at least one wetting agent. It has.

[0069] In some embodiments according to the present invention, the gelation temperature measured at a 2% weight concentration in water is at least 50°C, and the viscosity at mPa·s measured at a 2% weight concentration in water at 25°C is up to 11.

[0070] In some embodiments according to the present invention, the aqueous treatment formulation is (a) At 25°C, at least one modified polysaccharide having a solubility in water of at least 2%, or at least 3%, or at least 4%, or at least 5%, or at least 7%, or at least 8%, or at least 10% by weight, (b) at least one wetting agent, and (c) A carrier liquid containing water, wherein the water constitutes at least 50%, at least 55%, at least 60%, or at least 65% by weight of the aqueous treatment compound. Includes, The aqueous treatment formulation optionally further comprises at least one, at least two, or all three of the following: a water absorbent, a nonionic surfactant, and a silicone surfactant.

[0071] In some embodiments according to the present invention, the aqueous (treated) formulation further comprises at least one particle material selected from (i) at least one thermoplastic polymer particle material, (ii) at least one thermosetting polymer particle material, or (iii) a combination thereof.

[0072] In some embodiments according to the present invention, the aqueous treatment formulation is (a) Optionally, at 25°C, at least 2%, or at least 3%, or at least 4%, or at least 5%, or at least 7%, or at least 8%, or at least 10% by weight of at least one modified polysaccharide, (b) at least one wetting agent, (c) A carrier liquid containing water, wherein the water constitutes at least 50%, at least 55%, at least 60%, or at least 65% by weight of the aqueous treatment compound. (d) At least one particle material selected from (i) at least one thermoplastic polymer particle material, (ii) at least one thermosetting polymer particle material, or (iii) a combination thereof. Includes, The aqueous treatment formulation optionally further comprises at least one, at least two, or all three of the following: a water absorbent, a nonionic surfactant, and a silicone surfactant.

[0073] In some embodiments according to the present invention, at least one modified polysaccharide may be a cellulose derivative.

[0074] In some embodiments according to the present invention, at least one modified polysaccharide may be a cellulose ether.

[0075] In some embodiments according to the present invention, the cellulose ether may be methylcellulose or comprises methylcellulose.

[0076] In some embodiments according to the present invention, the cellulose ether may be hydroxypropyl methylcellulose.

[0077] In some embodiments according to the present invention, the wetting agent may be polyethyleneimine.

[0078] In some embodiments of the present invention, the aqueous treatment formulation comprises methylcellulose, polyethyleneimine, a water absorbent, a surfactant, and a carrier liquid (for example, containing water).

[0079] In some embodiments according to the present invention, methylcellulose is hydroxypropylmethylcellulose.

[0080] In some embodiments of the present invention, the aqueous treatment formulation comprises hydroxypropyl methylcellulose, polyethyleneimine, a water absorbent, a surfactant, and a carrier liquid (for example, containing water).

[0081] In some embodiments according to the present invention, the aqueous treatment formulation may contain polyethyleneimine.

[0082] In some embodiments according to the present invention, the aqueous treatment formulation may contain a surfactant.

[0083] In some embodiments according to the present invention, the aqueous treatment formulation may include a water absorbent.

[0084] In some embodiments according to the present invention, the aqueous treatment formulation may include polyethyleneimine and a water absorbent.

[0085] In some embodiments according to the present invention, the aqueous treatment formulation may include polyethyleneimine and a surfactant.

[0086] In some embodiments according to the present invention, the aqueous treatment formulation may include polyethyleneimine and a nonionic surfactant.

[0087] In some embodiments according to the present invention, the aqueous treatment formulation may include polyethyleneimine and a silicone surfactant.

[0088] In some embodiments according to the present invention, the aqueous treatment formulation may include polyethyleneimine, a water absorbent, and a surfactant.

[0089] In some embodiments according to the present invention, the aqueous treatment formulation may include polyethyleneimine, a water absorbent, a surfactant, and an antimicrobial agent.

[0090] In some embodiments according to the present invention, the modified polysaccharide may have a gelation temperature measured at a 2% weight concentration in water at at least 50°C. In some embodiments, the modified polysaccharide has a viscosity of up to 11 mPa·s, measured at a 2% weight concentration in water at 25°C.

[0091] In some embodiments according to the present invention, the aqueous treatment formulation has a weight ratio of modified polysaccharide to polyethyleneimine in the range of 4:1 to 200:1.

[0092] In some embodiments according to the present invention, the aqueous treatment formulation has a weight ratio of modified polysaccharide to polyethyleneimine of 4:1 to 100:1.

[0093] In some embodiments according to the present invention, the aqueous treatment formulation has a weight ratio of modified polysaccharide to polyethyleneimine of 4:1 to 60:1.

[0094] In some embodiments according to the present invention, the aqueous treatment formulation has a weight ratio of modified polysaccharide to polyethyleneimine of 4:1 to 35:1.

[0095] In some embodiments according to the present invention, the aqueous treatment formulation has a weight ratio of 4:1 to 25:1 of the modified polysaccharide to polyethyleneimine.

[0096] In some embodiments according to the present invention, the aqueous treatment formulation has a weight ratio of 5:1 to 100:1 of modified polysaccharides to polyethyleneimine.

[0097] In some embodiments according to the present invention, the aqueous treatment formulation has a weight ratio of 5:1 to 50:1 of the modified polysaccharide to polyethyleneimine.

[0098] In some embodiments according to the present invention, the aqueous treatment formulation has a weight ratio of 5:1 to 35:1 of the modified polysaccharide to polyethyleneimine.

[0099] In some embodiments according to the present invention, the aqueous treatment formulation has a weight ratio of 6:1 to 50:1 of the modified polysaccharide to polyethyleneimine.

[0100] In some embodiments according to the present invention, the aqueous treatment formulation has a weight ratio of 6:1 to 35:1 of the modified polysaccharide to polyethyleneimine.

[0101] In some embodiments according to the present invention, the aqueous treatment formulation has a weight ratio of 8:1 to 35:1 of modified polysaccharides to polyethyleneimine.

[0102] In some embodiments according to the present invention, the aqueous treatment formulation has a weight ratio of 8:1 to 25:1 of modified polysaccharides to polyethyleneimine.

[0103] As used herein, the term "modified polysaccharide" refers to a polymer carbohydrate molecule composed of long chains of monosaccharide units linked together by glycosidic bonds, wherein at least one hydrogen atom of the hydroxyl group in the monosaccharide unit is substituted with another group, for example, R.

[0104] In some embodiments according to the present invention, the modified polysaccharides may be linear or branched. Non-limiting examples of modified polysaccharides include starch, glycogen, and structural polysaccharides such as cellulose and chitin.

[0105] In some embodiments of the present invention, the modified polysaccharides are homogeneous, that is, they have the same repeating units of monosaccharides (i.e., homopolysaccharides).

[0106] In some embodiments of the present invention, the modified polysaccharides are heterogeneous and contain two or more types of monosaccharides (i.e., heteropolysaccharides).

[0107] In some embodiments of the present invention, the monosaccharide is one or more of glucose, fructose, and glyceraldehyde.

[0108] In some embodiments according to the present invention, the repeating units in the modified polysaccharide are hexoses.

[0109] In some embodiments according to the present invention, the repeating units in the modified polysaccharide are pentose sugars.

[0110] In some embodiments according to the present invention, the number of monosaccharide units in the modified polysaccharide is between approximately 4 and approximately 3000.

[0111] In some embodiments according to the present invention, the number of monosaccharide units in the modified polysaccharide is between approximately 10 and approximately 3000.

[0112] In some embodiments according to the present invention, the modified polysaccharide may include disaccharide units selected from the group consisting of trehalose, cellobiose, cellulose, isomaltulose, lactulose, melibiose, sucrose, lactose, maltose (hydrolysis product of polysaccharide starch), chitobiose (hydrolysis product of polysaccharide chitin), kojibiose, nigerose, isomaltose, sophorose, laminaribiose, gentiobiose, turanose, maltulose, palatinose, gentiobiulose, mannobiose, melibiulose, rutinose, rutinulose, and xylobiose.

[0113] In some embodiments of the present invention, the modified polysaccharide has structure A, where R in the structure may be the same or different, selected from the group consisting of H, CH3, CH2COOH and CH2CH(OH)CH3, and n is an integer of 3 or more, sometimes at least 4. [Formula 1]

[0114] In some embodiments of the present invention, the modified polysaccharide is a "modified cellulose" or "cellulose derivative" having structure B, wherein structure B is a structure having 1 to 4 chain-linked anhydrous glucose units with OR group substitutions at positions 2, 3, and 6, and in the structure R is H, CH3, [CH2CH2O] m H, [CH2CH(CH3)O] m H, CH2COONa, CH2CH(OH)CH3, COOCH3, CH2COOH, CH2COO - This includes, but is not limited to, an integer where m is at least 1 and n is at least 1. [Case 2]

[0115] Examples include, but are not limited to, methylcellulose, ethylcellulose, hydroxyethylmethylcellulose, hydroxypropylcellulose, and carboxymethylcellulose.

[0116] In some embodiments according to the present invention, the modified polysaccharide is methylcellulose having structure B, where at least one of the R groups is CH3 and the remainder may consist of H without further substitution with other alkyl groups.

[0117] Methylcellulose is characterized by its weight percentage of methoxyl groups. The determination of % methoxyl in methylcellulose (MC) polymers is performed according to the United States Pharmacopeia (USP 37, "Methylcellulose," pages 3776–3778). The weight percentage is the average weight percentage based on the total weight of cellulose repeating units, including all substituents. The methoxyl group content is reported based on the mass of methoxyl groups (i.e., -OCH3).

[0118] In some embodiments according to the present invention, the methylcellulose has 18% or more, or 25% % methoxyl.

[0119] In some embodiments according to the present invention, the cellulose derivative has 50% or less, or 40% or less, and / or 35% or less of methoxyl.

[0120] As explained, methylcellulose can be characterized by the viscosity of a 2 wt.-% aqueous solution at 25°C, according to the United States Pharmacopeia (USP 37, "Methylcellulose," pages 3776-3778).

[0121] In some embodiments according to the present invention, the modified polysaccharide is hydroxypropyl methylcellulose, or "HPMC". In some embodiments, HPMC may refer to structure C, where R may be the same or different, H, CH3, or CH2CH(OH)CH3, and n is at least 1. [C3]

[0122] Hydroxypropyl methylcellulose is characterized by the weight percentages of methoxyl and hydroxypropyl groups. The weight percentages are based on the total weight of hydroxypropyl methylcellulose. By convention, the weight percentage is the average weight percentage based on the total weight of the cellulose repeating units, including all substituents. The methoxyl group content is reported based on the mass of methoxyl groups (i.e., -OCH3). The hydroxypropoxyl group content is reported based on the mass of hydroxypropoxyl groups (i.e., -O-C3H6OH). The determination of % methoxyl and % hydroxypropoxyl in HPMC is performed according to the United States Pharmacopeia (USP 37, "Hypromellose," pages 3296-3298). Hydroxypropyl methylcellulose can be characterized by the viscosity of a 2 wt.% aqueous solution at 25°C, according to the United States Pharmacopeia (USP 37, "Hypromellose," pages 3296-3298). Methods for preparing hydroxypropyl methylcellulose are described in international patent applications, publications WO2012 / 051034 and WO2012 / 173838. Examples of hydroxypropyl methylcellulose include, but are not limited to, Methocel® K (HPMC 2208), Methocel® E (HPMC 2910), and Methocel® F (HPMC 2906).

[0123] In some embodiments according to the present invention, the modified polysaccharide may be a cellulose derivative, a cellulose ether, methylcellulose, or HPMC instead.

[0124] In some embodiments according to the present invention, the modified polysaccharide is methylcellulose, and at least 2% of R is a methyl (CH3) group.

[0125] In some embodiments according to the present invention, HPMC may have a gelation temperature measured at a 2% weight concentration in water at at least 50°C, or at least 55°C, or at least 57°C and at least 60°C.

[0126] In some embodiments according to the present invention, HPMC may have a viscosity of up to 11, up to 10, or up to 9 in mPa·s, measured at a 2% weight concentration in water at 25°C.

[0127] In some embodiments according to the present invention, the aqueous treatment formulation has a weight ratio of methylcellulose, e.g., HPMC or a cellulose derivative (e.g., cellulose ether), to polyethyleneimine in the range of 5 to 200:1. In some embodiments, the weight ratio of methylcellulose, e.g., HPMC or a cellulose derivative (e.g., cellulose ether), to polyethyleneimine may be 5 to 50:1. In some embodiments according to the present invention, the weight ratio of methylcellulose, e.g., HPMC or a cellulose derivative (e.g., cellulose ether), to polyethyleneimine may be 7 to 35:1. In some embodiments according to the present invention, the weight ratio of methylcellulose, e.g., HPMC or a cellulose derivative (e.g., cellulose ether), to polyethyleneimine may be 10 to 20:1.

[0128] In some embodiments according to the present invention, the modified polysaccharide may be a non-thermoplastic polymer and / or a charged polysaccharide.

[0129] In some embodiments according to the present invention, the charged polysaccharide may be an acidic polysaccharide containing a carboxyl group and / or a sulfate ester group, or may include an acidic polysaccharide.

[0130] In some embodiments of the present invention, the charged polysaccharide may be a positively charged polysaccharide or may include a positively charged polysaccharide.

[0131] In some embodiments of the present invention, the aqueous treatment formulation may further comprise at least one water-absorbing agent. Water-absorbing agents are well known in the art. Non-limiting examples of applicable water-absorbing agents include those illustrated herein and may be selected from sugars and sugar alcohols.

[0132] In some embodiments according to the present invention, the water-absorbing agent may be solid in its pure state at a temperature range of at least 25°C to 60°C.

[0133] In some embodiments of the present invention, when an aqueous treatment compound is evaporated to form a solid thin film, the water absorbent acts as a moisture absorbent.

[0134] In some embodiments of the present invention, the aqueous treatment formulation includes a solid water absorbent selected to absorb moisture from the ink when the water absorbent is placed within a solid drying treatment thin film.

[0135] In some embodiments, such a solid water absorbent may have a melting point (i.e., in its pure state) of up to 60°C, or up to 50°C, or up to 40°C, or up to 30°C, or up to 25°C. In some embodiments, the concentration of the solid water absorbent may be—for example, at least 1.5%, or at least 2%, or at least 2.5%, or at least 3%, or at least 4%, or at least 5% wt. / wt. In some embodiments, the concentration of the solid water absorbent may be—for example, up to 10%, or up to 8%, or up to 6%. In some embodiments, the concentration of the solid water absorbent may be—for example, between 1–15%, or 2–10%, or 3–8%, or 4–7%. Examples of such water absorbents include, but are not limited to, sucrose, urea, sorbitol, and isomalt.

[0136] In some embodiments of the present invention, the aqueous treatment formulation may further include a surfactant. In some embodiments, the surfactant may include a first nonionic surfactant, a silicone surfactant, or both, having a solubility in water of at least 5% by weight or at least 7% at 25°C. In some embodiments, the first nonionic surfactant may be in an amount of at least 6%, at least 7%, at least 8%, at least 9%, or at least 10% by weight of the first nonionic surfactant, or up to 18%, up to 16%, up to 15%, up to 14%, or up to 13% by weight, or within the range of 5.5–18%, 5.5–16%, 6.5–18%, 6.5–16%, 7.5–18%, 7.5–16%, 8.5–18%, 8.5–16%, 9.5–18%, 9.5–16%, 10.5–18%, or 10.5–16%. In some embodiments, the first nonionic surfactant may have a cloud point temperature of at least 60°C, at least 70°C, at least 80°C, at least 90°C, at least 100°C, at least 105°C, at least 110°C, at least 115°C, at least 120°C, or at least 130°C, as optionally determined by the ASTM D7689-11 test method.

[0137] In some embodiments of the present invention, the aqueous treatment formulation contains at least 5%, at least 6%, at least 7%, at least 8%, at least 9%, or at least 10% by weight of the first nonionic surfactant.

[0138] In some embodiments according to the present invention, the aqueous treatment formulation may further comprise a second or the aforementioned nonionic silicone-containing surfactant, optionally a polysiloxane-polyoxyalkylene copolymer, further optionally the concentration of the polysiloxane-polyoxyalkylene copolymer being at least 0.3%, at least 0.5%, at least 0.75%, or at least 1.0% by weight, and further optionally up to 5%, up to 4%, up to 3%, up to 2.5%, up to 2%, or up to 1.75% by weight.

[0139] In some embodiments according to the present invention, the nonionic silicone-containing surfactant has a solubility in at least 1% water at 25°C.

[0140] In some embodiments according to the present invention, the aqueous treatment formulation comprises, by weight, at least 5% of a first nonionic surfactant having a solubility in water of at least 7% at 25°C, and a second nonionic silicone-containing surfactant having a solubility in water of at least 1% at 25°C.

[0141] In some embodiments according to the present invention, the aqueous treatment formulation has the following characteristics: i. Gelation temperature measured at a 2% weight concentration in water or aqueous treatment formulation, between 50°C, or at least 55°C, or at least 57°C, or at least 60°C, or at least 62°C, or at least 65°C, or at least 68°C, or at least 70°C, or at least 75°C, and optionally, between 120°C, 110°C, or 105°C, or between 60–120°C, or 60–110°C, or 60–100°C, or 65–110°C, or 65–105°C, or 65–100°C, or 70–110°C, or 70–100°C, or 75–110°C, or 75–100°C, or 80–100°C. ii. Viscosity in mPa·s measured at a 2% weight concentration in water at 25°C, with a maximum of 11, 10, 9, 8, 7, 6, 5, 4, and optionally, at least 0.5, or at least 1, or at least 2, or viscosity within the range of 0.5–10, 1–8, 2–8, 2–5, or 2–4. iii. Hydroxypropyl substitution in amounts of at least 1%, 2%, 4%, 6%, 7% or between 1–30%, 5–25%, 5–20%, 5–10%, 7–9% or 7.3–8.3%, or hydroxypropyl substitution in amounts of at least 0.1, or at least 0.15, or at least 0.2, or between 0.1–1.0, 0.1–0.9, 0.1–0.7 or 0.1–0.3 on a molar basis. iv. Number average molecular weights of up to 13,000, or up to 12,000, or up to 11,000, or up to 10,000, or up to 9,000, or up to 8,000 in Dalton. It may include at least one modified polysaccharide (e.g., cellulose ether, e.g., ethylcellulose, methylcellulose, e.g., HPMC, and other cellulose derivatives) having at least one of the above.

[0142] In some embodiments of the present invention described herein, the aqueous treatment formulation has a weight ratio of methylcellulose to polyethyleneimine in the range of 5 to 200:1. The weight ratio of methylcellulose to polyethyleneimine may be 5 to 50:1. The weight ratio of methylcellulose to polyethyleneimine may be 7 to 35:1. The weight ratio of cellulose methylcellulose to polyethyleneimine may be 10 to 20:1.

[0143] In some embodiments according to the present invention, the aqueous treatment formulation has a weight ratio of hydroxypropyl methylcellulose to polyethyleneimine in the range of 5 to 200:1. Sometimes, the weight ratio of hydroxypropyl methylcellulose to polyethyleneimine may be 5 to 50:1. Sometimes, the weight ratio of hydroxypropyl methylcellulose to polyethyleneimine may be 7 to 35:1. Sometimes, the weight ratio of hydroxypropyl methylcellulose to polyethyleneimine may be 10 to 20:1.

[0144] In some embodiments according to the present invention, the modified polysaccharide is a cellulose derivative (e.g., cellulose ether) or methylcellulose.

[0145] In some embodiments according to the present invention, methylcellulose is HPMC.

[0146] In some embodiments of the present invention, a cellulose derivative (e.g., cellulose ether) or methylcellulose may have at least one of the following characteristics: i. Gelation temperature measured at a 2% weight concentration in water or aqueous treatment formulation, between 50°C, or at least 55°C, or at least 57°C, or at least 60°C, or at least 62°C, or at least 65°C, or at least 68°C, or at least 70°C, or at least 75°C, and optionally, between 120°C, 110°C, or 105°C, or between 60–120°C, or 60–110°C, or 60–100°C, or 65–110°C, or 65–105°C, or 65–100°C, or 70–110°C, or 70–100°C, or 75–110°C, or 75–100°C, or 80–100°C. ii. Viscosity in mPa·s measured at a 2% weight concentration in water at 25°C, with a maximum of 11, 10, 9, 8, 7, 6, 5, 4, and optionally, at least 0.5, or at least 1, or at least 2, or viscosity within the range of 0.5–10, 1–8, 2–8, 2–5, or 2–4. iii. Hydroxypropyl substitution in amounts of at least 1%, 2%, 4%, 6%, 7% or between 1–30%, 5–25%, 5–20%, 5–10%, 7–9% or 7.3–8.3%, or hydroxypropyl substitution in amounts of at least 0.1, or at least 0.15, or at least 0.2, or between 0.1–1.0, 0.1–0.9, 0.1–0.7 or 0.1–0.3 on a molar basis. iv. In Dalton, the number average molecular weight is up to 13,000, or up to 12,000, or up to 11,000, or up to 10,000, or up to 9,000, or up to 8,000.

[0147] The inclusion of modified polysaccharides (e.g., cellulose derivatives such as cellulose ethers and hydroxypropyl methylcellulose) may be particularly useful in promoting the formation of polymer thin films or matrices within a dried thin film that has sufficient adhesion for good transfer onto various printing substrate media, such as plastics (e.g., PET (polyethylene terephthalate), PE (polyethylene), BOPP (biaxially oriented polypropylene)), or aluminum.

[0148] In some embodiments according to the present invention, the substrate medium may be entirely plastic.

[0149] The combination of polyethyleneimine and modified polysaccharides (e.g., cellulose derivatives such as cellulose ether and hydroxypropyl methylcellulose) may be particularly useful for promoting the formation of polymer thin films or matrices within a dried thin film that has sufficient adhesion for good transfer to various printing substrate media with high ink image quality.

[0150] In some embodiments according to the present invention, the cellulose derivative (e.g., cellulose ether) is methylcellulose. In some embodiments according to the present invention, the methylcellulose is hydroxypropylmethylcellulose.

[0151] In some embodiments according to the present invention, methylcellulose or hydroxypropyl methylcellulose has a gelation temperature measured at a 2% weight concentration in water at at least 50°C. Sometimes, methylcellulose or hydroxypropyl methylcellulose has a gelation temperature measured at a 2% weight concentration in water at at least 55°C. Sometimes, methylcellulose or hydroxypropyl methylcellulose has a gelation temperature measured at a 2% weight concentration in water at at least 57°C. Sometimes, methylcellulose or hydroxypropyl methylcellulose has a gelation temperature measured at a 2% weight concentration in water at at least 60°C, or at least 62°C, or at least 65°C, or at least 68°C, or at least 70°C, or at least 75°C, and optionally up to 120°C, up to 110°C, or up to 105°C. Sometimes, methylcellulose or hydroxypropyl methylcellulose has a gelation temperature measured at a 2% weight concentration in water between 60 and 120°C. Sometimes, methylcellulose or hydroxypropyl methylcellulose has a gelation temperature measured at a 2% weight concentration in water between 60 and 110°C. Sometimes, methylcellulose or hydroxypropyl methylcellulose has a gelation temperature measured at a 2% weight concentration in water between 60 and 100°C. Sometimes, methylcellulose or hydroxypropyl methylcellulose has a gelation temperature measured at a 2% weight concentration in water between 65 and 110°C. Sometimes, methylcellulose or hydroxypropyl methylcellulose has a gelation temperature measured at a 2% weight concentration in water between 65 and 100°C, or 65 and 100°C, or 70 and 110°C, or 70 and 100°C, or 75 and 110°C, or 75 and 100°C, or 80 and 100°C.

[0152] In some embodiments of the present invention, the modified polysaccharide is methylcellulose or contains methylcellulose.

[0153] In some embodiments according to the present invention, methylcellulose has at least one of the following structural features: i. Hydroxypropyl substitution in amounts of at least 2%, or at least 4%, or at least 6%, or at least 7%, or up to 20%, or up to 15%, or up to 14%, or up to 12%, or between 4–15%, or between 7–12%, ii. Hydroxypropyl molar substitution greater than 0.1, or greater than 0.15, or greater than 0.2, and iii. Number-average molecular weight measured in Dalton, up to 13,000, or up to 12,000, or up to 11,000, or up to 10,000, or up to 9,000, or up to 8,000.

[0154] In some embodiments of the present invention, the aqueous treatment formulation comprises a water absorbent, a surfactant, a carrier liquid containing water, and hydroxypropyl methylcellulose having a gelation temperature measured at a 2% weight concentration in water at at least 50°C. Sometimes, the hydroxypropyl methylcellulose may have a gelation temperature measured at a 2% weight concentration in water at at least 55°C. Sometimes, the hydroxypropyl methylcellulose may have a gelation temperature measured at a 2% weight concentration in water at at least 60°C. While we do not wish to be bound by theory, this may be particularly optimal for replenishing the treatment formulation as it may facilitate a reduction in the need to mechanically scrape it off the blanket after transfer to the substrate. This may also affect the large-scale speed of the belt function.

[0155] In some embodiments according to the present invention, the modified polysaccharide may be a non-thermoplastic polymer. In some embodiments according to the present invention, the modified polysaccharide may include a charged polysaccharide. In some embodiments according to the present invention, the charged polysaccharide may be a positively charged polysaccharide or may include a positively charged polysaccharide. Non-limiting examples of such polysaccharides include, optionally, acidic polysaccharides containing carboxyl groups and / or sulfate ester groups.

[0156] In some embodiments according to the present invention, the charged polysaccharide may be an acidic polysaccharide (e.g., a carboxyl group (e.g., pectin) and / or a sulfate ester group (e.g., carrageenan)).

[0157] In some embodiments of the present invention, the charged polysaccharide may be a positively charged polysaccharide.

[0158] In some embodiments according to the present invention, the modified polysaccharide may be a cellulose derivative such as hydroxypropyl methylcellulose (e.g., cellulose ether).

[0159] In some embodiments according to the present invention, the modified polysaccharide, cellulose derivative (e.g., cellulose ether), or HPMC may have a solubility of at least 2% by weight in water or an aqueous treatment formulation. Sometimes, at least 3% by weight at 25°C. Sometimes, at least 4% by weight at 25°C. Sometimes, at least 5% by weight at 25°C. Sometimes, at least 7% by weight at 25°C. Sometimes, at least 8% by weight at 25°C. Sometimes, at 10% by weight at 25°C.

[0160] In some embodiments according to the present invention, modified polysaccharides, such as methylcellulose or HPMC, have viscosities in mPa·s of up to 11, up to 10, up to 9, up to 8, up to 7, up to 6, up to 5, up to 4, and optionally at least 0.5, at least 1, or at least 2, measured at a 2% weight concentration in water at 25°C, or in the range of 0.5 to 10, 1 to 8, 2 to 8, 2 to 5, or 2 to 4. Sometimes, modified polysaccharides, such as cellulose derivatives such as cellulose ether (e.g., methylcellulose or HPMC), have a viscosity of up to 10 mPa·s, measured at a 2% weight concentration in water at 25°C. Sometimes, modified polysaccharides, such as cellulose derivatives such as cellulose ether (e.g., methylcellulose or HPMC), have a viscosity of up to 7 mPa·s, measured at a 2% weight concentration in water at 25°C. Sometimes, modified polysaccharides, such as cellulose ethers (e.g., methylcellulose or HPMC), have a viscosity of up to 4 mPa·s, measured at a 2% weight concentration in water at 25°C. Sometimes, modified polysaccharides, such as cellulose ethers (e.g., methylcellulose or HPMC), have a viscosity of at least 1 mPa·s, measured at a 2% weight concentration in water at 25°C. Sometimes, modified polysaccharides, such as cellulose ethers (e.g., methylcellulose or HPMC), have a viscosity of at least 0.5 mPa·s, measured at a 2% weight concentration in water at 25°C. Sometimes, modified polysaccharides, such as cellulose ethers (e.g., methylcellulose or HPMC), have a viscosity of 0.5 to 10 mPa·s, measured at a 2% weight concentration in water at 25°C.

[0161] In some embodiments according to the present invention, modified polysaccharides, such as cellulose derivatives like cellulose ether (e.g., methylcellulose or HPMC), have a viscosity of 1 to 8 mPa·s measured at a 2% weight concentration in water at 25°C. Sometimes, modified polysaccharides, such as cellulose derivatives like cellulose ether (e.g., methylcellulose or HPMC), have a viscosity of 2 to 8 mPa·s measured at a 2% weight concentration in water at 25°C. Sometimes, modified polysaccharides, such as cellulose derivatives like cellulose ether (e.g., methylcellulose or HPMC), have a viscosity of 2 to 5 mPa·s measured at a 2% weight concentration in water at 25°C. Sometimes, modified polysaccharides, such as cellulose derivatives like cellulose ether (e.g., methylcellulose or HPMC), have a viscosity of 2 to 4 mPa·s measured at a 2% weight concentration in water at 25°C. Significantly, despite a noticeably lower viscosity range compared to conventional technologies, there was no adverse effect on the digital ink quality on the surface of the processed formulation or on its transfer to the printing substrate.

[0162] In some embodiments according to the present invention, the viscosity of the treated formulation is 15–30 or 20–25 or 20–25 mPa·s, measured at 25°C.

[0163] In some embodiments according to the present invention, methylcellulose has at least one of the following structural features: i. Hydroxypropyl-substituted, greater than 2%, or greater than 4%, or greater than 6%, or greater than 7%, or up to 20%, or up to 15%, or up to 14%, or up to 12%, or between 1 and 30%, or between 4 and 15%, or between 7 and 12%, or between 5 and 25%, or between 5 and 20%, or between 5 and 10%, or between 7 and 9%, or between 7.3 and 8.3%. ii. Hydroxypropyl-methoxyl group molar substitution greater than 0.1, greater than 0.15, greater than 0.2, or between 0.1 and 1.0, or between 0.1 and 0.9, or between 0.1 and 0.7, or between 0.1 and 0.3. iii. Degrees of polymerization less than 70, or 65, or 60, or 60, or 55, and iv. Average molecular weight measured in Dalton, up to 13,000, or up to 12,000, or up to 11,000, or up to 10,000, or up to 9,000, or up to 8,000.

[0164] In some embodiments according to the present invention, the methylcellulose has more than 2% hydroxypropyl substitutions, sometimes more than 4%, sometimes more than 6%, and sometimes more than 7%.

[0165] In some embodiments according to the present invention, methylcellulose has a molar substitution of greater than 0.1, sometimes greater than 0.15, and sometimes greater than 0.2.

[0166] In some embodiments according to the present invention, the methylcellulose has a degree of polymerization of less than 70. Sometimes less than 65. Sometimes less than 60. Sometimes less than 55.

[0167] In some embodiments according to the present invention, the methylcellulose has methoxyl substitutions of less than 25% or in the range of 15-25%.

[0168] In some embodiments according to the present invention, the methylcellulose has hydroxypropyl substitutions in the range of 7 to 12%.

[0169] In some embodiments of the present invention, the modified polysaccharide has a solubility in water or an aqueous treatment formulation of at least 1.5%, at least 2%, at least 3%, at least 4%, at least 5%, at least 7%, at least 8%, or at least 10% by weight at 25°C.

[0170] In some embodiments according to the present invention, the cellulose derivative (e.g., cellulose ether) is hydroxypropylcellulose.

[0171] In some embodiments according to the present invention, methylcellulose is hydroxypropylmethylcellulose.

[0172] In some embodiments according to the present invention, the methylcellulose has less than 25% methoxyl substitution.

[0173] In some embodiments according to the present invention, the methylcellulose has methoxyl substitutions in the range of 15 to 25%.

[0174] In some embodiments according to the present invention, the methylcellulose has methoxyl substitutions in the range of 15-25% and hydroxypropyl substitutions greater than 2%.

[0175] In some embodiments according to the present invention, the methylcellulose has methoxyl substitutions in the range of 15-25% and hydroxypropyl substitutions greater than 4%.

[0176] In some embodiments according to the present invention, the methylcellulose has methoxyl substitutions in the range of 15-25% and hydroxypropyl substitutions greater than 6%.

[0177] In some embodiments according to the present invention, the methylcellulose has methoxyl substitutions in the range of 15-25% and hydroxypropyl substitutions exceeding 7%.

[0178] In some embodiments according to the present invention, the methylcellulose has both methoxyl substitutions in the range of 15-25% and hydroxyproproxyl substitutions in the range of 7-12%.

[0179] Non-limiting examples of HPMCs for use in the present invention include Methocel® E, Methocel® F, Methocel® J, and Methocel® K. Specifically, in some examples, the present invention employs Methocel® K3 LV, Methocel® E3 LV, Methocel® E5 LV, Methocel® E6 LV, and Methocel® VLV.

[0180] In some embodiments according to the present invention, the concentration of polyethyleneimine by weight in the formulation is at least 0.01%, at least 0.05%, at least 0.1%, or at least 0.2%, and optionally up to 1%, up to 0.8%, up to 0.7%, up to 0.6%, or up to 0.5%, or within the range of 0.1–1%, 0.1–0.8%, 0.1–0.7%, 0.1–0.6%, 0.1–0.5%, 0.2–0.7%, 0.2–0.6%, or 0.2–0.5%. Sometimes, the concentration of polyethyleneimine by weight in the formulation is at least 0.01%. Sometimes, the concentration of polyethyleneimine by weight in the formulation is at least 0.05%. Sometimes, the concentration of polyethyleneimine by weight in the formulation is at least 0.1%. Sometimes, the concentration of polyethyleneimine by weight in the formulation is at least 0.2%. Sometimes, the concentration of polyethyleneimine by weight in the formulation is up to 1%. Sometimes, the concentration of polyethyleneimine by weight in the formulation is up to 0.8%. Sometimes, the concentration of polyethyleneimine by weight in the formulation is up to 0.7%. Sometimes, the concentration of polyethyleneimine by weight in the formulation is up to 0.6%. Sometimes, the concentration of polyethyleneimine by weight in the formulation is up to 0.5%. Sometimes, the concentration of polyethyleneimine by weight in the formulation is in the range of 0.1–1%. Sometimes, the concentration of polyethyleneimine by weight in the formulation is in the range of 0.1–0.8%. Sometimes, the concentration of polyethyleneimine by weight in the formulation is in the range of 0.1–0.7%. Sometimes, the concentration of polyethyleneimine by weight in the formulation is in the range of 0.1–0.6%. Sometimes, the concentration of polyethyleneimine by weight in the formulation is within the range of 0.1–0.5%. Sometimes, the concentration of polyethyleneimine by weight in the formulation is within the range of 0.2–0.7%. Sometimes, the concentration of polyethyleneimine by weight in the formulation is within the range of 0.2–0.6%. Sometimes, the concentration of polyethyleneimine by weight in the formulation is within the range of 0.2–0.5%.

[0181] In some embodiments according to the present invention, the average molecular weight of the polyethyleneimine is at least 200,000, at least 350,000, at least 500,000, at least 700,000, at least 750,000, and optionally up to 3,000,000, up to 2,500,000, or up to 2,000,000.

[0182] In some embodiments according to the present invention, the average molecular weight of the polyethyleneimine is 750,000.

[0183] In some embodiments according to the present invention, the weight ratio of a cellulose derivative, such as cellulose ether, methylcellulose, or hydroxypropylmethylcellulose, to polyethyleneimine is 5 to 200:1, or 5 to 50:1, or 7 to 35:1, or 10 to 20:1.

[0184] In some embodiments according to the present invention, the weight ratio of the modified polysaccharide to polyethyleneimine is 5 to 200:1, or 5 to 50:1, or 7 to 35:1, or 10 to 20:1.

[0185] In some embodiments of the present invention, the formulation may further comprise a silicone surfactant, a nonionic surfactant having a water solubility of at least 5% or at least 7% by weight, or both. This may help ensure that the dried thin film is useful for promoting good dot gain.

[0186] In some embodiments according to the present invention, the nonionic surfactant in the aqueous treatment formulation is in the range of 5.5-18%, 5.5-16%, 6.5-18%, 6.5-16%, 7.5-18%, 7.5-16%, 8.5-18%, 8.5-16%, 9.5-18%, 9.5-16%, 10.5-18%, or 10.5-16% by weight. The first nonionic surfactant is a polyethoxylated sorbitan ester, or mainly comprises a polyethoxylated sorbitan ester, or comprises a polyethoxylated sorbitan ester. The polyethoxylated sorbitan ester may comprise at least one chemical species selected from the group consisting of PEG-4 sorbitan monolaurate, PEG-20 sorbitan monolaurate, PEG-20 sorbitan monopalmitate, PEG-20 sorbitan monostearate, and PEG-20 sorbitan monooleate. The HLB number of the first nonionic surfactant is at least 11, at least 12, at least 13, at least 14, or at least 14.5, and optionally up to 22, up to 21, up to 20, up to 19, up to 18, or up to 17, and further optionally up to 11-25, 11-23, 11.5-21, 11.5-20, 11.5-18, 12.5-21, 12.5-20, 12.5-18, 13.5-21, 13.5-20, 13.5-18, 14-20.5, 14-18.5, 14.5-20, 14.5-19, 14.5-18, or 14.5-17.5.

[0187] In some embodiments according to the present invention, the second nonionic silicone-containing surfactant comprises a polysiloxane-polyoxyalkylene copolymer, optionally, the concentration of the polysiloxane-polyoxyalkylene copolymer being at least 0.3%, at least 0.5%, at least 0.75%, or at least 1.0% by weight, and further optionally, up to 5%, up to 4%, up to 3%, up to 2.5%, up to 2%, or up to 1.75% by weight.

[0188] In some embodiments according to the present invention, the treated formulation comprises, by weight, at least 0.3%, at least 0.5%, at least 0.75%, or at least 1.0%, and optionally, up to 5%, up to 4%, up to 3%, up to 2.5%, up to 2%, or up to 1.75%, of the second nonionic silicone-containing surfactant.

[0189] In some embodiments according to the present invention, the aqueous treatment formulation may have a cloud point temperature of the first nonionic surfactant which is at least 60°C, at least 70°C, at least 80°C, at least 90°C, at least 100°C, at least 105°C, at least 110°C, at least 115°C, at least 120°C, or at least 130°C, as determined by the ASTM D7689-11 test method, which is optional.

[0190] In some embodiments according to the present invention, the treated formulation may further contain a water-absorbing agent.

[0191] In some embodiments of the present invention, the water absorbent is a sugar or a sugar alcohol. In some embodiments, the water absorbent is a sugar.

[0192] In some embodiments of the present invention, the treatment formulation may further contain a biocide.

[0193] In some embodiments according to the present invention, the treated formulation may contain up to 0.3% or up to 0.1% of a quaternary ammonium salt.

[0194] In some embodiments of the present invention, the treated formulation may substantially lack quaternary ammonium salts.

[0195] In some embodiments according to the present invention, the treated formulation may contain up to 0.3% or up to 0.1% of a thermoplastic polymer.

[0196] In some embodiments of the present invention, the treated formulation may substantially lack thermoplastic polymers such as polyvinylpyrrolidone, polyvinylpyrrolidone copolymers, and polyvinyl alcohol.

[0197] In some embodiments of the present invention, the treated formulation may contain up to 0.3% or up to 0.1% polyvinyl alcohol (PVA).

[0198] In some embodiments of the present invention, the treated formulation may substantially lack polyvinyl alcohol (PVA).

[0199] In some embodiments of the present invention, the treated formulation may be substantially devoid of starch and, in particular, waxy starch.

[0200] In some embodiments according to the present invention, the treated formulation may contain, in total, up to 1%, up to 0.5%, up to 0.3%, or up to 0.1%, or substantially none of the following: quaternary ammonium salts, starches, or particularly waxy starches, thermoplastic polymers, and more specifically, PVA.

[0201] In some embodiments according to the present invention, the treated formulation may contain or substantially lack any methylcellulose without hydroxypropyl substitution in amounts of up to 0.3%, up to 0.1%.

[0202] In some embodiments of the present invention, the treated formulation may contain or substantially lack a hygroscopic plasticizer in amounts ranging from up to 0.3% to up to 0.1%.

[0203] In some embodiments according to the present invention, the total solid content by weight of the formulation is at least 8%, or at least 9%, or at least 10%, or at least 14%, or at least 16%, or at least 18%, or at least 20%, or between 10-30%, or between 15-25%.

[0204] In some embodiments according to the present invention, the cellulose derivative, cellulose ether, methylcellulose, or hydroxypropylmethylcellulose is present in an amount of at least 1.5%, at least 2.0%, at least 2.5%, at least 3.0%, at least 3.1%, or at least 3.2% by weight.

[0205] In some embodiments according to the present invention, the first nonionic surfactant is present in an amount of at least 5% by weight.

[0206] In some embodiments according to the present invention, the silicone surfactant is present in an amount of at least 0.5% by weight.

[0207] In some embodiments according to the present invention, the treated formulation contains modified polysaccharides in an amount of at least 1.5%, 2.0%, 2.5%, or 3% by weight.

[0208] In some embodiments according to the present invention, the treated formulation has a static surface tension in the range of 25 to 40 mN / m at 25°C.

[0209] In some embodiments of the present invention, the treated formulation has a kinematic viscosity at 25°C of at least 10 cP, or at least 12 cP, or at least 14 cP, or within the range of 10 cP to 100 cP, 12 cP to 100 cP, 14 cP to 100 cP, 10 cP to 60 cP, or 12 cP to 40 cP. As will be explained below, and without intending to be bound by theory, high viscosity is considered useful in counteracting any surface tension-driven tendencies toward beading.

[0210] In some embodiments according to the present invention, the ratio of the solubility of the modified polysaccharide at 80°C to the solubility of the modified polysaccharide at 25°C is up to 0.9, up to 0.7, up to 0.5, up to 0.3, and up to 0.1.

[0211] In some embodiments of the present invention, the treatment formulation may further include at least one wetting agent, such as a polyethersiloxane copolymer, such as Tego280®.

[0212] In some embodiments according to the present invention, the concentration of methylcellulose is in the range of 2.0 to 8%, 2.5 to 6.5%, 2.5 to 6%, 2.5 to 5.5%, or 2.5 to 5% by weight, and the evaporation load is in the range of 2.3:1 to 4.5:1, 2.3:1 to 4:1, 2.5:1 to 4.2:1, 2.5:1 to 4:1, 2.5:1 to 3.8:1, or 2.5:1 to 3.6:1.

[0213] In some embodiments according to the present invention, the aqueous treatment formulation has a total concentration of surfactants in the range of at least 6%, at least 7%, at least 8%, at least 10%, or at least 12% by weight, and optionally in the range of 6-40%, 6-30%, 6-20%, 7-30%, 7-20%, 7-15%, 8-25%, 8-20%, 8-15%, 8-13%, 9-25%, 9-20%, 9-15%, 9-13%, 10-25%, 10-20%, 10-15%, or 10-13%.

[0214] Furthermore, due to the specific thickness of the residue relative to the aqueous treatment solution, and the given heat output delivered to the aqueous treatment solution, the viscosity of the aqueous treatment formulation increases rapidly as a function of evaporation, achieving a high absolute viscosity that effectively counteracts surface tension. Physically, inducing the flow of a fluid with high viscosity is more difficult than inducing the flow of a fluid with low viscosity—that is, a greater driving force is required to induce the flow of a fluid with higher viscosity. The combination of at least a moderate initial viscosity (i.e., kinematic viscosity at 25°C of at least 10 cP) and a rapid viscosity increase after evaporation on the ITM surface (e.g., due to a low evaporation load) ensures that the aqueous treatment formulation reaches a relatively "high" viscosity (e.g., at least 10,000 cP) in a relatively short period (e.g., up to 1 second or up to 0.5 seconds). Therefore, even if there is some thermodynamic tendency toward beading, actual beading, which could adversely affect the properties of the dried treatment thin film, is prevented or significantly mitigated.

[0215] In some embodiments according to the present invention, the aqueous treatment formulation dissolves completely at 25°C, for example, when no particulate material is present in the formulation.

[0216] In some embodiments according to the present invention, the total concentration of organic solvents in the aqueous treatment formulation is, by weight, at most 3%, at most 2%, at most 1%, or at most 0.5%, or the formulation does not contain organic solvents.

[0217] In a further aspect of that embodiment, the present invention provides a method for indirect printing onto a substrate, the method comprising: i. providing an intermediate transfer member (ITM); ii. providing an aqueous treatment formulation substantially as disclosed herein; iii. applying the aqueous treatment formulation to the ITM to form a wet treatment layer; iv. optionally, at least partially drying the wet treatment layer to form at least a partially dried treatment thin film layer; v. depositing (e.g., by jetting) aqueous ink droplets onto the at least partially dried treatment layer to form a wet ink image; vi. at least partially drying the wet ink image on the aqueous treatment layer to form a partially dried ink image thin film; and vii. transferring the partially dried ink image thin film to the printing substrate by pressure contact between the ITM and the printing substrate. comprises.

[0218] In some embodiments according to the present invention, the aqueous treatment formulation is provided at a temperature below about 55°C.

[0219] In some embodiments according to the present invention, at least partially drying the wet treatment layer to form at least a partially dried treatment layer occurs at an ITM (e.g., blanket) temperature of at least 80°C.

[0220] In some embodiments according to the present invention, at least partially drying the wet ink image on the aqueous treatment layer occurs at at least 100°C, or at least 120°C or at least 130°C to form a partially dried ink image thin film.

[0221] In some embodiments of the present invention, the transfer to the substrate is performed at a temperature of at least 75°C, or at least 80°C, or between 75 and 150°C, or between 80 and 120°C.

[0222] In some embodiments of the present invention, the aqueous treatment formulation is selected such that the wetting treatment layer is in the form of an aqueous gel layer on the image-receiving surface of the ITM.

[0223] In some embodiments according to the present invention, the temperature of the aqueous gel layer on the image-receiving surface may be in the range of 50-100°C, 55-100°C, 57-100°C, 60-100°C, 62-100°C, 65-100°C, 67-100°C, 70-100°C, 75-100°C, or 80-100°C.

[0224] In some embodiments according to the present invention, the printing substrate onto which the ink image thin film (e.g., residue) is transferred has a contact surface made of at least plastic [e.g., PET (polyethylene terephthalate), PE (polyethylene), BOPP (biaxially oriented polypropylene)] or aluminum.

[0225] In some embodiments according to the present invention, the substrate medium may be a printing substrate selected from the group consisting of plastics, polyethylene terephthalate (PET), polyethylene (PE), biaxially oriented polypropylene (BOPP), aluminum, and combinations thereof.

[0226] In some embodiments according to the present invention, the substrate medium is entirely plastic.

[0227] In some embodiments of the present invention, the method for indirect printing further comprises removing an ink image residue thin film from the image receiving surface, wherein the ink image residue includes a treatment compound residue from the aqueous treatment compound. In some embodiments, the method further comprises removing at least 70%, at least 80%, at least 90%, or substantially all of the treatment compound by redissolution. In some embodiments, the method lacks any mechanical washing or mechanical residue removal operations.

[0228] In one further embodiment, the present invention provides a method for indirect printing onto a substrate, the method is i. To provide an intermediate transfer member (ITM), ii. To provide aqueous treatment formulations substantially as disclosed herein, iii. Applying an aqueous treatment compound to the ITM to form a wet treatment layer. iv. Optionally, the wet treatment layer is partially dried to form at least a partially dried treatment layer. v. Forming a wet ink image by depositing aqueous ink droplets onto a partially dried processing layer (for example, by ejecting them). vi. To form a partially dried ink image thin film by at least partially drying the wet ink image on the aqueous treatment layer. vii. Transferring a partially dried ink image thin film to the printing substrate by pressurized contact between the ITM and the printing substrate. Includes, The method further comprises resolubilizing the dried thin film in an aqueous treatment formulation, and after step vii), the peeled surface is washed with the aqueous treatment solution, and the process returns to step iii) to start a new printing cycle.

[0229] In some embodiments according to the present invention, the coating on the ITM is an aqueous treatment formulation with a uniform submicron thickness and / or high printing speed over a wide area of ​​the ITM.

[0230] In some embodiments according to the present invention, the wet aqueous treatment formulation has a thickness of up to 0.8 μm, up to 0.5 μm, up to 0.4 μm, up to 0.3 μm, up to 0.2 μm, or up to 0.15 μm, and optionally at least 0.05 μm or at least 0.10 μm, and further optionally in the range of 0.05 to 0.8 μm, 0.10 to 0.5 μm, or 0.10 to 0.25 μm.

[0231] In some embodiments of the present invention, the ITM has a silicone-based release layer surface, the surface being sufficiently hydrophilic such that the receding contact angle of distilled water droplets adhering to the silicone-based release layer surface is up to 60°.

[0232] In some embodiments of the present invention, the surface of the silicone-based release layer is sufficiently hydrophilic such that the 10-second dynamic contact angle (DCA) of distilled water droplets adhering to the surface of the silicone-based release layer is up to 108°.

[0233] In some embodiments according to the present invention, the provided ITM includes a support layer and the surface of the silicone-based release layer and a release layer having a second surface that (i) faces the surface of the silicone-based release layer and (ii) is attached to the support layer, wherein the release layer is formed from an addition-curing silicone material, and the thickness of the release layer is optionally up to 800 micrometers (μm), and sometimes up to 500 micrometers (μm).

[0234] In some embodiments according to the present invention, the addition-curable silicone material consists essentially of an addition-curable silicone or comprises at least 95% by weight of the addition-curable silicone.

[0235] In some embodiments according to the present invention, the functional groups in the silicone-based release layer surface of the provided ITM constitute up to 3% by weight of the addition-curable silicone material.

[0236] In some embodiments according to the present invention, a polyether glycol-functionalized polydimethylsiloxane is impregnated into the addition-curable silicone material of the provided ITM.

[0237] In some embodiments according to the present invention, the release layer of the provided ITM is adapted such that the polar groups of the ink-receiving surface are either away from the second surface or oriented opposite to the second surface.

[0238] In some embodiments according to the present invention, the surface hydrophobicity of the silicone-based release layer surface of the provided ITM is less than the bulk hydrophobicity of the curable silicone material in the release layer, the surface hydrophobicity is characterized by the receding contact angle of distilled water droplets on the ink-receiving surface, and the bulk hydrophobicity is characterized by the receding contact angle of distilled water droplets adhering to the inner surface formed by exposing a region of curable silicone material in the release layer to form an exposed region.

[0239] In some embodiments according to the present invention, the wet treatment layer is formed and / or thinned by promoting a rounded surface toward the ITM or vice versa. i. The rounded surface has a radius of curvature of up to 2 mm, or up to 1.5 mm, or up to 1.25 mm, and / or ii. The facilitation is at a force density in the cross-printing direction of at least 250 g / cm², or at least 350 g / cm², or at least 400 g / cm² and / or up to 1 kg / cm², or up to 750 g / cm², or up to 600 g / cm², and / or iii. Prompting is performed by applying pressure between the ITM and the ITM, the magnitude of which is at least 0.1 bar, or at least 0.25 bar, or at least 0.35 bar, or at least 0.5 bar, and optionally, up to 2 bar, or up to 1.5 bar, or up to 1 bar.

[0240] In some embodiments of the present invention, the formation or thinning of a wet treatment layer involves flowing an aqueous treatment formulation such that a velocity gradient perpendicular to the ITM is established, with the magnitude of the velocity gradient being at least 10 6 sec -1 or at least 2 × 10 6 sec -1 That is the case.

[0241] In some embodiments according to the present invention, the drying process of the wet treatment layer is sufficiently rapid such that the viscosity of the aqueous treatment formulation increases sufficiently rapidly to prevent surface tension-driven beading, so that the dried treatment thin film has a smooth top surface.

[0242] In some embodiments according to the present invention, the smooth top surface of the dried treatment thin film has an average roughness R of up to 12 nanometers or up to 10 nanometers or up to 9 nanometers or up to 8 nanometers or up to 7 nanometers or up to 4 nanometers or up to 3 nanometers, and optionally, at least 1 nanometer or at least 2 nanometers a characterized thereby.

[0243] In some embodiments according to the present invention, the drying of the treatment solution is carried out sufficiently rapidly to prevent beading and to leave a continuous hydrophilic and adhesive polymer treatment thin film having a thickness of up to 200 nm, or up to 150 nm, or up to 120 nm, or up to 100 nm, or up to 80 nm, or up to 70 nm, or up to 60 nm, or up to 50 nm, or up to 40 nm, or up to 30 nm.

[0244] In some embodiments according to the present invention, the thickness of the dried treatment thin film to which the aqueous ink droplets are attached is up to 200 nm, or up to 120 nm, or up to 100 nm, up to 80 nm, up to 70 nm, up to 60 nm, up to 50 nm, up to 45 nm, or up to 40 nm.

[0245] In some embodiments according to the present invention, the thickness of the dried treatment thin film to which the aqueous ink droplets are attached is at least 15 nm or at least 20 nm or at least

[0246] 25 nm or at least 30 nm.

[0246] In some embodiments according to the present invention, the dried treatment thin film is continuous covering the entire rectangle of the release surface of the ITM, the rectangle having a width of at least 10 cm and a length of at least 10 meters.

[0247] In some embodiments according to the present invention, a dried thin film is applied to at least 50%, at least 75%, at least 90%, at least 95%, at least 99%, or 100% of a rectangular area, and the thickness of the dried thin film does not deviate by more than 50%, 40%, or 30% from the average thickness value within the rectangle.

[0248] In some embodiments according to the present invention, during the drying process of the wet-treated layer, its kinematic viscosity increases by at least 1000 times within a period of up to 250 milliseconds.

[0249] In some embodiments according to the present invention, ink image residue is transferred onto the printing substrate along with the non-printed areas of the dried thin film.

[0250] In some embodiments according to the present invention, the thickness of the dried thin film is up to 120 nm.

[0251] In some embodiments according to the present invention, the dried thin film is sufficiently tacky so that during the transfer of ink image residue, the dried thin film completely separates from the ITM and is transferred to the printing substrate along with the dried ink image in both the printed and non-printed areas.

[0252] In some embodiments according to the present invention, a method for indirect printing is: i. An ink dot set IDS is formed of ink dots present on the ink substrate. ii. The droplet plurality (DP) of aqueous ink droplets adhering to the drying thin film present in the ITM is such that a given droplet becomes an ink dot present on a given substrate and / or develops into an ink dot present on a given substrate. A. Each given droplet in droplet-multiple DP and B. Ink dots present on each of the given substrates in the ink dot set In order to have a correspondence between them, the ink dot set IDS of the ink dots present on the ink substrate is formed. iii. During the deposition, every time one droplet of the plurality of droplets collides with the drying treatment thin film on the ITM, the kinetic energy of the colliding droplet deforms the droplet, iv. Each maximum collision radius of the deformed droplets above the surface of the ITM has a maximum collision radius value R MAX_IMPACT and, v. After the collision, physicochemical forces spread the deformed droplets so that each ink dot of the ink dot set IDS present on the substrate has a dried dot radius R DRIED_DOT_ON_SUBSTRATE vi. For each droplet of the plurality of droplets and the corresponding ink dot of the ink dot set IDS, A. the dried dot radius R DRIED_DOT_ON_SUBSTRATE present on the substrate and MAX_IMPACT B. the maximum collision radius value R of the deformed droplet such that the ratio therebetween is at least 1.1 is carried out.

[0253] In some embodiments according to the present invention, a method for indirect printing is i. The plurality of droplets DP of droplets adhering to the drying treatment thin film present on the ITM generates an ink dot set IDS of ink dots (i.e., firmly adhering to the upper surface of the substrate), and each droplet of the plurality of droplets DP corresponds to a different ink dot present on the substrate of the ink dot set IDS, ii. Each ink droplet of the plurality of droplets DP is deposited on the substrate according to ejection parameters, iii. The ejection parameters jointly define, together with the physicochemical properties of the ink droplets of the plurality of droplets DP, an inkjet paper dot radius R DIRECT-JETTING-ONTO-INK-JET-PAPER-THEORETICAL where the inkjet paper dot radius is the radius of the ink dot obtained when the ink droplet is directly inkjet onto the inkjet paper instead of the drying treatment thin film, and iv. (A) the dried dot radius R DRIED_DOT_ON_SUBSTRATE of the dots of the ink dot set IDS DIRECT-JETTING-ONTO-INK-JET-PAPER-THEORETICAL and (B) the inkjet paper dot radius R such that the ratio therebetween is at least 1.1

[0254] ​ In some embodiments according to the present invention, the density of the ink dot set is at least 5, or at least 10, or at least 20, or at least 50, or at least 100, and each ink dot of the ink dot set is distinct on the substrate. The ink dots of the ink dot set are contained within a square geometric projection projected onto the printing substrate, and each ink dot of the ink dot set is firmly attached to the surface of the printing substrate, and all of the ink dots within the square geometric projection are considered to be individual members of the ink dot set IDS.

[0255] In some embodiments according to the present invention, an aqueous treatment formulation is applied to at least portion(s) of an ITM moving at a speed of at least 1 m / s, at least 1.5 m / s, at least 2 m / s, at least 2.5 m / s, at least 3 m / s, optionally up to 5.5 m / s, up to 5.0 m / s, up to 4.5 m / s, or up to 4.0 m / s to form a wet treatment layer thereon.

[0256] In some embodiments according to the present invention, the dried thin film to which aqueous ink droplets are attached and the surface of the dried thin film have (i) an average roughness R a (ii) characterized by a dimensionless ratio between (ii) the thickness of the drying treatment layer, wherein the dimensionless ratio is up to 0.5, up to 0.4, up to 0.3, up to 0.25, up to 0.2, up to 0.15, or up to 0.1, and optionally at least 0.02, or at least 0.03, or at least 0.04, or at least 0.05, or at least 0.06, or at least 0.07, or at least 0.08.

[0257] In some embodiments of the present invention, the method utilizes a blanket having one or more of the features disclosed herein.

[0258] In one further embodiment, the present invention is i. Intermediate transfer member (ITM) including a silicone-based release layer surface, ii. A container containing an aqueous treatment formulation, which substantially includes an aqueous treatment formulation as disclosed herein. iii. A processing station for applying an aqueous treatment compound to the surface of a silicone-based release layer and forming a wet treatment layer thereon. iv. Optional drying stations for drying aqueous-treated formulations, v. At least one inkjet nozzle positioned in close proximity to the intermediate transfer member and configured to eject ink droplets onto an aqueous treatment mixture formed on the intermediate transfer member, vi. An ink processing station configured to at least partially dry the ink on an aqueous processing mixture formed on an intermediate transfer member to produce an ink image residue, and vii. Ink image residue transfer mechanism for transferring ink image residue to a printing substrate by pressurized contact between ITM and the printing substrate. We provide an indirect printing system that includes [this].

[0259] In some embodiments of the present invention, the system does not rely on or lacks any mechanical formulation residue removal mechanism. Specifically, the system may lack any mechanical residue removal mechanism (e.g., scraping blade) adapted to mechanically remove an ink image thin film (e.g., ink image and treatment formulation residue) from the release layer surface. Alternatively, or in addition, the system further includes a cleaning station for removing an ink image thin film (e.g., ink image and residue or treatment formulation residue) from the silicone release layer surface. Optionally, the system may further include a treatment applicator means for reapplying the treatment formulation.

[0260] In one further embodiment, the present invention is To provide aqueous treatment formulations as disclosed herein, Applying an aqueous treatment compound to ITM to form a wet treatment layer, Optionally, the wet treatment layer is dried at least partially to form at least a partially dried treatment layer. Forming a wet ink image by ejecting water-based ink droplets onto a partially dried processing layer. To form a partially dried ink image thin film (e.g., aqueous coating) by at least partially drying a wet ink image on an aqueous treatment layer, and The partially dried ink image thin film is transferred to the printing substrate by pressurized contact between the ITM and the printing substrate. The present invention provides a method for indirect printing onto a substrate, including the application of the invention.

[0261] In some embodiments of the present invention, methods and apparatus are provided that are useful for consistently producing a dry-processed layer that does not tear when transferred to various "difficult" printing substrates, which are made of materials such as plastics [e.g., PET (polyethylene terephthalate), PE (polyethylene), BOPP (biaxially oriented polypropylene)] or aluminum, or which have at least a contact surface made of such materials.

[0262] In some embodiments of the present invention, the method shown in Figure 1 refers to the illustrations in Figures 2B.1 to 2B.5. Figure 1 is a flowchart of a printing process according to some embodiments of the present invention, in which an intermediate transfer member (ITM) (e.g., 210) is pre-treated with one of the aqueous treatment formulations disclosed in the present invention before an ink image is deposited thereon. In step S1 of Figure 1 (or as shown in Figure 2B.1), an aqueous treatment formulation of the present invention (e.g., 202) is applied to the surface of a hydrophobic ITM (e.g., 210) to pre-treat the ITM surface, and optionally dried to result in a partially dried thin film 204 on the ITM 210, as schematically provided in Figure 2B.2. In step S9 of Figure 1, droplets of aqueous ink are inkjet onto an optionally dried processed formulation (e.g., processed thin film 206) to form a wet ink image 222 (e.g., including the processed thin film 204 and the attached ink 221) on the surface of the ITM, as schematically provided in Figure 2B.3. In step S13 of Figure 1 (or as schematically shown in Figure 2B.4), the ink image (e.g., 222) is dried on the surface of the ITM to form at least a partially dried ink image thin film (224 as schematically provided in Figure 2B.4, as well as at least a partially dried processed thin film 206 and a partially dried attached ink 223). In step S17 of Figure 1 (or as schematically shown in Figure 2B.5), the dried ink image thin film 224 is transferred to the printing substrate 260, typically by pressurized contact.

[0263] Figure 2A is an illustrative flowchart of a method for indirect printing with aqueous ink onto a silicone-based release layer surface of an intermediate transfer member (ITM) having a layer of treatment or treatment formulation according to some embodiments of the present invention. In some embodiments, the method of Figure 2A refers to the illustrations in Figures 2B.1 to 2B.5. In some embodiments, the method of Figure 2A (or any combination thereof) may be performed using the apparatus (or components thereof) disclosed herein.

[0264] In some embodiments according to the present invention, any of the methods shown in Figures 2A, 2B, and 2C may be performed to produce an ink image characterized by any combination of the following features: uniform and controlled dot gain, good and uniform print gloss, and good image quality resulting from high-quality dots with consistent dot convexity and / or clearly defined boundaries. Steps S201 to S205 relate to the components or elements or consumables used in the printing process of Figure 2A, while steps S209 to S225 relate to the process itself.

[0265] In short, the steps in Figure 2A are as follows: In steps S201 and S205, the ITM (e.g., including a silicone-based release layer surface) and an aqueous treatment formulation (e.g., a solution) of the present invention are provided, each having specific properties as described herein. In step 209, the aqueous treatment formulation is applied to the release layer surface of the ITM to form a wetting treatment layer thereon. In step S213, the wetting treatment layer is subjected to a drying process to form a dried treatment thin film on the ITM. In step S217, droplets of aqueous ink are deposited on this at least partially dried treatment thin film to form an ink image on the ITM surface. In step S221, this ink image is dried to leave an ink image thin film or residue on the ITM surface, and in step S225, this ink image residue or thin film is transferred to a printing substrate.

[0266] In some embodiments of the present invention, methods and apparatus are provided that are useful for producing a uniform submicron-thickness wetted layer over a wide range of ITMs and / or at high printing speeds.

[0267] Explanation of step S201 in Figure 2A In some embodiments, the ITM provided in step S201 has a silicone-based release layer, but its release surface may be less hydrophobic, or clearly less hydrophobic, than many conventional silicone-based release layers. This structural property can be measured and characterized in various ways.

[0268] For example, as shown in step S201 of Figure 2A, the intermediate transfer member (ITM) includes a silicone-based release layer surface that is sufficiently hydrophilic to satisfy at least one of the following properties: namely, (i) the receding contact angle of distilled water droplets attached to the silicone-based release layer surface is at most 60°, and (ii) the 10-second dynamic contact angle (DCA) of distilled water droplets attached to the silicone-based release layer surface is at most 108°.

[0269] Any one of several techniques for reducing the hydrophobicity of the silicone-based release layer may be employed.

[0270] In some embodiments according to the present invention, polar functional groups are introduced into and / or generated in the silicone release layer. Sometimes, the functional groups may be added to a prepolymer batch (e.g., monomers in solution) - these functional groups may become integral parts of the silicone polymer network structure upon curing. Alternatively, or additionally, the silicone release layer may be pretreated (e.g., by corona discharge or electron beam) to increase its surface energy.

[0271] Alternatively, silicone-based release layers can be manufactured to have low hydrophobicity, even if they are substantially devoid of functional groups. Sometimes, the silicone polymer backbone of the release layer can be constructed so that its polar groups (e.g., O-Si-O) are oriented in a direction that is roughly perpendicular to the local plane of the ITM surface and "upward" toward the release layer surface.

[0272] Explanation of step S205 in Figure 2A In some embodiments according to the present invention, an aqueous treatment formulation 200 is provided, and the aqueous treatment formulation 200 is, a. Modified polysaccharides (e.g., cellulose ether) having solubility in at least 1.5%, or at least 2%, or at least 3%, or at least 4%, or at least 5%, or at least 7%, or at least 8%, or at least 10% by weight of water or aqueous treatment formulations at 25°C, and having at least one of the following properties: i. Gelation temperature measured at a 2% weight concentration in water or aqueous-treated formulation, at least 50°C, or at least 55°C, or at least 57°C, or at least 60°C, or at least 62°C, or at least 65°C, or at least 68°C, or at least 70°C, or at least 75°C, and optionally, up to 120°C, up to 110°C, up to 105°C, or between 60 and 120°C, or between 60 and 110°C, or between 60 and 100°C, or between 65 and 110°C, or between 65 and 105°C, or between 65 and 100°C, or between 70 and 110°C, or between 70 and 100°C, or between 75 and 110°C, or between 75 and 100°C, or between 80 and 100°C. ii. The viscosity at mPa·s, measured at a 2% weight concentration in water at 25°C, is within the range of a maximum of 11, a maximum of 10, a maximum of 9, a maximum of 8, a maximum of 7, a maximum of 6, a maximum of 5, a maximum of 4, and optionally, at least 0.5 or at least 1 or at least 2, or within the range of 0.5 to 10, 1 to 8, 2 to 8, 2 to 5, or 2 to 4. Modified polysaccharides (e.g., cellulose ethers) having the above, b. Water, and c. Optionally, comprising at least one, two, or all three of the following: a water absorbent, a surfactant, and a wetting agent, such as polyethyleneimine. Includes.

[0273] Alternatively, in some embodiments according to the present invention, an aqueous treatment formulation 200 is provided (S205), and the aqueous treatment formulation 200 is (a) Modified polysaccharides (e.g., cellulose ether) having solubility in at least 2%, or at least 3%, or at least 4%, or at least 5%, or at least 7%, or at least 8%, or at least 10% by weight of water or aqueous treatment formulations at 25°C, (b) polyethyleneimine (PEI), and (c) A carrier liquid containing water, wherein the water constitutes at least 50%, at least 55%, at least 60%, or at least 65% by weight of the aqueous treatment compound. Includes, The aqueous treatment formulation optionally includes at least one, at least two, or all three of the following: a water absorbent, a nonionic surfactant, and a silicone surfactant.

[0274] In some embodiments according to the present invention, the weight ratio of the modified polysaccharide to polyethyleneimine is within the range of 4:1 to 200:1, or 5 to 200:1, or 4:1 to 100:1, or 4:1 to 60:1, or 4:1 to 35:1, or 4:1 to 25:1, or 5:1 to 100:1, or 5:1 to 50:1, or 5:1 to 35:1, or 6:1 to 50:1, or 6:1 to 35:1, or 8:1 to 35:1, or 8:1 to 25:1, or 10:1 to 20:1 by weight.

[0275] In some embodiments according to the present invention, an aqueous treatment formulation 200 is provided, comprising a modified polysaccharide (e.g., cellulose ether, a cellulose derivative such as methylcellulose or hydroxypropylmethylcellulose), polyethyleneimine, a water absorbent, a surfactant, and a carrier liquid containing water (S205). Occasionally, the formulation may further comprise a suitable antimicrobial agent, such as 2-bromo-2-nitro-1,3-propanediol.

[0276] In some embodiments according to the present invention, the water absorbent may be selected from a list including sucrose, urea, sorbitol, isomalt, or any combination thereof.

[0277] In some embodiments of the present invention, the aqueous treatment formulation comprises a carrier liquid containing water, wherein the water constitutes at least 65% (e.g., at least 70% or at least 75%) of the weight of the aqueous treatment formulation.

[0278] Explanation of step S209 in Figure 2A, with reference to Figure 2B.1 In step S209, the aqueous treatment formulation 200 is applied to the surface of the silicone-based release layer of ITM210 to form a wet treatment layer 202 having a maximum thickness of 0.8 μm (for example, a maximum of 0.7 μm, or a maximum of 0.6 μm, or a maximum of 0.5 μm).

[0279] In some embodiments, step S209 is performed so that the wetting layer has a uniform thickness over a wide area, preferably over the entire surface of the release layer, and is defect-free. This can be particularly difficult when the wetting layer is submicron thick.

[0280] In step S209, the aqueous treatment compound 200 is applied to the surface of the silicone-based release layer to form a wet treatment layer 202 having a thickness of up to 0.8 μm, optionally.

[0281] In some embodiments of the present invention, apparatus and methods are provided for applying the wetting treatment layer such that the thickness is preferably uniform over a wide area of ​​the ITM.

[0282] In some embodiments according to the present invention, after coating the ITM surface with an initial coating of an aqueous treatment formulation, excess treatment formulation can be removed from the initial coating to obtain a wet treatment layer having a uniform thickness of, for example, up to 0.8 μm. Sometimes, this can be achieved by guiding a highly finished surface (e.g., of a doctor blade) toward or toward the ITM. For example, the radius of curvature of the highly finished surface may be up to 1.5 mm, 1.25 mm, or 1 mm.

[0283] Explanation of step S213 with reference to Figure 2B.2 In step S213, the wet-treated layer 202 is subjected to a drying process to form a dried-treated thin film. Sometimes, during the drying process of the wet-treated layer, its kinematic viscosity increases by at least 1000 times within a period of up to 0.5 seconds or up to 0.25 seconds.

[0284] In some embodiments according to the present invention, the thickness of the dried thin film (e.g., a tacky polymer-treated thin film) 204 is up to 150 nanometers, or up to 120 nanometers, or up to 100 nanometers, or up to 80 nanometers, or up to 60 nanometers.

[0285] In some embodiments according to the present invention, the dried thin film 204 has a smooth top surface. Sometimes, the drying process of the wet-treated layer is fast enough so that the viscosity of the aqueous-treated formulation increases sufficiently rapidly to prevent surface tension-driven beading, so that the dried thin film has a smooth top surface.

[0286] In some embodiments of the present invention, the smooth upper surface of the dried thin film has an average roughness R of up to 12 nanometers, or up to 10 nanometers, or up to 9 nanometers, or up to 8 nanometers, or up to 7 nanometers, or up to 5 nanometers. a It is characterized by the following. Experts should refer to Figure 2C and its accompanying explanation.

[0287] In some embodiments according to the present invention, the dried thin film is continuous and covers the entire rectangular surface of the ITM, the rectangle having a width of at least 10 cm and a length of at least 10 m.

[0288] In some embodiments according to the present invention, the treated thin film is transparent.

[0289] In some embodiments according to the present invention, one objective of the dried-treatment thin film is to prevent the ITM surface from coming into direct contact with droplets of aqueous ink adhering to the treated thin film. While we do not wish to be bound by theory, the inventors believe that the aqueous-treatment formulations according to the present invention provide improved protection against erosion by droplets of aqueous ink, even with very thin thicknesses of dried-treatment thin films (e.g., up to 150 or 120 or 100 or 80 nanometers).

[0290] In some embodiments according to the present invention, the cellulose derivative or more specifically, cellulose ether such as HPMC in the provided aqueous treatment formulation (for example, in step S205 in Figure 2A or step S95 in Figure 2C) is present in an amount of at least 2.0%, at least 2.5%, at least 3.0%, or at least 3.5% by weight.

[0291] Explanation of steps S217 and S221 with reference to Figures 2B.3 and 2B.4 In step S217, droplets of water-based ink adhere to the drying thin film (for example, by ink droplet adhesion), forming an ink image on the ITM surface. In step S221, this ink image dries, leaving an ink image residue or thin film on the ITM surface.

[0292] In some embodiments according to the present invention, the presence of water-absorbing agents such as sugars and nonionic surfactants in the dried thin film plays a role in promoting dot diffusion and / or dot gain (e.g., uniform dot diffusion and / or dot gain) when droplets are attached or immediately thereafter. As described above, the formation of a dried thin film (in step S213) having a uniform thickness and / or defect-free and / or very smooth upper surface can promote uniform flow of aqueous ink on the upper surface of the thin film.

[0293] Explanation of step S225 with reference to Figure 2B.5 In step S225, the ink image residue is transferred to the printing substrate. For example, the ink image residue may be transferred to the printing substrate together with the non-printing areas of the dried thin film.

[0294] In some embodiments according to the present invention, the dried thin film is sufficiently tacky so that during the transfer of ink image residue, the dried thin film completely separates from the ITM and is transferred to the printing substrate along with the dried ink image in both the printed and non-printed areas.

[0295] In some embodiments according to the present invention, the ITM temperature is in the range of 80°C to 120°C during transfer to the substrate. In some embodiments, the ITM temperature is a maximum of 120°C or a maximum of 110°C. In some embodiments, the ITM temperature is at least 80°C or at least 90°C or at least 110°C or at least 120°C.

[0296] In some embodiments according to the present invention, the selection of a water-soluble binder in the aqueous treatment solution provided in step S205 helps to ensure that the dried treatment thin film formed in step S213 is sufficiently tacky during transfer (i.e., by forming a polymer thin film or matrix).

[0297] In some embodiments according to the present invention, the printing substrate onto which the ink image residue thin film is transferred has a surface made of at least plastic (typically PET, PE, or BOPP) or aluminum. In some embodiments, the substrate medium is entirely plastic.

[0298] The selection of components and their concentrations in the ITM aqueous treatment formulations described in the present invention contributes to the unexpectedly high performance resulting, as described below, despite the use of polysaccharides, cellulose derivatives, methylcellulose, or HPMC having low viscosity in the wetted layer formed on the ITM, as described below in some embodiments.

[0299] The inventors of the present invention have found that the aqueous treatment formulations disclosed herein enable or provide a highly effective means of generating a high-quality image on an ITM, and, after drying, transferring a relatively dry, high-quality printed image from the ITM to various printing substrates made of materials including plastics (PET, PE, BOPP, etc.) and aluminum, in addition to various grades of paper substrates, both coated and uncoated, while simultaneously maintaining a high-quality ink image typically characterized by low graininess and high-quality ink dots (e.g., having large dot size and / or uniform dot gain).

[0300] Furthermore, formulations and methods of the present invention may be applied to produce ink images characterized by any combination of the following features: namely, uniform and controlled dot gain, good and uniform print gloss, and good image quality resulting from high-quality dots with consistent dot protrusion and / or clearly defined boundaries.

[0301] In some embodiments according to the present invention, one characteristic of the aqueous treatment formulation provided in step S205 is that the static surface tension of the aqueous treatment formulation is in the range of 20 to 40 dynes / cm. For example, the aqueous treatment formulation contains one or more surfactants. Thus, the aqueous treatment formulation of step S205 is less hydrophilic than many conventional treatment solutions and significantly less hydrophilic than water.

[0302] In some embodiments of the present invention, a combination of (i) a silicone-based release layer having low hydrophobicity (step S201) and (ii) an aqueous treatment formulation having low hydrophilicity reduces (but does not necessarily eliminate) the surface tension effect that promotes beading in conventional aqueous treatment solutions.

[0303] In addition to a static surface tension in the range of 20 to 40 dynes / cm, in some embodiments according to the present invention, the aqueous treatment formulation provided in step S205 may have the following properties: a. The aqueous treatment formulation contains at least 5% by weight of a nonionic surfactant. This may be useful to ensure that the dried treatment thin film (i.e., produced in step S213) is useful for promoting good dot gain. b. The aqueous treatment formulation comprises, by weight, at least 1% (e.g., at least 1.5%, at least 2%, or at least 3%) of at least one water-soluble polymer having a solubility in water of at least 5% at 25°C. This may be useful in promoting the formation of a polymer thin film or matrix in the dried treatment thin film (produced in step S213) which has sufficient adhesion for good transfer in step 225. c. Kinematic viscosity at 25°C is at least 10 cP. High viscosity is considered useful to counteract any surface tension-driven tendencies toward beading. d. The solid content of the composition is, by weight, at least 8%, or at least 9%, or at least 10%, or at least 12%, or at least 14%, or at least 16%, or at least 18%, or at least 20%, or 10–30%, or 12–30%, or 14–30%, or 16–30%, or 18–30%, or 20–30%, or 12–28%, or 14–28%, or 16–28%, or 18–28%, or 20–28%, or 12–26%, or 14–26%, or 16–26%, or 18–26%, or 20–26%.

[0304] Physically, inducing the flow of a high-viscosity fluid is more difficult than inducing the flow of a low-viscosity fluid—that is, a greater driving force is required to induce the flow of a higher-viscosity fluid. The combination of at least a moderate initial viscosity (i.e., kinematic viscosity at 25°C of at least 10 cP) and a rapid viscosity increase after evaporation on the ITM surface ensures that the aqueous-treated formulation reaches a relatively "high" viscosity (e.g., at least 10,000 cP) in a relatively short period (e.g., up to 0.4 seconds or up to 0.3 seconds). Therefore, any actual beading, even if there is some thermodynamic tendency toward beading, which could adversely affect the properties of the dried-treated thin film (e.g., formed in step S213), is prevented or significantly mitigated.

[0305] In some embodiments according to the present invention, the kinematic viscosity of the initial aqueous treatment formulation at 25°C may be at least 12 cP or at least 14 cP—for example, in the range of 10 to 100 cP, 12 to 100 cP, 14 to 100 cP, 10 to 60 cP, or 12 cP to 40 cP.

[0306] In some embodiments of the present invention, the combination of (A) a release layer surface that is sufficiently hydrophilic to satisfy at least one of the following characteristics: (i) a receding contact angle of distilled water droplets adhering to the surface of the silicone release layer is up to 60°, and (ii) a 10-second dynamic contact angle (DCA) of distilled water droplets adhering to the surface of the silicone release layer is up to 108°, and (B) a static surface tension of the aqueous treatment formulation in the range of 20 to 40 dynes / cm is useful in minimizing the magnitude of the thermodynamic driving force that can cause beading. Furthermore, the viscosity-related characteristics mentioned above are useful in counteracting this driving force.

[0307] This reduction in the magnitude of the thermodynamic force driving beading, along with counteracting this tendency, ensures that any tendency toward beading does not prevent the formation of a wet layer of the treated formulation in step S209 having a uniform thickness.

[0308] In some embodiments according to the present invention, the aqueous treatment formulation comprises a carrier liquid containing water, wherein the water constitutes at least 50%, at least 55%, at least 60%, at least 65%, or at least 70% by weight of the aqueous treatment formulation.

[0309] In some embodiments according to the present invention, water constitutes at least 55% by weight of the aqueous treatment formulation.

[0310] Embodiments of the present invention preferably relate to formulations, methods, apparatus and kits for achieving potentially competing targets of dot gain, image gloss and dot quality in production environments where high printing speed is paramount. According to several embodiments, the inventors have found it useful to perform the method of Figure 2A such that the dried thin film formed in step S213 is very thin (e.g., up to 150 nanometers or up to 120 nanometers or up to 100 nanometers or up to 80 nanometers or up to 70 nanometers or up to 60 nanometers or up to 50 nanometers, and optionally, at least 20 nanometers or at least 30 nanometers) and / or continuous over a wide area and / or characterized by a very smooth top surface (e.g., to promote dot gain) and / or has properties that promote good transfer from ITM to the substrate (i.e., properties of the thin film itself or the thin film to the ITM surface).

[0311] For example, a thicker treated film may negatively affect its gloss or uniformity after transfer, as dried ink residue may be present beneath the treated film and on the substrate surface. Therefore, it may be preferable to produce a very thin treated film.

[0312] For example, discontinuities in the processed thin film and / or processed thin films of different thicknesses may result in an image with uneven gloss on the substrate or produce ink image residue that loses its mechanical integrity when transferred to the substrate (in step S113). Therefore, it may be preferable to produce a processed thin film that is continuous over a wide range—preferably, has sufficient tackiness and / or thermorheological properties to maintain structural integrity when transferred to a printing substrate, and is therefore typically tackiness at transfer temperatures of 80–150°C.

[0313] Embodiments of the present invention relate to techniques for achieving these results simultaneously, even if these results involve potentially competing objectives. For example, the need to make the processed thin film very thin makes it more difficult to form a processed thin film that is continuous over a wide area and / or sufficiently tacky for good transfer to the substrate and / or has a very smooth and uniform top surface.

[0314] In some embodiments of the present invention, the aqueous treatment formulation is prepared by a process comprising providing or producing an aqueous solution of approximately 10% cellulose derivative or HPMC at 20°C to 30°C, and gradually mixing in components such as PEI, a water absorbent, a surfactant including any of various nonionic surfactants, an antimicrobial agent, or any optional component. In some embodiments, the HPMC is Methocel® E3 or Methocel® K3.

[0315] Some embodiments of the present invention relate to a printing process illustrated in Figure 2C. In some non-limiting examples, systems and apparatus described later herein may be employed to carry out the method of Figure 2C. The order of steps in Figure 2C is not intended to be limiting—specifically, steps S91 to S99 may be performed in any order. In some embodiments, steps S101 to S117 are performed in the order shown in Figure 2C.

[0316] In some embodiments, step S91 may be performed to provide any feature or combination of features of step S201 in Figure 2A.

[0317] In some embodiments, step S95 may be performed to provide any feature or combination of features of step S205 in Figure 2A.

[0318] In some embodiments, step S101 may be performed to provide any feature or combination of features of step S209 in Figure 2A.

[0319] In some embodiments, step S105 may be performed to provide any feature or combination of features of step S213 in Figure 2A.

[0320] In some embodiments, step S109 may be performed to provide any feature or combination of features of step S217 in Figure 2A.

[0321] In some embodiments, step S113 may be performed to provide any feature or combination of features of step S221 in Figure 2A.

[0322] In some embodiments, step S117 may be performed to provide any feature or combination of features of step S225 in Figure 2A.

[0323] In some embodiments of the present invention, steps S91 to S99 relate to components, elements, or consumables used in the process shown in Figure 2C, while steps S101 to S117 relate to the process itself. Briefly, (i) in step S101, a thin treatment layer of a wetting treatment formulation is applied to an intermediate transfer member (ITM) (e.g., having a hydrophobic release layer); (ii) in step S105, this treatment layer is dried (e.g., rapidly dried) to form a thin dried treatment film on the release surface of the ITM; (iii) in step S109, droplets of aqueous ink are attached (e.g., by spraying) onto the thin dried treatment film; (iv) in step S113, the ink image is dried, leaving an ink image residue on the dried treatment film to form an ink image film on the ITM; and (v) in step S117, the ink image film is transferred to a printing substrate.

[0324] The components of steps S91 to S99 and the details of process steps S101 to S117 are described above and below in this specification.

[0325] In some embodiments according to the present invention, steps S91 to S117 are performed as follows: (A) In step S91, an ITM is provided - for example, one that is at most moderately hydrophobic and / or hydrophobic and / or has a silicone-based release layer and / or is only moderately hydrophobic and / or lacks functional groups. (B) In step S95, an aqueous treatment solution is provided - for example, (i) having a high solids content and / or (ii) being rich in surfactants and / or (iii) being moderately hydrophilic and / or (iv) containing a water-soluble polymer and / or (v) containing a nonionic surfactant such as polyethoxylated sorbitan ester and / or (vi) having a viscosity low enough that the solution can spread into a uniform thin layer and / or (vii) containing a hygroscopic agent and / or (viii) substantially lacking organic solvents and / or (ix) having a flocculant containing polyvalent cations in a maximum or low concentration, (C) In step S99, water-based ink is provided. (D) In ​​step S101, the aqueous treatment compound is applied to the peeling surface of the ITM (e.g., the ITM in transit) to form a thin wet treatment layer (e.g., thickness ≤ 0.8 μm) thereon. (E) In step S105, the thin wet treatment layer can be air-dried (e.g., passively) or subjected to an active drying process (e.g., a rapid drying process) on the ITM peeling surface, leaving a thin, at least partially dried treatment film (e.g., thickness ≤ 0.08 μm) of the water-soluble polymer on the ITM peeling surface. For example, the thin dried treatment film may have one or both of the following properties: (i) for example, the treatment film is a continuous and / or adhesive film, and (ii) the upper surface of the dried treatment film is characterized by extremely low roughness. (F) In step S109, droplets of aqueous ink are deposited onto a thin drying film (for example, by inkjet) to form an ink image thereon. (G) In step S113, the ink image is dried, leaving an ink image thin film containing ink image residue on the dried thin film (for example, to achieve good ink dot diffusion). (H) In step S117, the ink image thin film is transferred from the ITM surface to the printing substrate (e.g., paper substrate or plastic substrate) (e.g., at a relatively low temperature) (e.g., together with the dried thin film).

[0326] In some embodiments according to the present invention, the process shown in Figure 2C is performed such that when the aqueous treatment solution is applied to the ITM in step S101, there is little to no beading, and the resulting thin dried treatment film (i.e., obtained in step S105) has a continuous and / or smooth (e.g., extremely smooth) top surface. This smooth top surface may be important for obtaining a high-quality ink image present on the substrate, as can be seen in Figures 8A and 9A compared with Figures 8B and 9B.

[0327] One characteristic associated with the conventional process in which the ITM is pre-treated and the ink image is applied on top of the pre-treated ITM is that, after transfer to the substrate, a dried treatment thin film may be present on top of the ink image (e.g., after drying), potentially adding an undesirable gloss to the ink image. To overcome or minimize this potentially undesirable effect, a thin dried treatment thin film is obtained in step S105 (e.g., having a thickness of up to 400 nanometers, or up to 200 nanometers, or up to 100 nanometers, or even less). Furthermore, in some embodiments, this thin dried treatment thin film (i.e., obtained in step S105) is continuous, which may be beneficial as described below.

[0328] While not a limitation, in some embodiments the process in Figure 2C is performed such that the image transfer in step S117 (e.g., onto an uncoated substrate) is performed at a low temperature—for example, up to 90°C, or up to 85°C, up to 80°C, or up to 75°C, up to 70°C, or up to 65°C, up to 60°C—for example, at about 60°C.

[0329] Explanation of step S91 in Figure 2C In some embodiments according to the present invention, the ITM (i.e., the ITM provided in step S91 of Figure 2C or step S201 of Figure 2A) may provide one or more of the following features A1 to A5 (i.e., any combination thereof):

[0330] A1: Silicone-based release layer - The release layer is formed from a silicone material (e.g., addition-curing type) - This provides a hydrophobic ITM useful in step S117.

[0331] A2: Curable Silicone Release Layer - Before use in the method shown in Figure 2C, the silicone release layer is produced in a manner that reduces its hydrophobicity. For example, instead of relying on the addition of functional, reactive groups to give the release layer hydrophilicity, it is possible to cure the silicone release layer so that polar atoms in the polar groups (e.g., oxygen atoms in the polar Si-O-Si moiety) are aligned outward with respect to the surface of the release layer, or otherwise face outward. In this example, the oxygen atoms of "Si-O-Si" cannot chemically bond to the material in the treatment solution, to the dried ink image, and / or to the dried treatment thin film under typical process conditions in step S117. However, it is possible to benefit from the hydrophilicity of the outward-facing, polar "O".

[0332] A3: Hydrophobicity of the delamination layer - The delamination surface of ITM may have moderate hydrophobicity, but not excessively hydrophobic. Therefore, the delamination surface may have a surface energy (at 25°C) of at least 23 dynes / cm, and more typically at least 25 dynes / cm, at least 28 dynes / cm, at least 30 dynes / cm, at least 32 dynes / cm, at least 34 dynes / cm, or at least 36 dynes / cm, and / or up to 48 dynes / cm, up to 46 dynes / cm, up to 44 dynes / cm, up to 42 dynes / cm, up to 40 dynes / cm, up to 38 dynes / cm, or up to 37 dynes.

[0333] A4: Receding Contact Angle of Distilled Water Droplets - The receding contact angle of distilled water droplets on an ink-receiving surface or release layer surface is typically at least 30° and more typically 30°–75°, 30°–65°, 30°–55°, or 35°–55°.

[0334] A5: The exfoliation layer of functional groups -ITM in the exfoliation layer may lack or substantially lack functional groups bonded in the crosslinked polymer structure, and the inventors believe that such functional groups may increase or promote undesirable adhesion.

[0335] Explanation of step S95 in Figure 2C In step S95, an aqueous treatment formulation is provided. In some embodiments, this treatment formulation comprises at least 50% wt / wt, at least 55% wt / wt, at least 60% wt / wt, or at least 65% wt / wt of water carrier liquid.

[0336] In some embodiments, the aqueous treatment formulation (i.e., the aqueous treatment formulation in its initial state before application in step S101 of Figure 2C or the aqueous treatment formulation in its initial state before application in step S205 of Figure 1) may provide one or more of the following features (i.e., any combination thereof):

[0337] B1: High solid load - In some embodiments, the initial aqueous treatment formulation has a high solid load or high concentration solution having a total solid percentage of at least 8%, or at least 9%, or at least 10%, or at least 12%, or at least 14%, or at least 16%, or at least 18%, or at least 20%, or up to 30%, or up to 28%, or up to 26%, or between 12–30%, or between 14–30%, or between 16–30%, or between 12–28%, or between 14–28%, or between 16–28%, or between 18–28%, for example, measured by the weight of the residue after evaporating the carrier liquid to dryness at 25°C.

[0338] B2: Rich in surfactants - In some embodiments, the initial aqueous treatment formulation contains at least 2% wt / wt, or at least 2.5% wt / wt, or at least 3% wt / wt, or at least 4% wt / wt, or at least 5% wt / wt, or at least 6% wt / wt, or at least 7% wt / wt, or at least 8% wt / wt, or at least 9% wt / wt, or at least 10% wt / wt of surfactant(s). In some embodiments, a relatively high concentration of surfactant in the initial aqueous treatment formulation may help to lower the hydrophilicity of the aqueous treatment formulation, thereby reducing the tendency for the aqueous treatment formulation to bead up on the exfoliated surface of the ITM in steps S101 and / or S105. In some embodiments, a relatively high concentration of surfactant may be useful during steps S109 and / or S113 to diffuse aqueous ink droplets onto the surface of the drying ink film (or to counteract the tendency of the ink droplets to shrink), thereby increasing the coverage area of ​​the resulting ink dots that ultimately exist on the substrate. Examples include, but are not limited to, PEG-20 sorbitan monolaurate, Tween 80®, Tween 60®, Tergitol, Pluronic, Dynol, or any water-soluble silicone or fluorinated surfactant in general.

[0339] B3: Presence of nonionic surfactants and / or silicone or fluorinated surfactants (e.g., at relatively high concentrations) - In some embodiments according to the present invention, the initial aqueous treatment formulation contains at least 5% (e.g., at least 6%, at least 7%, at least 8%, at least 9%, or at least 10%) wt. / wt. of nonionic surfactants. In some embodiments, the solubility of this nonionic surfactant in water is at least 5% or at least 7% at 25°C, and typically higher. The unit "dyne / cm" is used without distinction from "mN / m". Suitable surfactants include both nonionic surfactants. Silicone surfactants may be present in an amount of at least 0.5% by weight. Examples of nonionic surfactants include, but are not limited to, PEG-20 sorbitan monolaurate (e.g., Tween® 20, Tween® 60, Tween® 80), dyno surfactants (e.g., Dynol™ 800, Dynol™ 607, Dynol™ 960, Dynol™ 810), secondary alcohol ethoxylates (Tergitol® 15-S-9, Tergitol® 15-S-7, Tergitol® TMN6), and octylphenol ethoxylates (e.g., Triton® X-100, Triton® X35, Triton® X-15). Examples of silicone surfactants include, but are not limited to, polyether-modified polydimethylsiloxanes (e.g., BYK LPX® 23289, BYK® 347, BYK® 349, BYK® 333, BYK® 3455, BYK® 348) or polyethersiloxane copolymers (e.g., TEGO® 240, Tego® 280, Tego 492, Tego 482). Examples of fluorinated surfactants include, but are not limited to, Dynax 4000 and Dynax 4010.

[0340] B4: Moderately hydrophilic initial aqueous treatment formulation - In some embodiments according to the present invention, the initial aqueous treatment formulation is moderately hydrophilic - for example, having a static surface tension at 25°C of up to 32 dynes / cm (e.g., between 20 and 32 dynes / cm) or up to 30 dynes / cm (e.g., between 20 and 32 dynes / cm) or up to 28 dynes / cm (e.g., between 20 and 32 dynes / cm). Sometimes, the peeled surface of the ITM has moderately hydrophobic (or moderately hydrophilic) properties, so employing a highly hydrophilic initial aqueous treatment formulation that may cause beading of the aqueous treatment formulation on the surface of the ITM in steps S101 and / or S105 may not be useful. This may be particularly important for situations where the thickness of the wet treatment layer is thin, and it is desirable to avoid bare patches so that the resulting thin dried treatment film is continuous.

[0341] B5: Presence of polysaccharides or cellulose - In some embodiments, the presence of modified polysaccharides (cellulose ethers), specifically methylcellulose, more specifically hydroxypropyl-substituted methylcellulose, and more specifically methylcellulose having a gelling temperature of at least 55°C or at least 60°C, as measured at a 2% weight concentration in water. In some embodiments, the initial aqueous formulation contains, by weight, at least 1.5% (e.g., at least 2%, at least 2.5%, or at least 3%) of modified polysaccharides, specifically soluble hydroxypropyl-substituted methylcellulose having a solubility in water of at least 5% at 25°C, and more specifically, at least 50°C, or at least 55°C, or at least 57°C, or at least 60°C, or at least 62°C, or at least 65°C, or less All include having a gelation temperature of 68°C, or at least 70°C, or at least 75°C, and optionally, a maximum of 120°C, a maximum of 110°C, a maximum of 105°C, or between 60 and 120°C, or between 60 and 110°C, or between 60 and 100°C, or between 65 and 110°C, or between 65 and 105°C, or between 65 and 100°C, or between 70 and 110°C, or between 70 and 100°C, or between 75 and 110°C, or between 75 and 100°C, or between 80 and 100°C. In some embodiments, the formation of a polymer matrix facilitates the formation of a thin film and / or gives the dried thin film the desired elasticity and / or tackiness or tensile strength, even if the dried thin film is very thin. Modified polysaccharides, specifically soluble hydroxypropyl-substituted methylcellulose, have viscosities of at least 0.5, at least 1, or at least 2 mPa·s, measured at a 2% weight concentration in water at 25°C, up to 11, up to 10, up to 9, up to 8, up to 7, up to 6, up to 5, up to 4, and optionally, viscosities in the range of 0.5–10, 1–8, 2–8, 2–5, or 2–4. Modified polysaccharides, specifically soluble hydroxypropyl-substituted methylcellulose, may have a gelation temperature, measured at a 2% weight concentration in water.

[0342] B6: Relatively low viscosity before application to ITM in step S101 of Figure 2C (or before application to ITM in step S209 of Figure 2A) - As described below, in step S101 of Figure 2C (or step S209 of Figure 2A), the inventors found it desirable to apply a thin but relatively uniform wet layer of the aqueous treatment formulation. For this purpose, in some embodiments, the kinematic viscosity at 25°C of the initial aqueous treatment formulation may be up to 100 cP, or up to 80 cP, or up to 40 cP, or up to 30 cP. Alternatively, or additionally, the kinematic viscosity at 25°C of the initial aqueous treatment formulation may be at least 8 cP, or at least 10 cP, or at least 12 cP, or at least 14 cP - for example, in the range of 8–100 cP, 10–100 cP, 12–100 cP, 14–100 cP, 10–60 cP, or 12 cP–40 cP. In some embodiments, this feature would be particularly useful when applying a processing formulation to an ITM while the ITM is moving at high speed (for example, as it passes through an applicator device—for example, a stationary applicator device).

[0343] B7: Absence of organic solvents or sugar alcohols such as glycerol - In some embodiments according to the present invention, the presence of low vapor pressure organic solvents may delay the drying of the treated formulation on the surface of the ITM in step S105 and / or result in a treated thin film lacking the desired elasticity and / or tackiness or tensile strength desirable for transfer in step S117. In some embodiments, the formulation is devoid of organic solvents, regardless of their vapor pressure in their pure state, and / or contains up to 3%, up to 2%, up to 1%, or up to 0.5%, or up to 0.25%, or up to 0.1% by weight of organic solvents. Specifically, in some embodiments, the formulation is devoid of organic solvents and / or contains up to 3%, up to 2%, up to 1%, or up to 0.5%, or up to 0.25%, or up to 0.1% by weight of glycerol. In some embodiments, the formulation is completely devoid of glycerol.

[0344] B8: Inclusion of a water-absorbing agent - In some embodiments according to the present invention, the initial aqueous treatment formulation includes a solid water-absorbing agent selected to absorb moisture from the ink when the water-absorbing agent is placed in a solid, drying treatment thin film. For example, such a solid water-absorbing agent may have a melting point (i.e., in its pure state) of up to 60°C, or up to 50°C, or up to 40°C, or up to 30°C, or up to 25°C. The concentration of the solid water-absorbing agent may be, for example, at least 1.5%, or at least 2%, or at least 2.5%, or at least 3% wt. / wt. Such water-absorbing agents include, but are not limited to, sucrose, urea, sorbitol, and isomalt.

[0345] B9: Having a flocculant containing a polyvalent cation (such as calcium chloride) at a maximum or low concentration - In some embodiments, these compounds are considered detrimental to image quality.

[0346] B10: Having polyethyleneimine - In some embodiments according to the present invention, the concentration of polyethyleneimine may be at least 0.05%, at least 0.1%, or at least 0.2%, and optionally up to 1% or up to 0.8%, up to 0.7%, or up to 0.6%, up to 0.5%, or 0.1–1%, 0.1–0.8%, 0.1–0.7%, 0.1–0.6%, 0.1–0.5%, 0.2–0.7%, 0.2–0.6%, or 0.2–0.5%.

[0347] It should be noted that for one or more of the aforementioned features, one or more further features may be provided, as disclosed above and below in this specification, arising from the presence of one or more particulate materials in the aqueous treatment formulation.

[0348] Explanation of step S99 in Figure 2C Potential characteristics of water-based inks: Feature C1: In some embodiments according to the present invention (for example, relating to the method in Figure 2A or Figure 2C), the ink provides one or more features (any combination of features) disclosed in PCT / IB13 / 51755 or US2015 / 0025179, PCT / IB14 / 02395 or US14 / 917461, all of which are incorporated herein by reference. Exemplary features include, but are not limited to, having at least one of (i) a viscosity of 2 to 25 cP at at least one temperature in the range of 20 to 60°C and (ii) a surface tension of 50 millinewtons / m or less at at least one temperature in the range of 20 to 60°C, provided that at least one of the following two statements is true: (1) When the ink is substantially dry, (a) at at least one temperature in the range of 70 to 195°C, the dry ink has a first kinematic viscosity in the range of 1,000,000 (1 × 10⁶) cP to 300,000,000 (3 × 10⁸) cP, and (b) at at least one temperature in the range of 50 to 85°C, the dry ink has a second kinematic viscosity of at least 80,000,000 (8 × 10⁷) cP, the second kinematic viscosity being greater than the first kinematic viscosity, and (2) the weight ratio of the resin to the colorant is at least 1:1.

[0349] For example, an aqueous inkjet ink formulation comprises: a solvent containing water and optionally a cosolvent, wherein the water constitutes at least 8 wt.% of the formulation; at least one colorant dispersed or at least partially dissolved in the solvent, wherein the colorant constitutes at least 1 wt.% of the formulation; and an organic polymer resin dispersed or at least partially dissolved in the solvent, wherein the resin constitutes 6 to 40 wt.% of the formulation and the average molecular weight of the resin is at least 8,000.

[0350] Explanation of step S105 in Figure 2C Feature D1: In some embodiments according to the present invention, the drying layer formed in step S105 is thin but not monolayer (e.g., significantly thicker than a monolayer) - for example, having a thickness of at least 20 nanometers and typically up to 100 nanometers. In some embodiments, the drying layer is extremely thin and has a thickness of up to 80 nanometers, or up to 75 nanometers, or up to 70 nanometers, or up to 65 nanometers, or up to 60 nanometers, or up to 55 nanometers, or up to 50 nanometers, or up to 45 nanometers, or up to 40 nanometers or up to 35 nanometers. Nevertheless, in some embodiments, even if the drying thin film is extremely thin, it is thicker than a monolayer or monolayer-type component. Thus, in some embodiments, the thickness of the drying layer may be at least 25 nanometers, or at least 30 nanometers, or at least 40 nanometers, or at least 50 nanometers. In some embodiments, providing this many “bulks” (i.e., minimum thickness features—for example, along with other features (may be multiple) described below) facilitates the formation of a tacky and / or elastic dried thin film—which may be useful in step S117, where it is desirable that the dried thin film (i.e., having a dried ink image on it at that stage) retains its structural integrity when transferred from the ITM to the substrate.

[0351] In some embodiments of the present invention, the dried formulation or thin film may impart an undesirable gloss to the resulting product after transfer to the substrate—therefore, the ability to form a thin but adhesive dried layer may be useful. The thinness of the layer also facilitates evaporation and drying of the layer into a thin film.

[0352] Feature D2: In some embodiments according to the present invention, the dried thin film formed on the ITM in step S105 is continuous and, despite its thinness or extreme thinness, has no "exposed portions". As described below, in some embodiments, to achieve this (i.e., especially for thin or very thin layers), both of the following may be required: (i) the initial coating wet layer applied in step S101 is continuous and without exposed portions, even if the initial coating wet layer is relatively thin and has a thickness of up to about 1 μm (or up to 0.8 μm, or up to 0.6 μm, or up to 0.4 μm and typically up to 0.3 μm, up to 0.25 μm, or up to 0.2 μm, and / or at least 0.1 μm); and (ii) the drying process in step S105 occurs very rapidly and the viscosity of the dried formulation increases very rapidly (e.g., by at least 100 times, at least 1000 times, or at least 10,000 times, or at least 10,000 times, within up to 100 milliseconds, up to 50 milliseconds, up to 40 milliseconds, up to 30 milliseconds, up to 25 milliseconds, up to 20 milliseconds, up to 15 milliseconds, or up to 10 milliseconds). Since the ITM release layer is hydrophobic and the treatment formulation is aqueous and more hydrophilic, when an aqueous treatment formulation is applied to the ITM release layer, the aqueous treatment formulation may produce beading. However, if the viscosity increases rapidly after the application of the wet treatment layer, a treatment formulation with higher viscosity may resist beading better than a formulation with lower viscosity. In some embodiments, as described above in feature "B1", the aqueous treatment formulation may be rich in solid material to facilitate a rapid increase in viscosity.

[0353] Another beading prevention feature useful for obtaining a continuous drying thin film (i.e., beading prevention of the treatment formulation in steps S101-S105) may relate to the relative properties of (i) the delamination surface of the ITM, which in some embodiments is hydrophobic but not excessively hydrophobic (see feature (see feature "BA")) and (ii) the aqueous treatment formulation, which in some embodiments is hydrophilic but not excessively hydrophilic (see feature "B4"). If the static surface tension between the aqueous treatment formulation and the delamination layer of the ITM is relatively small, there is little driving force toward beading, and the viscosity of the aqueous treatment formulation may be sufficient to prevent beading (for example, when it increases rapidly).

[0354] As mentioned above, despite the moderate hydrophobicity of the ITM release layer (see feature "A3"), the ITM release layer may have certain properties (see feature "A5") that limit adhesion between the ITM release layer and the dried thin film. Thus, even if the treated surface is only moderately hydrophobic in steps S101 and / or S105 to avoid beading of the treated formulation on it, if it is later desired to minimize adhesion between the ITM release layer and the dried thin film, it may be possible to avoid paying the "compensation" for this benefit in step S117 (for example, at least in part thanks to feature "B2").

[0355] Feature D3: In some embodiments according to the present invention, the dried thin film formed on the ITM in step S105 is characterized by an extremely low surface roughness - in some embodiments, the surface roughness is an average roughness R of up to 20 nanometers or up to 18 nanometers or up to 16 nanometers or up to 15 nanometers or up to 14 nanometers or up to 12 nanometers or up to 10 nanometers or up to 9 nanometers or up to 8 nanometers or up to 7 nanometers or up to 6 nanometers. a It can be characterized by (commonly used one-dimensional roughness parameters). The dried thin film formed on the ITM has at least 3 nanometers or at least 5 nanometers of R a It may have.

[0356] In some embodiments, even for thin or extremely thin drying-treated films formed in step S105—for example, with an average roughness R a Even when the ratio of the thickness of the drying layer to the thickness of the drying layer is at least 0.02 or at least 0.03 or at least 0.04 or at least 0.05 or at least 0.06 or at least 0.07 or at least 0.08 or at least 0.9 or at least 0.1 or at least 0.11 or at least 0.12 or at least 0.13 or at least 0.14 or at least 0.15 or at least 0.16 or at least 0.17 or at least 0.18 or at least 0.19 or at least 0.2, such a low average roughness R a It may be possible to achieve this.

[0357] In some embodiments according to the present invention, the dried thin film to which aqueous ink droplets are attached and the surface of the dried thin film (e.g., its upper surface) are characterized by a dimensionless ratio between (i) average roughness Ra and (ii) the thickness of the dried layer, where the dimensionless ratio is up to 0.5, up to 0.4, up to 0.3, up to 0.25, up to 0.2, up to 0.15, or up to 0.1, and optionally at least 0.02, or at least 0.03, or at least 0.04, or at least 0.05, or at least 0.06, or at least 0.07, or at least 0.08.

[0358] Feature D4: In some embodiments according to the present invention, at least the entire rectangle of 10 cm × 1 m, or 1 m 2 , 3m 2 , or 10m 2 It is possible to obtain a continuous, dry thin film that covers the entire surface. The thin film may have a thickness or average thickness of up to 120 nm, up to 100 nm, up to 80 nm, up to 60 nm, up to 50 nm, or up to 40 nm, and typically at least 20 nm, at least 25 nm, or at least 30 nm.

[0359] Explanation of Steps S109-S117 In some embodiments according to the present invention, steps S109 and / or S113 and / or S117 may be performed to provide one or more of the following process-related features:

[0360] Feature E1 - In some embodiments, step S117 is performed at a high transfer temperature (e.g., up to 120°C or up to 110°C or 100°C).

[0361] In some embodiments, both the dried thin film and the dried ink image are tacky at the transfer temperature and therefore easily peel off cleanly from the release layer.

[0362] Feature E2: Diffusion - In some embodiments, the manner in which droplets adhere to the thin film (e.g., wetting angle) and the physical and / or chemical properties of the treated thin film [A2 and / or A3 and / or A8 - nanoparticles in the ink may also contribute] are such that the radius of the ink dot exceeds the radius of the precursor droplet immediately after impact with the dried treated thin film - for example, each droplet increases in size beyond the size resulting from the diffusion of the droplet caused by the impact energy of that droplet. [Dmax=2·Rmax, or Dimpact-max=2·Rimpact-max]

[0363] As described above, the aqueous treatment formulation may further comprise at least one particulate material disclosed herein.

[0364] As a result, in some embodiments according to the present invention, the aqueous formulation is At least one water-soluble polymer, (i) a cationic emulsion of at least one oxidized polyethylene wax particle material, (ii) a dispersion and / or emulsion of at least one coating wax particle material, and (iii) a dispersion of at least one thermosetting polymer particle material, A carrier liquid containing water, and Optionally, one or more of the following: (a) at least one surfactant, (b) at least one water-retaining agent, and (c) at least one wetting agent, e.g., PEI. Includes.

[0365] In some embodiments according to the present invention, the aqueous formulation is At least one water-soluble polymer, At least one surfactant (which may optionally be a first nonionic surfactant having at least 7% solubility in water at 25°C and / or optionally a second nonionic, silicone-containing surfactant having at least 1% solubility in water at 25°C), (i) at least one thermoplastic polymer particulate material (optionally in the form of an emulsion or dispersion), (ii) at least one thermosetting polymer particulate material (optionally in the form of an emulsion or dispersion), or (iii) a combination thereof, at least one particulate material selected from these, A carrier liquid containing water, optionally comprising at least about 55% by weight of an aqueous formulation, and Optionally, one or more of the following: (a) at least one water-retaining agent, and (b) at least one wetting agent, e.g., PEI. Includes.

[0366] In some embodiments of the present invention, the aqueous formulation is At least one water-soluble polymer, excluding thermoplastic water-soluble polymers, At least one surfactant, (i) at least one thermoplastic polymer particulate material (optionally in the form of an emulsion or dispersion), (ii) at least one thermosetting polymer particulate material (optionally in the form of an emulsion or dispersion), or (iii) a combination thereof, at least one particulate material selected from these, A carrier liquid containing water, optionally comprising at least about 55% by weight of an aqueous formulation, and Optionally, one or more of the following: (a) at least one water-retaining agent, and (b) at least one wetting agent, e.g., PEI. Includes.

[0367] In some embodiments of the present invention, the aqueous formulation is At least one water-soluble polymer having a solubility of at least 1.5% by weight and at least 5% in water at 25°C, A first nonionic surfactant having a solubility in water of at least 5% by weight and at least 7% at 25°C, A second nonionic, silicone-containing surfactant having solubility in at least 1% water at 25°C, (i) at least one thermoplastic polymer particulate material (optionally in the form of an emulsion or dispersion), (ii) at least one thermosetting polymer particulate material (optionally in the form of an emulsion or dispersion), or (iii) a combination thereof, at least one particulate material selected from these, A carrier liquid containing water, wherein the water constitutes at least about 55% by weight of the aqueous formulation, and Optionally, one or more of the following: (a) at least one water-retaining agent, and (b) at least one wetting agent. Includes.

[0368] In some embodiments according to the present invention, the aqueous formulation may further contain additional surfactants other than the first and second nonionic surfactants.

[0369] As used herein with respect to the formulations of the present invention, the term "aqueous" refers to a formulation whose contents are primarily aqueous, for example, in which water constitutes more than 50% of the weight of the formulation.

[0370] As used herein, the term “aqueous formulation” refers, unless otherwise specified, to an aqueous formulation used with an intermediate transfer member in an indirect printing system, such as those described herein. Sometimes, the term “aqueous processed formulation” is interchangeable with the term “aqueous processed formulation.”

[0371] The terms “basic aqueous treatment formulation,” “basic solution,” “basic formulation,” or any linguistic variations thereof used herein are interchangeable and, unless otherwise specified, refer to aqueous treatment formulations lacking particulate material according to the present invention.

[0372] In some embodiments according to the present invention, the particulate material is provided in the form of an emulsion.

[0373] As used herein, the term "emulsion" or any linguistic variation thereof refers to a mixture of at least two immiscible liquids.

[0374] In some embodiments according to the present invention, the emulsion may be an oil-in-water (o / w) emulsion having a continuous aqueous phase.

[0375] In some embodiments according to the present invention, the emulsion may be a water-in-oil (w / o) emulsion having a continuous oil phase.

[0376] In some embodiments according to the present invention, the emulsion is an aqueous emulsion.

[0377] In some embodiments of the present invention, the emulsion is a cationic emulsion, i.e., a positively charged emulsion (such as, but not limited to, an emulsion containing an ammonium salt emulsifier).

[0378] In some embodiments according to the present invention, the particulate material is provided in the form of a dispersion.

[0379] As used herein, the term "dispersion" or any linguistic variation thereof refers to a solution consisting of solid particles uniformly dispersed in a liquid phase.

[0380] In some embodiments according to the present invention, the dispersion is an aqueous dispersion.

[0381] In some embodiments according to the present invention, the dispersion is an oil dispersion.

[0382] In some embodiments according to the present invention, the particulate material of the present invention is dispersed in an emulsion, for example, in the aqueous phase of an emulsion.

[0383] Figure 3 shows an indirect printing process 300 according to several embodiments of the present invention, in which the peel surface 301 of the intermediate transfer member 302 is pre-treated (e.g., coated) with an aqueous formulation according to the present invention before the ink image is applied thereto. The aqueous formulation (also referred herein as the aqueous treatment formulation) is applied to the surface 301 of the ITM (e.g., hydrophobic ITM) (which may be substantially smooth as detailed below herein) to form a thin wetting treatment layer thereon, which is then passed through a drying process on the ITM peel surface to leave a thin substantially dried treatment film 304 on the ITM 302 peel surface 301. Subsequently, droplets of aqueous ink are applied to the thin substantially dried treatment film 304 (e.g., by inkjet) to form an ink image thereon. The formed ink image is then passed through a drying process to leave ink residue on the dried treatment film, which is represented as ink dots 306 in Figure 3. The dried ink image (e.g., ink dot 306) is then transferred (308) from the 302 ITM surface 301 to the final substrate 310 together with a thin dried film 304. The transferred ink dot 312 adheres firmly to the final printing substrate 310 together with the transferred dried film 314, and the transferred dried film 314 covers the substrate even in areas without ink. It should be noted that the relative dimensions of each component in Figure 3 are for illustrative purposes only of the printing process and products of the present invention and should not be considered as limitations. It should be further noted that in some embodiments, the ink dot and the dried film, which may form an ink film, are separate films, i.e., no mixing of components between the films occurs during the process of the present invention. In some embodiments, for example, components from the ink may penetrate to some extent into the dried film during the printing process.

[0384] Figure 3 shows that in the illustrated process 300, the dried thin film 314 becomes the top layer of the final printed substrate. Therefore, the thin film allows for the modification of printed image surface properties such as friction coefficient, mechanical strength (e.g., abrasion resistance and / or scratch resistance), and humidity sensitivity. Sometimes, the dried thin film 314 can also function as a protective layer against the ink image surface (e.g., ink dots 312).

[0385] In some embodiments according to the present invention, the dried thin film comprises one or more polymer particle materials described herein (not shown in Figure 3). In some embodiments, the surface of the dried thin film 316, distal to the surface of the substrate, is substantially smooth (e.g., has low surface roughness). This is achieved, for example, by utilizing an ITM having a substantially smooth peel surface 301, as detailed above and below herein, the substantially smooth peel surface 301 affects the surface of the dried thin film placed thereon, which becomes the surface of the dried thin film 316 after transfer 308 (in this regard, although not wishing to be bound by theory, the inventors of the present invention believe that the relative flatness or smoothness of the ink thin film of the present invention may largely be attributable to the smoothness of the peel layer on the surface of the ITM, as well as to the inventive system and process such that the newly emerged ink thin film surface substantially complements that of its surface layer, and the resulting ink thin film image substantially or completely retains its complementary shape through transfer onto the printing substrate).

[0386] Accordingly, in some embodiments of the present invention, the particulate material is substantially embedded in the dried thin film and does not protrude from the surface 316 of the dried thin film, thus maintaining the substantially smooth properties of the surface 316. For this purpose, although we do not wish to be bound by theory, the improved abrasion resistance of the printed images produced according to the present invention is thought to be due to a buffering mechanism, for example, particulate material filling the "empty" spaces in the dried thin film.

[0387] Similar to Figures 2A and 2C, Figures 4A to 4C and 5 show flowcharts of a method for indirect printing with aqueous ink onto the surface of a silicone-based release layer of an intermediate transfer member having a layer of treatment or treatment formulation according to several embodiments of the present invention.

[0388] It should be noted that one or more embodiments / features described in detail herein in relation to Figures 2A and 2C may be applicable to the exemplary disclosures in Figures 4A–4C and 5.

[0389] The particle material used in accordance with the present invention can have any shape and size, provided that its size and dimensions, such as diameter, length, width, and thickness, are on the nanoscale.

[0390] In some embodiments according to the present invention, the particle material has a particle size (e.g., diameter or longest axis) between about 1 nm and about 500 nm.

[0391] In some embodiments according to the present invention, the shape of the particle material can be selected from spherical, dot-shaped, rod-shaped, wire-shaped, cubic, cylindrical, polygonal, whisker-shaped, disc-shaped, plate-shaped, multipod-shaped, frame-shaped, and others.

[0392] In some embodiments according to the present invention, the particle material is of a size (e.g., diameter or longest axis) between about 1 and about 500 nm, or any size between those. In some embodiments, the size is between 1 and 400 nm, between 1 and 450 nm, between 1 and 350 nm, between 1 and 250 nm, between 1 and 200 nm, between 1 and 150 nm, between 1 and 100 nm, between 1 and 50 nm, between 1 and 90 nm, between 1 and 80 nm, between 1 and 70 nm, between 1 and 60 nm, between 1 and 50 nm, between 10 and 500 nm, between 20 and 500 nm, between 30 and 500 nm. These ranges are between nm, between 40 and 500 nm, between 50 and 500 nm, between 60 and 500 nm, between 70 and 500 nm, between 80 and 500 nm, between 90 and 500 nm, between 100 and 500 nm, between 150 and 500 nm, between 200 and 500 nm, between 250 and 500 nm, between 300 and 500 nm, between 350 and 500 nm, between 400 and 500 nm, and between 450 and 500 nm.

[0393] In some embodiments according to the present invention, the particle material has a size between about 1 and about 500 nm. In some embodiments, the particle material has a size between about 50 and about 200 nm. In some embodiments, the particle material has a size between about 300 and about 400 nm. In some embodiments, the particle material has sizes of about 50 nm, about 100 nm, about 200 nm, about 300 nm, and about 400 nm.

[0394] In some embodiments according to the present invention, the particulate material has a substantially two-dimensional disk shape (i.e., the diameter constitutes the longest access point of the particulate material).

[0395] In some embodiments of the present invention, one or more particulate materials may be included in the treatment formulation of the present invention. Sometimes the particulate materials may have substantially the same size or may have different sizes.

[0396] As used herein, the term “thermosetting polymer particulate material” or any linguistic variation thereof refers to a particulate material that is a polymer material (e.g., having a relatively high molecular weight) that hardens irreversibly when cured by, for example, heat or appropriate irradiation. Once hardened, this material cannot be remelted.

[0397] As used herein, the term “thermoplastic polymer particulate material” or any linguistic variation thereof refers to a particulate material that is a polymer material (e.g., having a relatively high molecular weight) that becomes flexible or moldable above a certain temperature and solidifies upon cooling. This material can be remelted and reformatted.

[0398] In some embodiments according to the present invention, the particulate material is uniformly dispersed in an aqueous formulation.

[0399] In some embodiments according to the present invention, the concentration of the emulsion of particulate material in the aqueous formulation is at least about 0.5% and up to about 15% by weight relative to the total weight of the formulation. In some embodiments, the concentration is about 0.5%, sometimes about 1%, sometimes about 1.5%, sometimes about 2.0%, sometimes about 2.5%, sometimes about 3.0%, sometimes about 3.5%, sometimes about 4.0%, sometimes about 4.5%, sometimes about 5.0%, sometimes about 5.5%, sometimes about 6.0%, sometimes about 6.5%, sometimes about 7.0%, sometimes about 7.5%, sometimes about 8.0%, sometimes about 8.5%, sometimes about 9.0%, sometimes about 9.5%, sometimes about 10.0%, sometimes about 10.5%, sometimes about 11.0%, sometimes about 11.5%, sometimes about 12.0%, sometimes about 12.5%, sometimes about 13.0%, sometimes about 13.5%, sometimes about 14.0%, sometimes about 14.5%, and sometimes about 15.0%.

[0400] In some embodiments according to the present invention, the concentration of the dispersion of particulate material in the aqueous formulation is at least about 0.5% and up to about 15% by weight relative to the total weight of the formulation. In some embodiments, the concentration is about 0.5%, sometimes about 1%, sometimes about 1.5%, sometimes about 2.0%, sometimes about 2.5%, sometimes about 3.0%, sometimes about 3.5%, sometimes about 4.0%, sometimes about 4.5%, sometimes about 5.0%, sometimes about 5.5%, sometimes about 6.0%, sometimes about 6.5%, sometimes about 7.0%, sometimes about 7.5%, sometimes about 8.0%, sometimes about 8.5%, sometimes about 9.0%, sometimes about 9.5%, sometimes about 10.0%, sometimes about 10.5%, sometimes about 11.0%, sometimes about 11.5%, sometimes about 12.0%, sometimes about 12.5%, sometimes about 13.0%, sometimes about 13.5%, sometimes about 14.0%, sometimes about 14.5%, and sometimes about 15.0%.

[0401] In some embodiments according to the present invention, the thermosetting polymer particle material is a hydrophilic particle material.

[0402] In some embodiments according to the present invention, the thermosetting polymer particle material is a hydrophobic particle material.

[0403] In some embodiments according to the present invention, the thermosetting polymer particulate material is a hydrophobic particulate polymer selected from polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), fluorinated ethylene propylene (FEP), or any combination thereof.

[0404] In some embodiments according to the present invention, the hydrophobic particle material is PTFE (i.e., Teflon).

[0405] In some embodiments according to the present invention, the PTFE particle material is of a size (e.g., diameter or longest axis) between approximately 1 and approximately 500 nm (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, and 500 nm).

[0406] In some embodiments according to the present invention, the PTFE particle material is between approximately 50 nm and approximately 200 nm in size (for example, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, and 200 nm).

[0407] In some embodiments according to the present invention, the PTFE particle material is about 200 nm in size, and the concentration of its dispersion in the aqueous formulation is between about 4% and about 12% by weight relative to the total weight of the formulation (e.g., 4, 5, 6, 7, 8, 9, 10, 11, 12%).

[0408] In some embodiments according to the present invention, the solid content of the particulate material, e.g., PTFE, in the aqueous formulation of the present invention is between about 2% and 7% (e.g., 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0%, 5.5%, 6.0%, 6.5%, and 7.0%).

[0409] In some embodiments according to the present invention, the PTFE particle material has a size of approximately 300 nm to approximately 400 nm (e.g., 300, 310, 320, 330, 340, 350, 360, 370, 380, 390 and 400 nm).

[0410] In some embodiments according to the present invention, the PTFE particle material is approximately 300 nm to approximately 400 nm in size, and the concentration of its dispersion in the aqueous formulation is approximately 8% by weight relative to the total weight of the formulation.

[0411] In some embodiments according to the present invention, the PTFE dispersion is an aqueous dispersion having the following properties: a. Viscosity - about 13cP b.Surface tension - approx. 31.4mN / m c.pH-about 9.95 d. Solid content - about 60% e. Particle size - about 200nm.

[0412] In some embodiments according to the present invention, the thermoplastic polymer particle material is a wax particle material.

[0413] Non-limiting examples of wax particle materials include paraffin wax, polyethylene wax, oxidized polyethylene wax, ethylene copolymer wax, montan ester wax, polyether wax, poly(methylene), polypropylene wax, microcrystalline wax, polyolefin wax, paraffin-ethylene acrylic acid copolymer wax, carnauba wax, or any combination thereof.

[0414] In some embodiments according to the present invention, the wax particle material is polyethylene oxide.

[0415] The molecular weight of the wax material can vary. Exemplary, unlimited MWs are between approximately 700 and 1500 gr / mol (e.g., 700, 800, 900, 1000, 1100, 1200, 1300, 1400, and 1500). In some embodiments, the MW is less than 700 gr / mol. In some embodiments, the MW is greater than 1500 gr / mol.

[0416] Examples of thermoplastic particulate material emulsions, such as wax emulsions, may include nonionic emulsions, anionic emulsions, cationic emulsions, and aqueous emulsions.

[0417] In some embodiments according to the present invention, the thermoplastic particle material emulsion is a cationic emulsion.

[0418] In some embodiments according to the present invention, the wax emulsion is an aqueous emulsion.

[0419] In some embodiments according to the present invention, the wax is provided as a cationic emulsion.

[0420] In some embodiments according to the present invention, the wax particle material is an oxidized polyethylene wax particle material.

[0421] In some embodiments according to the present invention, the granular polyethylene oxide wax has a size (e.g., diameter or longest axis) between about 1 nm and about 500 nm.

[0422] In some embodiments according to the present invention, the granular oxidized polyethylene wax is about 1 to about 500 nm in size, and the concentration of its emulsion in the aqueous formulation is between about 1.5% and about 5% by weight relative to the total weight of the formulation (e.g., about 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, and 5.0%).

[0423] In some embodiments, the solid content of the particulate material in the aqueous formulation of the present invention, for example, granular oxidized polyethylene wax, is between about 0.3% and 1.75% (e.g., 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.70, and 1.75%).

[0424] In some embodiments according to the present invention, the granular polyethylene oxide wax has a glass transition temperature (Tg) value of about 130°C.

[0425] As used herein, the term “glass transition temperature” or any linguistic variation thereof refers to the softening temperature.

[0426] In some embodiments according to the present invention, the thermoplastic particulate material (e.g., granular polyethylene oxide wax) has a Tg value of about 80°C to about 160°C (e.g., 80, 85, 90, 95, 100, 115, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, or 160°C). Sometimes the Tg value is about 100°C to about 160°C.

[0427] In some embodiments according to the present invention, the thermoplastic particle material (e.g., the coating wax particle material NanoBYK 3620) has a Tg value of about 125°C, and sometimes about 130°C.

[0428] While we do not wish to be bound by theory, the inventors of this invention believe that thermoplastic materials (e.g., waxes) need to have a relatively high Tg to ensure that the particle shape and / or size are maintained, particularly after substantial drying of the treated layer. Low Tg, such as below 80°C, can cause the particles to change during the process, resulting in a lack of activity (e.g., no improvement in abrasion resistance).

[0429] In some embodiments according to the present invention, the emulsion of at least one thermoplastic polymer particle material is a cationic emulsion.

[0430] In some embodiments according to the present invention, the cationic emulsion is an emulsion of granular oxidized polyethylene wax.

[0431] In some embodiments according to the present invention, the cationic emulsion of granular polyethylene oxide wax has the following properties: a. Viscosity at -20°C is approximately 80 cP b. Density - about 1g / cm 3 c. pH - Approximately 9.5 at a concentration of about 1%. d. Solid content - about 25-29% e. Particle size - less than approximately 500 nm.

[0432] In some embodiments according to the present invention, the thermoplastic polymer particle material is a coating wax particle material.

[0433] In some embodiments according to the present invention, the wax is coated with particles such as silicon dioxide.

[0434] In some embodiments according to the present invention, the coating wax particle material is a granular wax material coated with silicon dioxide.

[0435] In some embodiments of the present invention, the coating wax particle material is approximately 100 nm in size (e.g., diameter or longest axis).

[0436] In some embodiments according to the present invention, the coating wax particle material is about 100 nm in size (e.g., diameter or longest axis), and the concentration of its emulsion (or dispersion) in the aqueous formulation is at least about 10% by weight relative to the total weight of the formulation.

[0437] In some embodiments, formulations according to the present invention are substantially free of aggregates (for example, free of aggregates of any of the particulate materials. Such aggregates may be formed of the same particles or combinations of one or more different particles).

[0438] In some embodiments according to the present invention, particulate materials may be redispersible in an aqueous formulation according to the present invention, and other non-particulate components of the formulation may be remelted and redispersible, and then remelted in the aqueous formulation after being dried (e.g., on an ITM as detailed herein) so that the resulting formulation retains the properties of the aqueous-treated formulation. For this purpose, the system utilized in the present invention may further include a washing station configured to remove the residual dried-treated thin film from the ITM (e.g., by using one or more knives and / or one or more brushes, or other suitable means). Such a system is disclosed in WO 2017 / 208246 to the present applicant, the contents of which are incorporated herein by reference.

[0439] In some embodiments, the aqueous formulation according to the present invention may further contain at least one antimicrobial agent.

[0440] In some embodiments, aqueous formulations according to the present invention have the following characteristics: i. Static surface tension in the range of 20 to 40 mN / m at 25℃, ii. A kinematic viscosity at 25°C of at least 10 cP, and iii. Weight-based 60°C evaporation load of up to 7.5:1.

[0441] In some embodiments of the present invention, the aqueous treatment formulation may further comprise at least one water-retaining agent, which is optionally a sugar.

[0442] As used herein, the term "water-soluble polymer" refers to a polymer that is partially soluble in water at 25°C.

[0443] In some embodiments according to the present invention, the water-soluble polymer has a solubility in at least 5% water at 25°C.

[0444] In some embodiments according to the present invention, the solubility of at least one water-soluble polymer in water at 25°C is at least 7%, at least 10%, at least 12%, at least 15%, at least 20%, or at least 25%, and optionally up to 80% or up to 60%.

[0445] In some embodiments according to the present invention, the water-soluble polymer is a binder, specifically a soluble binder.

[0446] In some embodiments according to the present invention, the water-soluble polymer is selected from the group consisting of polyvinyl alcohol, water-soluble cellulose, polyvinylpyrrolidone (PVP), polyethylene oxide, and water-soluble acrylate.

[0447] In some embodiments according to the present invention, the water-soluble polymer is a modified polysaccharide as described herein.

[0448] In some embodiments, the processed formulations according to the present invention lack a water-soluble thermoplastic polymer.

[0449] In some embodiments of the present invention, the concentration of the water-soluble polymer in the formulation of the present invention is in the range of 2.0–8%, 2.5–6.5%, 2.5–6%, 2.5–5.5%, or 2.5–5%, and optionally up to 10%, 8%, 6%, or 5%.

[0450] In some embodiments according to the present invention, the surfactant is a nonionic surfactant, for example, a nonionic silicone-containing surfactant.

[0451] In some embodiments, the aqueous formulation has a total concentration of surfactants in the range of at least 0.3%, at least 0.5%, at least 0.75%, at least 1%, at least 2%, at least 3%, at least 4%, at least 5%, at least 6%, at least 7%, at least 8%, at least 9%, at least 10%, at least 11%, at least 12%, and optionally 6-40%, 6-30%, 6-20%, 7-30%, 7-20%, 7-15%, 8-25%, 8-20%, 8-15%, 8-13%, 9-25%, 9-20%, 9-15%, 9-13%, 10-25%, 10-20%, 10-15%, or 10-13%.

[0452] In some embodiments, the aqueous formulation comprises, by weight, at least 6%, at least 7%, at least 8%, at least 9%, or at least 10% of the first nonionic surfactant.

[0453] In some embodiments according to the present invention, the aqueous formulation comprises, by weight, up to 18%, up to 16%, up to 15%, up to 14%, or up to 13% of the first nonionic surfactant.

[0454] In some embodiments according to the present invention, the concentration of the first nonionic surfactant in the aqueous treatment formulation by weight is within the range of 5.5–18%, 5.5–16%, 6.5–18%, 6.5–16%, 7.5–18%, 7.5–16%, 8.5–18%, 8.5–16%, 9.5–18%, 9.5–16%, 10.5–18%, or 10.5–16%.

[0455] In some embodiments according to the present invention, the solubility of the first nonionic surfactant in water at 25°C in the aqueous formulation is at least 8%, at least 10%, at least 12%, at least 15%, at least 20%, at least 25%, or at least 30%, and optionally up to 80% or up to 60%.

[0456] In some embodiments according to the present invention, the second nonionic silicone-containing surfactant in the aqueous formulation comprises a polysiloxane-polyoxyalkylene copolymer, optionally, the concentration of the polysiloxane-polyoxyalkylene copolymer being at least 0.3%, at least 0.5%, at least 0.75%, or at least 1.0% by weight, and further optionally, up to 5%, up to 4%, up to 3%, up to 2.5%, up to 2%, or up to 1.75% by weight.

[0457] In some embodiments according to the present invention, the aqueous formulation comprises, by weight, at least 0.3%, at least 0.5%, at least 0.75%, or at least 1.0% of the second nonionic silicone-containing surfactant, and optionally, up to 5%, up to 4%, up to 3%, up to 2.5%, up to 2%, or up to 1.75% by weight.

[0458] In some embodiments according to the present invention, the first nonionic surfactant is a polyethoxylated sorbitan ester, or mainly comprises a polyethoxylated sorbitan ester, or comprises a polyethoxylated sorbitan ester.

[0459] In some embodiments according to the present invention, the polyethoxylated sorbitan ester comprises at least one or at least two chemical species selected from the group consisting of PEG-4 sorbitan monolaurate, PEG-20 sorbitan monolaurate, PEG-20 sorbitan monopalmitate, PEG-20 sorbitan monostearate, and PEG-20 sorbitan monooleate.

[0460] In some embodiments according to the present invention, the HLB number of the first nonionic surfactant is at least 11, at least 12, at least 13, at least 14, or at least 14.5, and optionally up to 22, up to 21, up to 20, up to 19, up to 18, or up to 17, and further optionally up to 11-25, 11-23, 11.5-21, 11.5-20, 11.5-18, 12.5-21, 12.5-20, 12.5-18, 13.5-21, 13.5-20, 13.5-18, 14-20.5, 14-18.5, 14.5-20, 14.5-19, 14.5-18, or 14.5-17.5.

[0461] In some embodiments according to the present invention, the aqueous formulation comprises, by weight, at least 6%, at least 7%, at least 8%, at least 9%, or at least 10% of the first nonionic surfactant.

[0462] In some embodiments according to the present invention, the aqueous formulation comprises, by weight, up to 18%, up to 16%, up to 15%, up to 14%, or up to 13% of the first nonionic surfactant.

[0463] In some embodiments according to the present invention, the amount of the first nonionic surfactant in the aqueous treatment formulation by weight is in the range of 5.5-18%, 5.5-16%, 6.5-18%, 6.5-16%, 7.5-18%, 7.5-16%, 8.5-18%, 8.5-16%, 9.5-18%, 9.5-16%, 10.5-18%, or 10.5-16%.

[0464] In some embodiments according to the present invention, the second nonionic silicone-containing surfactant comprises a polysiloxane-polyoxyalkylene copolymer, optionally, the concentration of the polysiloxane-polyoxyalkylene copolymer being at least 0.3%, at least 0.5%, at least 0.75%, or at least 1.0% by weight, and further optionally, up to 5%, up to 4%, up to 3%, up to 2.5%, up to 2%, or up to 1.75% by weight.

[0465] In some embodiments according to the present invention, the aqueous formulation comprises, by weight, at least 0.3%, at least 0.5%, at least 0.75%, or at least 1.0% of the second nonionic silicone-containing surfactant, and optionally, up to 5%, up to 4%, up to 3%, up to 2.5%, up to 2%, or up to 1.75% by weight.

[0466] In some embodiments according to the present invention, the cloud point temperature of the first nonionic surfactant is at least 60°C, at least 70°C, at least 80°C, at least 90°C, at least 100°C, at least 105°C, at least 110°C, at least 115°C, at least 120°C, or at least 130°C, as optionally determined by the ASTM D7689-11 test method.

[0467] In some embodiments, the aqueous formulation has a total concentration of surfactants in the range of at least 6%, at least 7%, at least 8%, at least 9%, at least 10%, or at least 12%, and optionally in the range of 6–40%, 6–30%, 6–20%, 7–30%, 7–20%, 7–15%, 8–25%, 8–20%, 8–15%, 8–13%, 9–25%, 9–20%, 9–15%, 9–13%, 10–25%, 10–20%, 10–15%, or 10–13%.

[0468] In some embodiments according to the present invention, the solubility of the at least one water-soluble polymer in water at 25°C is at least 7%, at least 10%, at least 12%, at least 15%, at least 20%, or at least 25%, and optionally up to 80% or up to 60%.

[0469] In some embodiments, the solubility of the first nonionic surfactant in water at 25°C is at least 8%, at least 10%, at least 12%, at least 15%, at least 20%, at least 25%, or at least 30%, and optionally up to 80% or up to 60%.

[0470] In some embodiments according to the present invention, the concentration of the first nonionic surfactant in the aqueous treatment formulation is within the range of 1-18%, 1-15%, 1-12%, 1-10%, 1-8%, 2-18%, 2-15%, 2-12%, 2-10%, 2-8%, 3-18%, 3-15%, 3-12%, 3-10%, 3-8%, or 4-18%, 4-15%, 4-12%, 4-10%, or 4-8% by weight.

[0471] In some embodiments according to the present invention, the aqueous formulation includes a wetting agent.

[0472] In some embodiments according to the present invention, the wetting agent is PEI.

[0473] In some embodiments according to the present invention, the concentration of PEI in the aqueous formulation is in the range of 0.1–1%, 0.1–0.8%, 0.1–0.7%, 0.1–0.6%, 0.1–0.5%, 0.2–0.7%, 0.2–0.6%, or 0.2–0.5% by weight.

[0474] In some embodiments according to the present invention, the concentration of PEI in the aqueous formulation is, by weight, at least 0.05%, at least 0.1%, or at least 0.2%, and optionally up to 1%, up to 0.8%, up to 0.7%, up to 0.6%, up to 0.5%, or 0.1–1%, 0.1–0.8%, 0.1–0.7%, 0.1–0.6%, 0.1–0.5%, 0.2–0.7%, 0.2–0.6%, or 0.2–0.5%.

[0475] In some embodiments according to the present invention, the PEI has an average molecular weight of at least 200,000, at least 350,000, at least 500,000, at least 700,000, at least 750,000, and optionally up to 3,000,000, up to 2,500,000, or up to 2,000,000.

[0476] In some embodiments according to the present invention, PEI can act as a surfactant.

[0477] In some embodiments, the formulation according to the present invention contains at least 55% water by weight.

[0478] In some embodiments, the formulation according to the present invention may further contain at least one selected agent, thereby absorbing moisture from the aqueous treatment solution when the aqueous treatment solution evaporates to form a solid thin film. In some embodiments, the agent is solid in its pure state at a temperature of at least 25°C to 60°C, thereby acting as a moisture absorbent when the aqueous treatment formulation evaporates to form a solid thin film.

[0479] The aqueous treatment formulations of the present invention provide improved durability of printed products resulting from their manufacture. Improvements may be observed in one or more mechanical properties of the printed products. In some embodiments, the improved mechanical property is abrasion resistance.

[0480] As used herein, the term “abrasion resistance” or any linguistic variation thereof refers to the degree to which a printed image can retain its surface and structural integrity under prolonged friction, scratching, and abrasion.

[0481] In some embodiments of the present invention, the improved property is abrasion resistance. In some embodiments, the improved property is scratch resistance. In some embodiments, the improved property is abrasion resistance.

[0482] In some embodiments, the mechanical property being improved is surface adhesion (adhesion to other surfaces).

[0483] In some embodiments, the improved mechanical properties are reflected in the coefficient of friction of the printed product and / or printed pattern.

[0484] It should be noted that the embodiments disclosed herein in relation to printed products are applicable to printed patterns, with modifications as necessary.

[0485] As used herein, the term “coefficient of friction” (CoF) refers to the force required to slide two surfaces passing each other. A lower force results in a lower CoF value and higher sliding. Higher friction (lower sliding) generally correlates with higher wear. Therefore, an improvement in CoF means a lower CoF value. In some embodiments, the CoF value is less than 1 (e.g., 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, 0.85, 0.90, 0.95).

[0486] In some embodiments, the CoF value is between approximately 0.5 and 0.6 (e.g., 0.51, 0.52, 0.53, 0.54, 0.55, 0.56, 0.57, 0.58, 0.59, 0.60). In some embodiments, the CoF value is approximately 0.5, sometimes 0.6.

[0487] As used herein, the term "scratch resistance" refers to a surface's ability to resist damage caused by sharp objects moving across the surface, resulting in fine cuts.

[0488] As used herein, the term "rub resistance" refers to resistance to wear caused by repeated friction over a surface area.

[0489] Improvements in friction resistance can be achieved through various mechanisms such as abrasive wear, adhesive wear, and shock absorption. In some embodiments, friction resistance is achieved by abrasive wear mechanisms, sometimes by adhesive wear, and sometimes by shock absorption.

[0490] As will be understood by those familiar with the art, any one of the mechanical properties detailed herein can be measured by known methods and apparatus. For example, abrasion resistance can be measured by sweeping an abrasive block several times over each sample and comparing the optical density of the sample to a baseline value established for those samples before the abrasion test. Samples can be placed in a TMI (Testing Machines Incorporated) ink abrasion tester (model #10-18-01), and a dry ink abrasion test can be performed using a 1.8 kg test block with Condat Gloss® paper (135 gsm) placed on it. The optical density of the sample can be measured before the test and after 100 abrasion cycles. This abrasion resistance measurement procedure is recommended by the TMI Instruction Manual and is based on ASTM Procedure D5264.

[0491] In some embodiments of the present invention, improvements in wear resistance are observed using TMI.

[0492] Accordingly, in some embodiments according to the present invention, particulate materials (e.g., oxidized polyethylene wax particulate materials, coating wax particulate materials, thermosetting polymer particulate materials, thermoplastic polymer particulate materials, or any combination thereof) can improve at least one mechanical property (e.g., abrasion resistance, scratch resistance, coefficient of friction, surface tackiness, etc.) of a printed product (e.g., an ink image on a substrate) produced by utilizing an aqueous formulation together with an intermediate transfer member of a printing system, wherein the improvement in mechanical properties is the same as that of the aqueous formulation of the present invention, but in comparison to a printed product (e.g., an ink image on a substrate) produced using an aqueous formulation lacking the particulate material.

[0493] In some embodiments according to the present invention, the mechanical property is abrasion resistance.

[0494] In some embodiments according to the present invention, the improvement in abrasion resistance is at least about 5%, at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, or at least about 95% (based on visual detection of the printed product, for example).

[0495] In another embodiment, the present invention is a. To provide an intermediate transfer member including a release layer surface. b. To provide an aqueous formulation according to the present invention. c. Apply an aqueous formulation to the surface of the ITM release layer and form a wet layer thereon having a maximum thickness of approximately 1.0 μm (for example, a maximum of 0.8 μm). d. Optionally, the wet layer is subjected to a drying process to form a dry thin film layer on the surface of the ITM release layer from the wet layer, wherein the dry thin film layer has a thickness of at least about 20 nm and a maximum of about 200 nm. e. Deposition of droplets of aqueous ink onto a dry thin film to form an ink image on the surface of the ITM release layer. f. Drying the ink image to leave ink image residue on the surface of the ITM release layer, and g. Transferring ink image residue onto the printing substrate by pressurized contact between the ITM and the printing substrate. This provides a method of indirect printing, including [specific details omitted].

[0496] It should be noted that (a) and (b) above are not restricted to their order and can be ordered interchangeably. This applies to the corresponding steps described above and below in this specification in relation to the disclosed method.

[0497] In some embodiments according to the present invention, the aqueous ink is an aqueous ink formulation comprising at least one binder and at least one colorant.

[0498] In some embodiments according to the present invention, at least one colorant in the ink formulation is at least one colorant composed of a pigment.

[0499] In some embodiments according to the present invention, at least one binder in the ink formulation is a negatively charged organic polymer resin.

[0500] In some embodiments according to the present invention, the average molecular weight of the negatively charged organic polymer resin is at least 8,000.

[0501] In some embodiments according to the present invention, at least one binder in the ink formulation is an acrylic polymer and / or styrene acrylate copolymer (for example, having an average molecular weight of about 60,000 g / mol).

[0502] In one further embodiment, the present invention is a. To provide an intermediate transfer member including a release layer surface. b. To provide an aqueous formulation, wherein the aqueous formulation is At least one water-soluble polymer, (i) at least one thermoplastic polymer particle material, (ii) at least one thermosetting polymer particle material, or (iii) a combination thereof, at least one particle material selected from these, A carrier liquid containing water, and Optionally, one or more of (iv) at least one surfactant, (v) at least one water-retaining agent, and (vi) at least one wetting agent, Including, c. Apply an aqueous formulation to the surface of the ITM release layer and form a wet layer thereon having a maximum thickness of approximately 1.0 μm (for example, a maximum of 0.8 μm). d. The wet layer is subjected to a drying process to form a dry thin film layer on the surface of the ITM release layer from the wet layer, wherein the dry thin film layer has a thickness of at least about 20 nm and a maximum of about 200 nm. e. Deposition of droplets of aqueous ink onto a dry thin film to form an ink image on the surface of the ITM release layer. f. Drying the ink image to leave ink image residue on the surface of the ITM release layer, and g. Transferring ink image residue onto the printing substrate by pressurized contact between the ITM and the printing substrate. This provides a method of indirect printing, including [specific details omitted].

[0503] In some embodiments according to the present invention, the particle material has a particle size (e.g., diameter or longest axis) between about 1 nm and about 500 nm.

[0504] In some embodiments according to the present invention, the particulate material has a substantially two-dimensional disk shape (i.e., the diameter constitutes the longest access point of the particulate material).

[0505] In some embodiments of the present invention, the diameter or longest axis of the particulate material in the dried (treated) thin film on the surface of the ITM peeling layer is substantially parallel to the ITM.

[0506] In some embodiments according to the present invention, the thickness of the dried (treated) thin film to which aqueous ink droplets are attached is up to 200 nm, up to 120 nm, up to 100 nm, up to 80 nm, up to 70 nm, up to 60 nm, up to 50 nm, up to 45 nm, or up to 40 nm.

[0507] In some embodiments according to the present invention, the thickness of the dried thin film to which the aqueous ink droplets are attached is at least 15 nm, or at least 20 nm, or at least 25 nm, or at least 30 nm.

[0508] In some embodiments according to the present invention, the thickness of the dried thin film to which aqueous ink droplets are attached is approximately 50 nm at most.

[0509] In some embodiments according to the present invention, the thickness of the dried thin film to which aqueous ink droplets are attached is approximately 100 nm at most.

[0510] In some embodiments according to the present invention, the thickness of the dried thin film to which aqueous ink droplets are attached is approximately 120 nm at most.

[0511] In some embodiments according to the present invention, the thickness of the dried thin film to which aqueous ink droplets are attached is approximately 150 nm at most.

[0512] In some embodiments according to the present invention, the dried thin film is continuous and covers the entire rectangular surface of the ITM, the rectangle having a width of at least 10 cm and a length of at least 10 m.

[0513] In some embodiments according to the present invention, a dried thin film is applied to at least 50%, at least 75%, at least 90%, at least 95%, at least 99%, or 100% of a rectangular area, and the thickness of the dried thin film does not deviate by more than 50%, 40%, or 30% from the average thickness value within the rectangle.

[0514] In some embodiments according to the present invention, ink image residue is transferred onto the printing substrate along with the non-printed areas of the dried thin film.

[0515] In some embodiments according to the present invention, the dried thin film is sufficiently tacky so that during the transfer of ink image residue, the dried thin film completely separates from the ITM and is transferred to the printing substrate along with the dried ink image in both the printed and non-printed areas.

[0516] In some embodiments according to the present invention, the ITM is a hydrophobic ITM.

[0517] In some embodiments of the present invention, the ITM includes a silicone-based release layer surface that is sufficiently hydrophilic to satisfy at least one of the following properties: (i) The receding contact angle of distilled water droplets adhering to the surface of the silicone-based release layer is a maximum of 60°, and (ii) The 10-second dynamic contact angle (DCA) of distilled water droplets adhering to the surface of the silicone release layer is a maximum of 108°.

[0518] Other non-limiting examples of applicable ITMs (e.g., blankets) are detailed below in this specification.

[0519] In some embodiments, the methods disclosed herein provide a printed product with improved one or more mechanical properties (e.g., abrasion resistance, scratch resistance, coefficient of friction, surface tackiness, etc.), the improvement in one or more mechanical properties being compared to a printed product produced using the said method but lacking the said particulate material.

[0520] In another embodiment, the present invention provides a system for printing, the system is a. Intermediate transfer member including the surface of the release layer, b. Aqueous formulations according to the present invention, c. A processing station for applying an aqueous formulation onto an ITM surface and forming a wet layer thereon having a maximum thickness of approximately 1.0 μm (e.g., maximum 0.8 μm). d. An image forming station for forming an ink image on an ITM by depositing droplets of aqueous ink onto the ITM surface after a wet layer has dried to become a dry thin film, such that droplets of aqueous ink are coated onto a dry thin film, wherein the dry thin film layer has a thickness of at least about 20 nm and a maximum of about 200 nm, and e. Transfer station for transferring ink images from ITM to substrate. Includes.

[0521] In another embodiment, the present invention provides a printing system, which is a. An intermediate transfer member (ITM) including a flexible endless belt mounted on multiple guide rollers, b. An image forming station configured to form an ink image on the surface of an ITM, wherein first and second guide rollers are positioned upstream and downstream of the image forming station to define an upper run and a lower run passing through the image forming station. c. A printing station through which the lower run of the ITM passes, located downstream of the image forming station, and configured to transfer an ink image from the surface of the ITM to a substrate, and d. A processing station located downstream of the printing station and upstream of the image forming station, for forming a uniform thin layer of liquid formulation on the ITM surface in its lower run, comprising: e. A coating apparatus for coating ITM with an aqueous formulation according to the present invention, and f. A coating thickness adjustment assembly for removing excess liquid to leave only a desired uniform wet thin layer of a formulation, wherein the layer has a maximum thickness of approximately 1.0 μm (e.g., a maximum of 0.8 μm), and the coating thickness adjustment assembly includes a rounded tip facing the ITM surface in the lower run. Includes.

[0522] In another embodiment, the present invention provides a system for printing, the system is a. Intermediate transfer member including the surface of the release layer, b. Aqueous formulations, At least one water-soluble polymer, (i) at least one thermoplastic polymer particle material, (ii) at least one thermosetting polymer particle material, or (iii) a combination thereof, at least one particle material selected from these, A carrier liquid containing water, and Optionally, one or more of (iv) at least one surfactant, (v) at least one water-retaining agent, and (vi) at least one wetting agent, Aqueous formulations including, c. A processing station for applying an aqueous formulation to the ITM surface and forming a wet layer thereon having a maximum thickness of approximately 1.0 μm (e.g., maximum 0.8 μm). d. An image forming station for forming an ink image on an ITM by depositing droplets of aqueous ink onto the ITM surface after a wet layer has dried to become a dry thin film, such that droplets of aqueous ink are coated onto a dry thin film, wherein the dry thin film layer has a thickness of at least about 20 nm and a maximum of about 200 nm, and e. Transfer station for transferring ink images from ITM to substrate. Includes.

[0523] In another embodiment, the present invention provides a printing system, which is a. An intermediate transfer member including a flexible endless belt mounted on multiple guide rollers, b. An image forming station configured to form an ink image on the surface of an ITM, wherein first and second guide rollers are positioned upstream and downstream of the image forming station to define an upper run and a lower run passing through the image forming station. c. A printing station through which the lower run of the ITM passes, located downstream of the image forming station, and configured to transfer an ink image from the surface of the ITM to a substrate, and d. A processing station located downstream of the printing station and upstream of the image forming station, for forming a uniform thin layer of liquid formulation on the ITM surface in its lower run, comprising: e. A coating apparatus for coating ITM with an aqueous formulation, wherein the aqueous formulation is At least one water-soluble polymer, (i) at least one thermoplastic polymer particle material, (ii) at least one thermosetting polymer particle material, or (iii) a combination thereof, at least one particle material selected from these, A carrier liquid containing water, and Optionally, one or more of (iv) at least one surfactant, (v) at least one water-retaining agent, and (vi) at least one wetting agent, Including, and f. A coating thickness adjustment assembly for removing excess liquid to leave only a desired uniform wet thin layer of a formulation, wherein the layer has a maximum thickness of approximately 1.0 μm (e.g., a maximum of 0.8 μm), and the coating thickness adjustment assembly includes a rounded tip facing the ITM surface in the lower run. Includes.

[0524] The system of the present invention is described in further detail below.

[0525] In another embodiment, the present invention provides a method for improving at least one mechanical property of a printed ink image (on a substrate), the method being a. To provide an intermediate transfer member including a release layer surface. b. To provide an aqueous formulation according to the present invention, wherein the aqueous formulation comprises at least one particulate material disclosed herein. c. Apply an aqueous formulation to the surface of the ITM release layer and form a wet (treated) layer thereon having a maximum thickness of approximately 1.0 μm (for example, a maximum of 0.8 μm). d. Optionally, the wet (treated) layer of (c) is subjected to a drying process to form a dried (treated) thin film layer on the surface of the ITM peel layer from the wet (treated) layer, wherein the dried thin film layer has a thickness of at least about 20 nm and a maximum of about 200 nm. e. Deposition of droplets of aqueous ink onto a optionally dried (treated) thin film to form an ink image on the surface of the ITM release layer. f. Drying the ink image to leave ink image residue on the surface of the ITM release layer, and g. Transferring ink image residue onto the printing substrate by pressurized contact between the ITM and the printing substrate. The invention includes a method for generating a printed ink image on a substrate, wherein the printed ink image has at least one improved mechanical property compared to an ink image generated using the aqueous formulation, which is an aqueous formulation but does not contain the particulate material.

[0526] In one further embodiment, the present invention provides a method for improving at least one mechanical property of a printed ink image (on a substrate), the method being: a. To provide an intermediate transfer member including a release layer surface. b. To provide an aqueous formulation, the aqueous formulation is At least one water-soluble polymer, A carrier liquid containing water, and Optionally, one or more of the following: (i) at least one surfactant, (ii) at least one water-retaining agent, and (iii) at least one wetting agent. Including, c. Add one or more of the following to the aqueous formulation of (b): (i) a cationic emulsion of at least one oxidized polyethylene wax particle material, (ii) a dispersion of at least one coating wax particle material, and (iii) a dispersion of at least one thermosetting polymer particle material. d. The compound produced in (c) is applied to the surface of the ITM release layer to form a wet (treated) layer having a maximum thickness of approximately 1.0 μm (for example, a maximum of 0.8 μm). e. Optionally, the wet (treated) layer of (d) is subjected to a drying process to form a dried (treated) thin film layer on the surface of the ITM release layer from the wet (treated) layer, wherein the dried thin film layer has a thickness of at least about 20 nm and a maximum of 200 nm. f. Deposition of droplets of aqueous ink onto a optionally dried (treated) thin film to form an ink image on the surface of the ITM release layer. g. Drying the ink image to leave ink image residue on the surface of the ITM release layer, and h. Transferring ink image residue onto the printing substrate through pressurized contact between the ITM and the printing substrate. The invention comprises a method for generating a printed ink image on a substrate, wherein the printed ink image has at least one improved mechanical property compared to an ink image generated without adding the emulsion or dispersion of (c) to the aqueous formulation of (b).

[0527] Furthermore, in one further embodiment, the present invention provides a method for improving at least one mechanical property of a printed ink image (on a substrate), the method being a. To provide an intermediate transfer member including a release layer surface. b. To provide an aqueous formulation, the aqueous formulation is At least one water-soluble polymer, A carrier liquid containing water, and Optionally, one or more of the following: (i) at least one surfactant, (ii) at least one water-retaining agent, and (iii) at least one wetting agent. Including, c. Add one or more of the following to the aqueous formulation of (b): (i) a cationic emulsion of at least one oxidized polyethylene wax particle material, (ii) a dispersion of at least one coating wax particle material, and (iii) a dispersion of at least one thermosetting polymer particle material. d. The compound produced in (c) is applied to the surface of the ITM release layer to form a wet (treated) layer having a maximum thickness of approximately 1.0 μm (for example, a maximum of 0.8 μm). e. Optionally, the wet (treated) layer of (d) is subjected to a drying process to form a dried (treated) thin film layer on the surface of the ITM release layer from the wet (treated) layer, wherein the dried thin film layer has a thickness of at least about 20 nm and a maximum of 200 nm. f. Deposition of droplets of aqueous ink onto a optionally dried (treated) thin film to form an ink image on the surface of the ITM release layer. g. Drying the ink image to leave ink image residue on the surface of the ITM release layer, and h. Transferring ink image residue onto the printing substrate through pressurized contact between the ITM and the printing substrate. The invention comprises a method for generating a printed ink image on a substrate, wherein the printed ink image has at least one improved mechanical property compared to an ink image generated without adding the emulsion or dispersion of (c) to the aqueous formulation of (b).

[0528] In one further embodiment, the present invention provides a method for improving at least one mechanical property of a printed ink image (on a substrate), the method being a. To provide an intermediate transfer member including a release layer surface. b. To provide an aqueous formulation, the aqueous formulation is At least one water-soluble polymer having a solubility of at least 1.5% by weight and at least 5% in water at 25°C, A first nonionic surfactant having a solubility of at least 5% by weight and at least 7% in water at 25°C, A second nonionic, silicone-containing surfactant having solubility in at least 1% water at 25°C, A carrier liquid containing water, wherein the water constitutes at least about 55% by weight of the aqueous formulation, and Optionally, one or more of the following: (i) at least one water-retaining agent, and (ii) at least one wetting agent. Including, c. Add one or more of the following to the aqueous formulation of (b): (i) an emulsion or dispersion of at least one thermoplastic polymer particulate material, and (ii) an emulsion or dispersion of at least one thermosetting polymer particulate material. d. The compound produced in (c) is applied to the surface of the ITM release layer to form a wet (treated) layer having a maximum thickness of approximately 1.0 μm (for example, a maximum of 0.8 μm). e. Optionally, the wet (treated) layer of (d) is subjected to a drying process to form a dried (treated) thin film layer on the surface of the ITM peel layer from the wet (treated) layer, wherein the dried thin film layer has a thickness of at least about 20 nm and a maximum of 200 nm. f. Deposition of droplets of aqueous ink onto a optionally dried (treated) thin film to form an ink image on the surface of the ITM release layer. g. Drying the ink image to leave ink image residue on the surface of the ITM release layer, and h. Transferring ink image residue onto the printing substrate through pressurized contact between the ITM and the printing substrate. The invention comprises a method for generating a printed ink image on a substrate, wherein the printed ink image has at least one improved mechanical property compared to an ink image generated without adding the emulsion or dispersion of (c) to the aqueous formulation of (b).

[0529] In another embodiment, the present invention provides a kit for printing in an indirect printing system, the kit is a. Intermediate transfer member including the surface of the release layer, and b. Aqueous treatment formulation according to the present invention Includes.

[0530] In yet another embodiment, the present invention provides a kit for printing in an indirect printing system, the kit is a. Intermediate transfer member including the surface of the release layer, b. Aqueous formulations, At least one water-soluble polymer, (i) a cationic emulsion of at least one oxidized polyethylene wax particle material, (ii) an emulsion or dispersion of at least one coating wax particle material, and (iii) a dispersion of at least one thermosetting polymer particle material, A carrier liquid containing water, and Optionally, one or more of the following: (iv) at least one surfactant, (v) at least one water-retaining agent, and (vi) at least one wetting agent. Aqueous formulations containing Includes.

[0531] In one further embodiment, the present invention provides a kit for printing in an indirect printing system, the kit is a. Intermediate transfer member including the surface of the release layer, b. Aqueous treated compound, At least one water-soluble polymer, A carrier liquid containing water, and Optionally, one or more of the following: (i) at least one surfactant, (ii) at least one water-retaining agent, and (iii) at least one wetting agent. Aqueous treatment formulations including, c. One or more of the following: (i) a cationic emulsion of at least one oxidized polyethylene wax particle material, (ii) a dispersion or emulsion of at least one coating wax particle material, and (iii) a dispersion of at least one thermosetting polymer particle material. Includes.

[0532] Furthermore, in one further embodiment, the present invention provides a kit for printing in an indirect printing system, the kit is a. Intermediate transfer member including the surface of the release layer, b. Aqueous formulations, At least one water-soluble polymer having a solubility of at least 1.5% by weight and at least 5% in water at 25°C, A first nonionic surfactant having a solubility of at least 5% by weight and at least 7% in water at 25°C, A second nonionic, silicone-containing surfactant having solubility in at least 1% water at 25°C, (i) one or more dispersions and / or emulsions of at least one thermoplastic polymer particulate material, and (ii) one or more dispersions of at least one thermosetting polymer particulate material. A carrier liquid containing water, wherein the water constitutes at least about 55% by weight of the aqueous formulation, and Optionally, one or more of the following: (iii) at least one water-retaining agent, and (iv) at least one wetting agent. aqueous formulations containing Includes.

[0533] In one further embodiment, the present invention provides a kit for printing in an indirect printing system, the kit is a. Intermediate transfer member including the surface of the release layer, b. Aqueous formulations, At least one water-soluble polymer having a solubility of at least 1.5% by weight and at least 5% in water at 25°C, A first nonionic surfactant having a solubility in water of at least 5% by weight and at least 7% at 25°C, A second nonionic, silicone-containing surfactant having solubility in at least 1% water at 25°C, A carrier liquid containing water, wherein the water constitutes at least about 55% by weight of the aqueous formulation, and Optionally, one or more of the following: (i) at least one water-retaining agent, and (ii) at least one wetting agent. Aqueous formulations containing, and c. (i) a dispersion or emulsion of at least one thermoplastic polymer particulate material, and (ii) one or more dispersions or emulsions of at least one thermosetting polymer particulate material Includes.

[0534] In another embodiment, the present invention provides a kit for printing in an indirect printing system, the kit is a. Intermediate transfer member including the surface of the release layer, b. Aqueous formulations, At least one water-soluble polymer, (i) one or more dispersions and / or emulsions of at least one thermoplastic polymer particulate material, and (ii) one or more dispersions and / or emulsions of at least one thermosetting polymer particulate material. A carrier liquid containing water, and Optionally, one or more of the following: (iii) at least one surfactant, (iv) at least one water-retaining agent, and (v) at least one wetting agent. Aqueous treatment formulations containing Includes.

[0535] Furthermore, in one further embodiment, the present invention provides a kit for printing in an indirect printing system, the kit is a. Intermediate transfer member including the surface of the release layer, b. Aqueous treated compound, At least one water-soluble polymer, A carrier liquid containing water, and Optionally, one or more of the following: (i) at least one surfactant, (ii) at least one water-retaining agent, and (iii) at least one wetting agent. Aqueous treatment formulations containing, and c. (i) one or more dispersions and / or emulsions of at least one thermoplastic polymer particulate material, and (ii) one or more dispersions and / or emulsions of at least one thermosetting polymer particulate material. Includes.

[0536] In one further embodiment, the present invention is (i) Substrates (e.g., uncoated fiber printing substrates, product-coated fiber printing substrates, and plastic printing substrates), (ii) One or more ink dots that are continuous and can thereby form an ink thin film on the substrate, or which may be spaced apart from each other, Including providing a printable pattern on a substrate, The one or more ink dots are firmly attached to at least one area on the surface of the substrate. The pattern is formed within a defined boundary within the substrate, and so the region surrounding or separating one or more ink dots and the continuous or spaced dots is covered with a substantially dry thin film layer having a thickness of at least about 20 nm and up to about 200 nm (e.g., up to 200 nm, 190 nm, 180 nm, 170 nm, 160 nm, 150 nm, 140 nm, 130 nm, 120 nm, 110 nm, 100 nm, 90 nm, 80 nm, 70 nm, 60 nm, 50 nm, and optionally at least 20 nm or at least 30 nm), wherein the substantially dry thin film layer comprises one or more of (i) at least one thermoplastic polymer particle material, e.g., as disclosed herein, and (ii) at least one thermosetting polymer particle material, e.g., as disclosed herein.

[0537] The dried thin film layer of the printed pattern is formed using a formulation according to several embodiments of the present invention.

[0538] In some embodiments according to the present invention, the substantially dry thin film layer may further comprise at least one water-soluble polymer (optionally, at least one modified polysaccharide as disclosed herein).

[0539] In one further embodiment, the present invention is (i) Base material; (ii) One or more ink dots firmly attached to at least one area of ​​the surface of the substrate We provide printed products, including The one or more ink dots and the at least one region of the surface of the substrate are covered with a substantially dry thin film layer having a thickness of at least about 20 nm and up to about 200 nm, wherein the substantially dry thin film layer comprises one or more of (i) at least one thermoplastic polymer particle material, e.g., as disclosed herein, and (ii) at least one thermosetting polymer particle material, e.g., as disclosed herein.

[0540] In some embodiments according to the present invention, the substrate is selected from the group consisting of uncoated fiber printing substrates, product-coated fiber printing substrates, plastics, polyethylene terephthalate (PET), polyethylene (PE), biaxially oriented polypropylene (BOPP), aluminum, and any combination thereof.

[0541] The dried thin film layer of the printed product is formed using a formulation according to several embodiments of the present invention.

[0542] In some embodiments according to the present invention, non-printed areas in a printed pattern / printed product are covered with a drying treatment formulation according to the present invention. These areas exhibit beneficial mechanical properties such as abrasion resistance and / or scratch resistance. These areas are further characterized by friction coefficient values ​​such as those disclosed and illustrated herein.

[0543] In some embodiments according to the present invention, the average thickness of the ink dots in the printed pattern / printed product is in the range of 100–1,200 nm, 200–1,200 nm, 200–1,000 nm, 100–800 nm, 100–600 nm, 100–500 nm, 100–450 nm, 100–400 nm, 100–350 nm, 100–300 nm, 200–450 nm, 200–400 nm, or 200–350 nm. Sometimes it is at least 150 nm, at least 200 nm, at least 250 nm, at least 300 nm, or at least 350 nm. Sometimes it is within the range of 100–800nm, 100–600nm, 100–500nm, 100–450nm, 100–400nm, 100–350nm, 100–300nm, 200–450nm, 200–400nm, or 200–350nm. Sometimes it has an average thickness or height of up to 5,000nm, up to 4,000nm, up to 3,500nm, up to 3,000nm, up to 2,500nm, or up to 2,000nm. Sometimes it has an average thickness or height of up to 1,800nm, up to 1,500nm, up to 1,200nm, up to 1,000nm, up to 800nm, up to 650nm, up to 500nm, up to 450nm, or up to 400nm.

[0544] In some embodiments according to the present invention, for example, in a printed product and / or printed pattern, the thickness of the drying layer (e.g., covering / in direct contact with the printed ink dots and / or covering / in direct contact with the printing substrate in ink-free areas on the substrate) is substantially the same as the thickness of the ink dots. Sometimes, the drying layer is thinner than the thickness of the ink dots.

[0545] In some embodiments according to the present invention, the substrate is selected from the group consisting of uncoated fiber printing substrates, product-coated fiber printing substrates, and plastic printing substrates.

[0546] In some embodiments according to the present invention, the substrate is paper, optionally selected from the group of papers consisting of bonded paper, uncoated offset paper, coated offset paper, copy paper, newsprint, coated newsprint, free sheet paper, coated free sheet paper, and laser printer paper.

[0547] In some embodiments, in products according to the present invention, the particle material has a particle size (e.g., diameter or longest axis) between about 1 nm and about 500 nm.

[0548] In some embodiments, in products according to the present invention, the particulate material has a substantially two-dimensional disk shape (i.e., the diameter constitutes the longest access point of the particulate material).

[0549] In some embodiments, in a product according to the present invention, the diameter or longest axis of the particle material is substantially parallel to the surface of the substrate.

[0550] In some embodiments, the thickness of the dry thin film layer in a product according to the present invention is up to 200 nm, up to 120 nm, up to 100 nm, up to 80 nm, up to 70 nm, up to 60 nm, up to 50 nm, up to 45 nm, or up to 40 nm.

[0551] In some embodiments, the thickness of the dry thin film layer in the product according to the present invention is at least 15 nm, at least 20 nm, at least 25 nm, or at least 30 nm.

[0552] In some embodiments, the thickness of the dried thin film in the product according to the present invention is approximately 50 nm at most.

[0553] In some embodiments, the thickness of the dried thin film in the product according to the present invention is approximately 100 nm at most.

[0554] In some embodiments, the thickness of the dried thin film in the product according to the present invention is approximately 120 nm at most.

[0555] In some embodiments, the thickness of the dried thin film in the product according to the present invention is approximately 150 nm at most.

[0556] In some embodiments, in a product according to the present invention, the dried thin film is continuous and covers the entire surface of the substrate (for example, covering an area with or without ink dots).

[0557] In some embodiments, in a product according to the present invention, the dry thin film layer covers at least 50%, at least 75%, at least 90%, at least 95%, at least 95%, at least 99%, or 100% of the surface.

[0558] In some embodiments, the thin film layer in a product according to the present invention may further comprise one or more of the following: (i) at least one water-soluble polymer, (ii) at least one surfactant, (iii) at least one water-retaining agent, (iv) at least one wetting agent, and (v) at least one antimicrobial agent.

[0559] In some embodiments, the substantially dry thin film layer in a product according to the present invention may further comprise at least one water-soluble polymer (optionally, at least one modified polysaccharide as disclosed herein).

[0560] In some embodiments, products according to the present invention have one or more improved mechanical properties compared to printed products lacking particulate material.

[0561] In some embodiments, the improved mechanical properties are demonstrated in the region containing the ink on the substrate.

[0562] In some embodiments, the improved mechanical properties are exhibited in areas of the surface of the substrate coated with the substantially dry thin film layer and without ink.

[0563] In some embodiments, the mechanical properties are selected from one or more of the following: abrasion resistance, coefficient of friction, scratch resistance, and surface adhesion.

[0564] In some embodiments of the present invention, the particulate material is embedded in the dry thin film layer without substantially protruding from the surface of the layer, and the surface is distal to the surface of the substrate (i.e., a surface that is not in contact with the substrate and / or ink dots).

[0565] In some embodiments, one or more ink dots form a continuous thin film of ink on the substrate.

[0566] In another embodiment, the present invention provides a printed product / printed pattern manufactured according to the method of the present invention.

[0567] In one further embodiment, the present invention provides an intermediate transfer member (e.g., as disclosed and illustrated herein) including a release layer surface, the surface of which is substantially covered with a substantially dry (treated) continuous thin film (e.g., as disclosed and illustrated herein).

[0568] In some embodiments according to the present invention, the substantially dried (treated) continuous thin film layer has a thickness of at least about 20 nm and a maximum of about 200 nm.

[0569] In some embodiments according to the present invention, the thickness of the substantially dried (treated) continuous thin film layer is up to 200 nm, up to 120 nm, up to 100 nm, up to 80 nm, up to 70 nm, up to 60 nm, up to 50 nm, up to 45 nm, or up to 40 nm.

[0570] In some embodiments according to the present invention, the thickness of the substantially dried (treated) continuous thin film layer is at least 15 nm, or at least 20 nm, or at least 25 nm, or at least 30 nm.

[0571] In some embodiments according to the present invention, the substantially dried (treated) thin film layer comprises (i) at least one thermoplastic polymer particle material, e.g., as disclosed herein, and (ii) at least one thermosetting polymer particle material, e.g., as disclosed herein.

[0572] In some embodiments according to the present invention, a substantially dried (treated) thin film layer covers at least 50%, at least 75%, at least 90%, at least 95%, at least 99%, or 100% of the surface of the ITM's delamination layer.

[0573] In some embodiments according to the present invention, the substantially dried (treated) thin film layer may further comprise one or more of the following: (i) at least one water-soluble polymer, (ii) at least one surfactant, (iii) at least one water-retaining agent, (iv) at least one wetting agent, and (v) at least one antimicrobial agent.

[0574] In some embodiments according to the present invention, the substantially dry thin film layer may further comprise at least one water-soluble polymer (optionally, at least one modified polysaccharide as disclosed herein).

[0575] In some embodiments of the present invention, particulate material is embedded in a substantially dry (treated) thin film layer without substantially protruding from the surface of the layer.

[0576] In some embodiments according to the present invention, a substantially dried (treated) thin film layer is continuous and covers the entire rectangle of the exfoliated surface of the ITM, the rectangle having a width of at least 10 cm and a length of at least 10 m.

[0577] In some embodiments according to the present invention, a substantially dried (treated) thin film layer covers at least 50%, at least 75%, at least 90%, at least 95%, at least 99%, or 100% of a rectangular area, and the thickness of the substantially dried (treated) thin film layer does not deviate by more than 50%, 40%, or 30% from the average thickness value within the rectangle.

[0578] In some embodiments according to the present invention, the ITM is a hydrophobic ITM.

[0579] In some embodiments of the present invention, the release layer surface is a silicone-based release layer surface that is sufficiently hydrophilic to satisfy at least one of the following properties: (i) The receding contact angle of distilled water droplets adhering to the surface of the silicone-based release layer is a maximum of 60°, and (ii) The 10-second dynamic contact angle (DCA) of distilled water droplets adhering to the surface of the silicone release layer is a maximum of 108°.

[0580] Provided below in this specification are some non-limiting embodiments of a system according to the present invention.

[0581] As used herein, the terms “receding contact angle” or “RCA” refer to the receding contact angle measured using the Drop Shape Method with a Dataphysics OCA15 Pro Contact Angle measuring device or an equivalent Video-Based Optical Contact Angle Measuring System. The similar terms “advancing contact angle” or “ACA” refer to the advancing contact angle measured in substantially the same manner.

[0582] As used herein, the term “bulk hydrophobicity” is characterized by the receding contact angle of distilled water droplets adhering to the inner surface of the release layer, which is formed by exposing areas of cured silicone material within the release layer.

[0583] As used herein, the terms “image transfer member,” “intermediate transfer member,” or “transfer member” refer to components of a printing system to which ink is first applied by a print head, for example, by an inkjet head, and the ejected image is then transferred to another substrate or a set of substrates, typically the final printing substrate.

[0584] As used herein, the term “blanket” refers to a flexible transfer member that can be mounted in a printing apparatus to form a belt-like structure on two or more rollers, wherein at least one of the two or more rollers is capable of rotating or moving the blanket (for example, by moving its belt) so that it moves around the roller.

[0585] In this specification, the terms “blanket,” “intermediate transfer member,” and “ITM” are used without distinction and refer to a flexible member comprising a stack of layers used as an intermediate member configured to receive a wet aqueous treatment formulation for receiving an ink image and transferring a dried ink image thin film to a target substrate, as described herein.

[0586] In this specification, when a portion of the ITM is moving at a speed of v meters / second, this means that a portion of the blanket ITM is moving at a speed of at least v meters / second in a direction parallel to its local surface / plane, for example, to a stationary applicator.

[0587] As used herein, the term “static surface tension” refers to the static surface tension at 25°C and atmospheric pressure.

[0588] In some embodiments, the term "thickness" of the wetted layer is defined as follows: When a volume vol of material covers the surface area of ​​a surface having an area SA with a wetted layer, the thickness of the wetted layer is considered to be vol / SA.

[0589] In some embodiments, the term “thickness” of a dry thin film is defined as follows: If a volume vol of a material that is x% liquid by weight wets or covers a surface area SA, and all the liquid evaporates and the wet layer becomes a dry thin film, then the thickness of that dry thin film is vol / ρ wet layer (100-x) / (SA·ρ dry layer ) It is thought that, in the formula, ρ wet layer ρ is the specific gravity of the wet layer, dry layer This is the specific gravity of the dry layer.

[0590] As used herein, the term “continuous wet layer” or any linguistic variation thereof refers to a continuous wet layer covering a convex region where there are no exposed subregions within the boundary of the convex region.

[0591] As used herein, the term “continuous thin dry film” or any linguistic variation thereof refers to a continuous dry film that covers a convex region without any interruption within the boundary of the convex region.

[0592] As used herein, the term “adhesive film / tensile strength” refers to a component that remains together when peeled from the surface to which it is attached—that is, when peeled from the surface, the “adhesive film” maintains its structural integrity and peels off like a skin rather than tearing into small pieces.

[0593] In some embodiments, the hygroscopic material may be a liquid hygroscopic material. As used herein, the term “liquid hygroscopic material / material” refers to a hygroscopic material / material that is liquid at at least one temperature in the range of 25°C to 90°C and has a vapor pressure of up to 0.05 ata, and more typically up to 0.02 ata, up to 0.01 ata, or up to 0.003 ata, at 90°C in its pure state. The term “liquid hygroscopic material / material” is particularly intended to refer to materials such as glycerol.

[0594] The terms "hydrophobic" and "hydrophilic" as used herein, and similar terms, may be used in a relative sense, not necessarily in an absolute sense.

[0595] As used herein, the term “(processing) formulation” means that the formulation is for use with an intermediate transfer member of a printing system, i.e., for use in treating the release surface of an ITM with the formulation, as described and illustrated herein.

[0596] Unless otherwise specified, physical properties of a liquid (e.g., a processed compound), such as viscosity and surface tension, refer to those at 25°C.

[0597] Unless otherwise specified, "concentration" refers to w / w-, that is, the weight of each component of a compound per unit of the total weight of the compound.

[0598] In this specification, unless otherwise specified, the "total percent solid" of an aqueous composition is calculated by multiplying the weight of the residue by 100 after complete drying at 25°C and dividing by the weight of the initial aqueous composition.

[0599] In this specification, dot gain refers to the increase in dot size relative to the initial spherical droplet diameter. Dot gain is determined by the ratio of the final dot diameter to the initial dot diameter. It is highly desirable to find a way to increase dot size without increasing droplet volume.

[0600] In some embodiments according to the present invention, the dot gain may be at least 1.3, 1.4, or 1.5, and more typically at least 1.6, 1.7, or at least 1.8, or in the range of 1.5–2.1, 1.5–2.1, 1.6–2.0, or 1.7–2.0. Occasionally, using droplets having a volume of 6.3 picoliters (D=22.9 micrometers) and using various aqueous treatment formulations of the present invention, the resulting dried ink dots were in the diameter range of 40–45 micrometers.

[0601] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as they are generally understood by one of the persons skilled in the art to whom this invention relates. In case of any conflict, this specification, including definitions, shall prevail.

[0602] In the descriptions and claims of this disclosure, each of the verbs “contain,” “include,” and “have,” and their cognates, is used to indicate that the object or plural object of the verb is not necessarily a complete list of members, components, elements, steps, or parts of the object or plural object of the verb. These terms encompass the terms “consist of” and “essentially consist of.”

[0603] In this specification, the singular forms “a,” “an,” and “the” include references to the plural form and mean “at least one” or “one or more” unless otherwise explicitly indicated.

[0604] Unless otherwise specified, the use of the expression "and / or" between the last two members of a list of options for selection indicates that selecting one or more of the listed options is appropriate and possible.

[0605] As used herein and in subsequent claim sections, the term “ratio” refers to a weight ratio unless otherwise indicated.

[0606] In this disclosure, unless otherwise specified, adjectives such as “substantially” and “about” that modify the state or relational characteristics of any or more features of the embodiments of the Art should be understood to mean that the state or characteristic is defined as being within an acceptable range for the implementation of the embodiment for its intended use. Sometimes, the term “about” indicates ±10% of the value it refers to.

[0607] While this disclosure describes certain embodiments and generally related methods, modifications and substitutions of embodiments and methods will be apparent to those skilled in the art. Furthermore, various embodiments detailed herein in relation to specific aspects may be applicable to all and / or other aspects of the present invention.

[0608] Detailed description of the embodiment The following examples are not intended in any way to limit the scope of the invention as claimed.

[0609] example Herein, along with the above description, refer to the following examples that illustrate the present invention in a non-limiting manner.

[0610] A. Typical ITM (banquet) delamination layer List of materials used: [Table 1]

[0611] The carrier used as a base material in the manufacture of the release layer surface includes an antistatic polyester film (Examples 1-7).

[0612] Example 1 The ITM delamination layer in Example 1 had the following composition (wt. / wt.): [Table 2]

[0613] The release layer was substantially prepared as described in the blanket preparation procedure provided below.

[0614] Blanket preparation procedure (due to the hardened release layer on the carrier surface) All components of the release layer formulation were thoroughly mixed. An initial release layer of the desired thickness was coated onto the PET sheet using a rod / knife (other coating methods may also be used), and then cured at 150°C for 3 minutes. Subsequently, Siloprene LSR 2530 was coated on top of the release layer using a knife to achieve the desired thickness. Then curing was carried out at 150°C for 3 minutes. An additional layer of Siloprene LSR 2530 was then coated on top of the previous (cured) silicone layer, incorporating the glass fiber fabric into this wet, fresh layer so that the wet silicone could penetrate the fibrous structure. Then curing was carried out at 150°C for 3 minutes. Finally, a final layer of Siloprene LSR 2530 was coated onto the glass fiber fabric, and curing was carried out again at 150°C for 3 minutes. The integrated blanket structure was then cooled to room temperature and the PET was removed.

[0615] Example 2 The ITM delamination layer in Example 2 has the following composition. [Table 3]

[0616] The blankets were prepared essentially as described in Example 1.

[0617] Example 3 The ITM delamination layer in Example 3 has the following composition. [Table 4]

[0618] The blankets were prepared essentially as described in Example 1.

[0619] Example 4 The ITM delamination layer in Example 4 has the following composition. [Table 5]

[0620] The blankets were prepared essentially as described in Example 1.

[0621] Example 5 The ITM release layer in Example 5 was prepared from Silopren® LSR 2530 (Momentive Performance Materials Inc., Waterford, New York, USA), a two-component liquid silicone rubber in which two components are mixed in a 1:1 ratio. The blanket was prepared substantially as described in Example 1.

[0622] Example 6 The ITM release layer of Example 6 has substantially the same composition as the ITM release layer of Example 4, but includes SR545 (Momentive Performance Materials Inc., Waterford, New York, USA), a commercially available polar group-containing silicone resin. The polar group is of the "MQ" type, where "M" represents Me3SiO and "Q" represents SiO4. The complete composition is provided below: [Table 6]

[0623] The blankets were prepared essentially as described in Example 1.

[0624] Example 7 The ITM release layer of Example 7 has substantially the same composition as the ITM release layer of Example 6, but contains polymer RV5000, which comprises a vinyl functional group polydimethylsiloxane having high-density vinyl groups, as previously described herein. The complete composition is provided below: [Table 7]

[0625] The blankets were prepared essentially as described in Example 1.

[0626] B. Aqueous treated formulations The list of materials used for the process is as follows: [Table 8]

[0627] Examples 8A-8B - Comparative Examples - Formulations containing PVA The following aqueous formulations were first prepared by preparing a stock solution of 15% PVA and 25% Loxanol P. The other components were then mixed for the final formulation in the weight percentages listed. Water was added to reach the desired solids content, and the mixture was stirred at room temperature for several minutes.

[0628] Formulation 8A is a "PVA formulation," while formulation 8B is a "high-concentration PVA" formulation. [Table 9]

[0629] Formulations 8A and 8B were then applied to the indirect printing apparatus described herein, specifically onto the surface of the ITM. The formulations were applied to a thickness of at least 150 μm (e.g., 150–200 μm, e.g., at least 200 μm). The remaining standard indirect printing process steps were then applied, including inkjet printing of the ink image and drying the formulation and ink image to provide a thin film. However, transfer to plastic using the processed formulation described in 8A resulted in the dried processed formulation cracking during the transfer. It should be noted that no such cracking was observed with similar formulations using Methocel instead of PVA.

[0630] In an attempt to solve this problem, many formulations were formulated and evaluated. Formulation 8B is one example that employs a higher concentration of PVA. Formulation 8B consistently showed no tearing without affecting print quality, but a new problem arose at the edges of the treated layer, where it could not be separated at the edges, as seen in Figure 6. It should be noted that this failure was not observed in similar formulations that used Methocel instead of PVA.

[0631] Transferring a relatively dry, high-quality printed image onto any substrate, such as plastic, without loss of mechanical integrity or tearing of the dried thin film during transfer can be difficult, as described in further detail in Example 8A. Tearing of the dried thin film also leads to the presence of residues that can accumulate on the blanket surface. When the concentration of polyvinyl alcohol in the formulation increases or the thickness of the polyvinyl alcohol-based thin film increases, delamination from the ITM surface does not leave a clean cut at the substrate edges, and the dried aqueous treatment layer cannot be cleanly separated at the substrate edges, as described in Example 8B.

[0632] Specifically, as described below, some embodiments of the present invention relate to compositions, methods, and apparatus that are subsequently heated to form a dry transfer composition particularly suitable for receiving an ink formulation, and can ultimately be transferred to a variety of substrate media, and are particularly useful in the context of plastic media for generating a wet-treated layer of uniform thickness over a wide range of ITMs and / or for high printing speeds.

[0633] Transferring a relatively dry, high-quality printed image onto any substrate, such as plastic, without loss of mechanical integrity or tearing of the dried thin film during transfer can be difficult, as described in further detail in Example 8A. Tearing of the dried thin film also leads to the presence of residues that can accumulate on the blanket surface. When the concentration of polyvinyl alcohol in the formulation increases or the thickness of the polyvinyl alcohol-based thin film increases, delamination from the ITM surface does not leave a clean cut at the substrate edges, and the dried aqueous treatment layer cannot be cleanly separated at the substrate edges, as described in Example 8B.

[0634] In contrast, the formulations and methods of the present invention can be applied to produce ink images characterized by any combination of the following features: uniform and controlled dot gain, good and uniform print gloss, and good image quality resulting from high-quality dots with consistent dot protrusion and / or clearly defined boundaries.

[0635] Example 9 - Formulation containing Methocel The aqueous formulation was first prepared by dissolving Methocel® K3 LV in water to a concentration of 10% by weight. Next, the other components were mixed for the final formulation in the weight percentages listed in the table below. Water was added to reach the desired solids content, and the mixture was stirred at room temperature for several minutes. [Table 10]

[0636] The treated formulations were applied to a silicone-based surface and then dried. They were then magnified and photographed using a wide-stand microscope. In Figure 7A, the dried sample of formulation 8A showed greater consistency in both the number of holes visible in the field of view and the varying thickness of the layers. Figure 7B, using formulation 9, shows a more uniform layer, as evidenced by reduced interruptions in the continuity of the layers and improved uniformity in thickness.

[0637] The treated formulations were also tested in indirect printing for ink image quality and printing on plastic. The same method was employed, except for the treated formulations, and the resulting ink images are shown in Figures 8A and 9A (using formulation 8A) and Figures 8B and 9B (using formulation 9). Note that Figures 8A and 9A have lower print quality in the form of erased areas compared to Figures 8B and 9B.

[0638] Example 10-12-Methocel formulation The aqueous formulation was first prepared by dissolving Methocel® K3 LV in water to a concentration of 10% by weight. Next, the other components were mixed for the final formulation in the weight percentages shown in the table below. Water was added to reach the desired solid content, and the mixture was stirred at room temperature for several minutes. [Table 11]

[0639] Next, each of formulations 10 to 12 was applied to the indirect printing apparatus described herein. Printing on plastic resulted in high-quality images without tearing during transfer. A photograph of the image resulting from the use of the treated formulation in Example 11 is shown in Figure 10. Note that although no surfactant was used, the photograph has reduced blemish and high quality.

[0640] C. Exemplary ink composition Pigment preparation The pigments used in the examples described below are generally supplied with an initial particle size of several micrometers. Such pigments were ground to the submicron range in the presence of a dispersant, and the two materials were fed as an aqueous mixture into a pulverizer (bead mill). The progress of pulverization was controlled based on particle size measurement (e.g., Malvern or Nanosizer instrument). Pulverization was stopped when the average particle size (dv50) reached 70–100 nm.

[0641] In this example, the preparation of the ink composition is described: As described, Heliogen® Blue D7079 was finely ground in Disperbyk® 190 and the materials were mixed in the following proportions: Heliogen® Blue D7079 30g Disperbyk® 190 (40%) 30g 140g water =============================A Total 200g

[0642] The finely ground concentrate at this time has a particle size of less than 100 nm, typically between 70 and 100 nm, D V It contained 50g of pigment, which was further diluted with 50g of water and extracted from a pulverizer at a pigment concentration of approximately 12 wt.%. The millbase concentrate was further processed as described below for the preparation of the ink composition.

[0643] In the first stage, 2.4 g of sodium dodecanoate was added to 200 g of a paste pigment concentrate to obtain a paste pigment. The mixture was stirred until homogeneous (using a magnetic stirrer at 50 rpm for 5 minutes) and incubated at 60°C for 1 day. The mixture was then left to cool to ambient temperature.

[0644] In the second stage, the ink components were added to the paste pigment as follows: Concentrated pigment paste (from stage 1) 202.4g Joncryl(registered trademark) 538 (46.5%) 154.8g BYK(registered trademark)349 5g BYK(registered trademark)333 2g Propylene glycol 240g Water 595.8g ================= Total 1200g

[0645] The mixture was stirred at ambient temperature for 30 minutes to obtain an inkjet-ready ink composition with a viscosity of less than 10 cP.

[0646] D. Processed formulations containing particulate materials Example 13 Preparation of basic aqueous treatment formulations Exemplary basic compositions of aqueous treatment formulations, to be used in conjunction with the present invention and referred to herein as V1, V2, and V3, are provided in Tables 1, 2, and 3, respectively.

[0647] These basic compositions were used as reference compositions, i.e., treatment compositions lacking the particulate material according to the present invention.

[0648] Basic composition V1 was prepared by mixing the components listed in Table 1 below. [Table 12]

[0649] Basic composition V2 was prepared by mixing the components listed in Table 2 below. [Table 13]

[0650] Basic composition V3 was prepared by mixing the components listed in Table 3 below. [Table 14]

[0651] It should be noted that the components of the basic treatment composition according to the present invention can be mixed in any suitable manner to form a composition that can be coated onto an intermediate transfer member. The components can be mixed in any suitable amount. Sometimes, the mixed components form a dispersion. For this purpose, the system of the present invention is configured to provide a mixing means for providing a uniform dispersion of the basic treatment composition. The same applies to the aqueous treatment composition of the present invention (containing particulate material).

[0652] Aqueous treatment formulation containing particulate material additives Various particulate materials were added to the basic treatment compositions listed in Tables 1-3 above.

[0653] Tables 4-6 below show various compositions tested with treated basic formulation V1. Table 4 further shows various compositions tested with treated basic formulation V2 (as indicated in the left column of Table 4). Tables 7-8 below show various compositions tested with treated basic formulations V2 and V3 (as indicated in the left column of Tables 7-8). The tables list the tested print color, additives containing particulate materials, their concentratio...

Claims

1. An aqueous compound for use with an intermediate transfer member in a printing system, At least one modified polysaccharide, At least one water-containing carrier liquid, (i) at least one thermoplastic polymer particle material, (ii) at least one thermosetting polymer particle material, or (iii) a combination thereof, and at least one particle material selected from these, Optionally, one or more of (a) at least one water-retaining agent, (b) at least one surfactant, and (c) at least one wetting agent. Aqueous formulations containing the above.

2. The aqueous formulation according to claim 1, wherein the modified polysaccharide is a cellulose derivative.

3. The aqueous formulation according to claim 2, wherein the cellulose derivative is methylcellulose.

4. The aqueous formulation according to claim 3, wherein the methylcellulose is hydroxypropylmethylcellulose.

5. The aqueous formulation according to any one of claims 1 to 4, wherein the modified polysaccharide is a non-thermoplastic polymer.

6. The aqueous formulation according to any one of claims 1 to 5, wherein the modified polysaccharide includes a charged polysaccharide.

7. The aqueous formulation according to claim 6, wherein the charged polysaccharide is an acidic polysaccharide or comprises an acidic polysaccharide, optionally containing a carboxyl group and / or a sulfate ester group.

8. The aqueous formulation according to claim 6, wherein the charged polysaccharide is a positively charged polysaccharide or contains a positively charged polysaccharide.

9. The aforementioned modified polysaccharide has the following structure: [Formula 1] It has, In the structure, n is an integer greater than or equal to 3. R is selected from the group consisting of H, CH3, CH2COOH, CH2CH(OH)CH3, and CH2CH(OH)CH3, and various R groups are the same or different. The aqueous formulation according to any one of claims 1 to 8.

10. The aqueous formulation according to any one of claims 1 to 9, wherein the modified polysaccharide is methylcellulose, and at least 2% of R is a methyl (CH3) group.

11. The modified polysaccharides described above have the following characteristics: i. Gelation temperature measured at a 2% weight concentration in water or aqueous-treated formulation, between 50°C, or at least 55°C, or at least 57°C, or at least 60°C, or at least 62°C, or at least 65°C, or at least 68°C, or at least 70°C, or at least 75°C, and optionally, between 120°C, 110°C, or 105°C, or 60–120°C, or 60–110°C, or 60–100°C, or 65–110°C, or 65–105°C, or 65–100°C, or 70–110°C, or 70–100°C, or 75–110°C, or 75–100°C, or 80–100°C. ii. Viscosity in mPa·s measured at a 2% weight concentration in water at 25°C, with a maximum of 11, 10, 9, 8, 7, 6, 5, 4, and optionally, at least 0.5, or at least 1, or at least 2, or viscosity within the range of 0.5–10, 1–8, 2–8, 2–5, or 2–4. iii. Hydroxypropyl substitution in amounts of at least 1%, 2%, 4%, 6%, 7% or between 1–30%, 5–25%, 5–20%, 5–10%, 7–9% or 7.3–8.3%, or hydroxypropyl substitution in amounts of at least 0.1, or at least 0.15, or at least 0.2, or between 0.1–1.0, 0.1–0.9, 0.1–0.7 or 0.1–0.3 on a molar basis. iv. In Dalton, the number average molecular weight is up to 13,000 or up to 12,000 or up to 11,000 or up to 10,000 or up to 9,000 or up to 8,000. An aqueous formulation according to any one of claims 1 to 10, having at least one of the following.

12. The aqueous formulation according to claim 11, wherein the modified polysaccharide is a cellulose derivative.

13. The aqueous formulation according to claim 12, wherein the cellulose derivative is methylcellulose.

14. The aqueous formulation according to claim 13, wherein the methylcellulose is HPMC.

15. The aqueous formulation according to any one of claims 1 to 14, wherein the modified polysaccharide is methylcellulose or contains methylcellulose.

16. The methylcellulose described above has the following structural characteristics: i. Hydroxypropyl substitution in amounts of at least 2%, or at least 4%, or at least 6%, or at least 7%, or up to 20%, or up to 15%, or up to 14%, or up to 12%, or between 4–15%, or between 7–12%, ii. Hydroxypropyl molar substitution greater than 0.1, or greater than 0.15, or greater than 0.2, and iii. Number average molecular weight measured in Dalton, up to 13,000 or up to 12,000, or up to 11,000, or up to 10,000, or up to 9,000, or up to 8,000. The aqueous formulation according to claim 15, having at least one of the following.

17. The aqueous formulation according to any one of claims 1 to 16, wherein the modified polysaccharide is methylcellulose having less than 25% or in the range of 15 to 25% methoxyl substitution.

18. The aqueous formulation according to any one of claims 1 to 17, wherein the modified polysaccharide is methylcellulose having hydroxypropyl substitutions in the range of 7 to 12%.

19. The aqueous formulation according to any one of claims 1 to 18, wherein the modified polysaccharide has a solubility in water or an aqueous formulation of at least 1.5%, at least 2%, at least 3%, at least 4%, at least 5%, at least 7%, at least 8%, or at least 10% by weight at 25°C.

20. The aqueous formulation according to any one of claims 11 to 19, wherein the gelation temperature measured at a 2% weight concentration in water is at least 50°C.

21. The aqueous formulation according to any one of claims 11 to 20, wherein the viscosity at mPa·s, measured at a 2% weight concentration in water at 25°C, is a maximum of 11.

22. The aqueous formulation according to any one of claims 1 to 21, further comprising at least one wetting agent.

23. The aqueous formulation according to claim 22, wherein the wetting agent is polyethyleneimine.

24. The aqueous formulation according to claim 23, wherein the ratio of the modified polysaccharide to polyethyleneimine is in the range of 4:1 to 200:1 by weight.

25. The aqueous formulation according to claim 24, wherein the ratio is in the range of 4:1 to 100:

1.

26. The aqueous formulation according to claim 25, wherein the ratio is in the range of 4:1 to 60:

1.

27. The aqueous formulation according to claim 26, wherein the ratio is within the range of 4:1 to 35:

1.

28. The aqueous formulation according to claim 27, wherein the ratio is within the range of 4:1 to 25:

1.

29. The aqueous formulation according to claim 24, wherein the ratio is within the range of 5:1 to 100:

1.

30. The aqueous formulation according to claim 29, wherein the ratio is within the range of 5:1 to 50:

1.

31. The aqueous formulation according to claim 30, wherein the ratio is within the range of 5:1 to 35:

1.

32. The aqueous formulation according to claim 24, wherein the ratio is in the range of 6:1 to 50:

1.

33. The aqueous formulation according to claim 32, wherein the ratio is within the range of 6:1 to 35:

1.

34. The aqueous formulation according to claim 24, wherein the ratio is within the range of 8:1 to 35:

1.

35. The aqueous formulation according to claim 34, wherein the ratio is within the range of 8:1 to 25:

1.

36. The aqueous formulation according to any one of claims 23 to 35, wherein the formulation comprises, by weight, at least 0.05%, at least 0.1%, or at least 0.2%, and optionally, a concentration of polyethyleneimine in the range of up to 1% or up to 0.8%, up to 0.7%, or up to 0.6%, up to 0.5%, or 0.1 to 1%, 0.1 to 0.8%, 0.1 to 0.7%, 0.1 to 0.6%, 0.1 to 0.5%, 0.2 to 0.7%, 0.2 to 0.6%, or 0.2 to 0.5%.

37. The aqueous formulation according to any one of claims 23 to 36, wherein the polyethyleneimine has an average molecular weight of at least 200,000, at least 350,000, at least 500,000, at least 700,000, and optionally, up to 3,000,000, up to 2,500,000, or up to 2,000,000.

38. The aqueous formulation according to any one of claims 23 to 37, wherein the weight ratio of the modified polysaccharide to the polyethyleneimine is 5 to 200:1, or 5 to 50:1, or 7 to 35:1, or 10 to 20:

1.

39. The aqueous formulation according to any one of claims 1 to 38, wherein the formulation comprises at least one carrier liquid containing water, the water constituting at least 50%, at least 55%, at least 60%, or at least 65% by weight of the aqueous treatment formulation.

40. The aqueous formulation according to claim 39, wherein the water constitutes at least 55% by weight of the aqueous treatment formulation.

41. The aqueous formulation according to any one of claims 1 to 40, further comprising at least one surfactant.

42. The aqueous formulation according to claim 41, wherein the surfactant is one or more nonionic surfactants and silicone surfactants.

43. The aqueous formulation according to any one of claims 1 to 42, further comprising a first nonionic surfactant, a silicone surfactant, or both, having a solubility in water of at least 5% by weight or at least 7% at 25°C.

44. The aqueous formulation according to claim 43, wherein the formulation contains, by weight, at least 5%, at least 6%, at least 7%, at least 8%, at least 9%, or at least 10% of the first nonionic surfactant.

45. The aqueous formulation according to claim 43 or 44, wherein the formulation comprises, by weight, up to 18%, up to 16%, up to 15%, up to 14%, or up to 13% of the first nonionic surfactant.

46. The aqueous formulation according to any one of claims 42 to 45, wherein the solubility of the first nonionic surfactant in water at 25°C is at least 8%, at least 10%, at least 12%, at least 15%, at least 20%, at least 25%, or at least 30%, and optionally up to 80% or up to 60%.

47. The aqueous formulation according to claim 42, wherein the nonionic surfactant in the aqueous treatment formulation is in the range of 5.5-18%, 5.5-16%, 6.5-18%, 6.5-16%, 7.5-18%, 7.5-16%, 8.5-18%, 8.5-16%, 9.5-18%, 9.5-16%, 10.5-18%, or 10.5-16% by weight.

48. The aqueous formulation according to any one of claims 42 to 47, wherein the cloud point temperature of the first nonionic surfactant is at least 60°C, at least 70°C, at least 80°C, at least 90°C, at least 100°C, at least 105°C, at least 110°C, at least 115°C, at least 120°C, or at least 130°C, as optionally determined by the ASTM D7689-11 test method.

49. The aqueous formulation according to any one of claims 1 to 48, further comprising a second or the nonionic silicone-containing surfactant.

50. The aqueous formulation according to claim 49, wherein the nonionic silicone-containing surfactant has a solubility in water of at least 1% at 25°C.

51. The aqueous formulation according to claim 49 or 50, wherein the nonionic silicone-containing surfactant is a polysiloxane-polyoxyalkylene copolymer, and optionally the concentration of the polysiloxane-polyoxyalkylene copolymer is at least 0.3%, at least 0.5%, at least 0.75%, or at least 1.0% by weight, and optionally up to 5%, up to 4%, up to 3%, up to 2.5%, up to 2%, or up to 1.75% by weight.

52. The aqueous formulation according to any one of claims 41 to 51, comprising, by weight, at least 5% of a first nonionic surfactant having at least 7% solubility in water at 25°C, and a second nonionic silicone-containing surfactant having at least 1% solubility in water at 25°C.

53. The aqueous formulation according to any one of claims 41 to 52, wherein the aqueous formulation has a total concentration of surfactant in the range of at least 0.3%, at least 0.5%, at least 0.75%, at least 1%, at least 2%, at least 3%, at least 4%, at least 5%, at least 6%, at least 7%, at least 8%, at least 9%, at least 10%, at least 11%, at least 12%, and optionally 6-40%, 6-30%, 6-20%, 7-30%, 7-20%, 7-15%, 8-25%, 8-20%, 8-15%, 8-13%, 9-25%, 9-20%, 9-15%, 9-13%, 10-25%, 10-20%, 10-15%, or 10-13%.

54. The aqueous formulation has the following characteristics: i. Static surface tension in the range of 20 to 40 mN / m at 25℃, ii. A kinematic viscosity at 25°C of at least 10 cP, and iii. Weight-based 60°C evaporation load of up to 7.5:1 An aqueous formulation according to any one of claims 1 to 53, having the following characteristics.

55. The aqueous formulation according to any one of claims 1 to 54, further comprising at least one water-retaining agent, optionally a sugar.

56. The aqueous formulation according to any one of claims 1 to 55, wherein the formulation comprises a modified polysaccharide in an amount of at least 1.5%, 2.0%, 2.5%, or 3% by weight.

57. The aqueous formulation according to any one of claims 1 to 56, wherein the formulation has a static surface tension in the range of 25 to 40 mN / m at 25°C.

58. The aqueous formulation according to any one of claims 1 to 56, wherein the formulation has a kinematic viscosity at 25°C of at least 10 mPa·s, or at least 12 mPa·s, or at least 14 mPa·s, or within the range of 10 mPa·s to 100 mPa·s, 12 to 100 mPa·s, 14 to 100 mPa·s, 10 to 60 mPa·s, or 12 to 40 mPa·s.

59. An aqueous formulation according to any one of claims 1 to 58, further comprising at least one antimicrobial agent.

60. The aqueous formulation according to any one of claims 1 to 59, wherein the particulate material is provided in the form of an emulsion and / or dispersion, and the concentration of the emulsion and / or dispersion in the aqueous formulation is at least about 0.5% and up to about 15% by weight relative to the total weight of the formulation.

61. The aqueous formulation according to any one of claims 1 to 60, wherein the particle material has a particle size between approximately 1 nm and approximately 500 nm.

62. The aqueous formulation according to any one of claims 1 to 61, wherein the particulate material is uniformly dispersed in the aqueous formulation.

63. The aqueous formulation according to any one of claims 1 to 62, wherein the thermosetting polymer particle material is a hydrophobic particle material.

64. The aqueous formulation according to claim 63, wherein the hydrophobic particle material is a polymer selected from polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), or fluorinated ethylene propylene (FEP).

65. The aqueous formulation according to claim 64, wherein the hydrophobic particle material is PTFE.

66. The aqueous formulation according to claim 65, wherein the PTFE particle material has a size between approximately 1 and approximately 500 nm.

67. The aqueous formulation according to claim 66, wherein the PTFE particle material has a size between approximately 50 nm and approximately 200 nm.

68. The aqueous formulation according to any one of claims 64 to 67, wherein the PTFE particle material is approximately 200 nm in size and is provided in the form of a dispersion, and the concentration of the dispersion in the aqueous formulation is between approximately 4% and approximately 12% by weight relative to the total weight of the formulation.

69. The aqueous formulation according to any one of claims 64 to 67, wherein the PTFE particle material is of a size of about 300 nm to about 400 nm and is provided in the form of a dispersion, and the concentration of the dispersion in the aqueous formulation is about 8% by weight relative to the total weight of the formulation.

70. The aforementioned PTFE dispersion has the following properties: i. Viscosity - about 13cP ii.Surface tension - approx. 31.4mN / m iii.pH-about 9.95 iv. Solids content - approximately 60% v. Particle size - about 200nm The aqueous formulation according to claim 68 or 69, which is an aqueous dispersion having the properties of the aqueous compound.

71. The aqueous formulation according to any one of claims 1 to 70, wherein the thermoplastic polymer particle material is a wax particle material.

72. The aqueous formulation according to claim 71, wherein the wax particle material is an oxidized polyethylene wax particle material.

73. The aqueous formulation according to claim 72, wherein the granular oxidized polyethylene wax has a size between approximately 1 nm and approximately 500 nm.

74. The aqueous formulation according to claim 73, wherein the granular oxidized polyethylene wax is of a size of about 1 to about 500 nm and is provided in the form of an emulsion, and the concentration of the emulsion in the aqueous formulation is between about 1.5% and about 5% by weight relative to the total weight of the formulation.

75. The granular oxidized polyethylene wax is an aqueous formulation according to any one of claims 72 to 74, having a glass transition temperature (Tg) of approximately 130°C.

76. The aqueous formulation according to any one of claims 1 to 75, wherein the at least one thermoplastic polymer particle material is provided in the form of an emulsion, and optionally the emulsion is a cationic emulsion.

77. The aqueous formulation according to claim 76, wherein the cationic emulsion is an emulsion of granular oxidized polyethylene wax.

78. The cationic emulsion of granular polyethylene oxide wax has the following properties: i. Viscosity: Approximately 80 cP at -20°C ii. Density - approximately 1 g / cm³ 3 iii. pH - Approximately 9.5 at a concentration of approximately 1% iv. Solids content - approximately 25-29% v. Particle size - less than approximately 500 nm The aqueous formulation according to claim 76 or 77, having the following characteristics.

79. The aqueous formulation according to any one of claims 1 to 75, wherein the thermoplastic polymer particle material is a coating wax particle material.

80. The aqueous formulation according to claim 79, wherein the coating wax particle material is a granular wax material coated with silicon dioxide.

81. The aqueous formulation according to claim 79 or 80, wherein the coating wax particle material is about 100 nm in size and is provided in the form of a dispersion, and the concentration of the dispersion in the aqueous formulation is at least about 10% by weight relative to the total weight of the formulation.

82. The coating wax particle material is an aqueous formulation according to any one of claims 79 to 81, having a glass transition temperature (Tg) value of about 125°C.

83. The aqueous formulation according to any one of claims 1 to 82, wherein the particle material can improve at least one mechanical property of a printed product and / or pattern produced by using the aqueous formulation together with the intermediate transfer member of the printing system, the improvement in the mechanical property being the same as that of the aqueous formulation according to any one of claims 1 to 82, but in comparison to a printed product and / or pattern produced using an aqueous formulation lacking the particle material.

84. The aqueous compound according to claim 83, wherein the aforementioned mechanical property is abrasion resistance.

85. An indirect printing method, a. To provide an intermediate transfer member including a release layer surface. b. To provide the aqueous formulation according to any one of claims 1 to 84, c. Applying the aqueous compound onto the surface of the ITM release layer to form a wet layer having a maximum thickness of approximately 1.0 μm thereon, d. The wet layer is subjected to a drying process to form a dry thin film layer on the surface of the ITM release layer from the wet layer, wherein the dry thin film layer optionally has a thickness of at least about 20 nm and a maximum of about 200 nm. e. Deposition of droplets of aqueous ink onto the dry thin film to form an ink image on the surface of the ITM release layer, f. Optionally, the ink image may be dried to leave ink image residue on the surface of the ITM release layer. g. Transferring the ink image residue onto the printing substrate by pressurized contact between the ITM and the printing substrate. Methods that include...

86. The method according to claim 85, wherein the particle material has a particle size between approximately 1 nm and approximately 500 nm.

87. The method according to claim 86, wherein the particle material has a substantially two-dimensional disk shape, the diameter of which constitutes the longest access point of the particle material.

88. The method according to any one of claims 85 to 87, wherein the diameter or longest axis of the particle material in the dried thin film on the surface of the ITM peeling layer is substantially parallel to the ITM.

89. The method according to any one of claims 85 to 88, wherein the thickness of the dried thin film to which the aqueous ink droplets are attached is a maximum of 200 nm, a maximum of 120 nm, a maximum of 100 nm, a maximum of 80 nm, a maximum of 70 nm, a maximum of 60 nm, a maximum of 50 nm, a maximum of 45 nm, or a maximum of 40 nm.

90. The method according to any one of claims 85 to 89, wherein the thickness of the drying thin film to which the aqueous ink droplets are attached is at least 15 nm, or at least 20 nm, or at least 25 nm, or at least 30 nm.

91. The method according to any one of claims 85 to 90, wherein the thickness of the drying thin film to which the aqueous ink droplets are attached is a maximum of about 50 nm.

92. The method according to any one of claims 85 to 90, wherein the thickness of the drying thin film to which the aqueous ink droplets are attached is a maximum of about 100 nm.

93. The method according to any one of claims 85 to 90, wherein the thickness of the drying thin film to which the aqueous ink droplets are attached is a maximum of approximately 120 nm.

94. The method according to any one of claims 85 to 90, wherein the thickness of the drying thin film to which the aqueous ink droplets are attached is a maximum of about 150 nm.

95. The method according to any one of claims 85 to 94, wherein the dried thin film is continuous and covers the entire rectangle of the peeled surface of the ITM, and the rectangle has a width of at least 10 cm and a length of at least 10 m.

96. The method according to claim 95, wherein the drying treatment thin film covers at least 50%, at least 75%, at least 90%, at least 95%, at least 99%, or 100% of the rectangular area, and the thickness of the drying treatment thin film does not deviate by more than 50%, 40%, or 30% from the average thickness value within the rectangle.

97. The method according to any one of claims 85 to 96, wherein the ink image residue is transferred onto the printing substrate together with the non-printed areas of the dried thin film.

98. The method according to any one of claims 85 to 97, wherein the dried thin film is sufficiently tacky so that during the transfer of the ink image residue, the dried thin film completely separates from the ITM and is transferred to the printing substrate together with the dried ink image in both the printed and non-printed areas.

99. The method according to any one of claims 85 to 98, wherein the ITM is a hydrophobic ITM.

100. The ITM includes a silicone-based release layer surface, and the silicone-based release layer surface has the following characteristics: (i) The receding contact angle of the distilled water droplets adhering to the surface of the silicone-based release layer is a maximum of 60°, and (ii) The 10-second dynamic contact angle (DCA) of distilled water droplets adhering to the surface of the silicone-based release layer is a maximum of 108°. The method according to any one of claims 85 to 99, wherein it is sufficiently hydrophilic to satisfy at least one of the following conditions.

101. The method according to any one of claims 85 to 100, wherein the dry thin film layer has a thickness of at least about 20 nm and a maximum of about 200 nm.

102. The method according to any one of claims 85 to 101, wherein the method provides one or more improved mechanical properties to a printed product and / or pattern, the improvement in the one or more mechanical properties being in comparison to a printed product produced using the method, but lacking the particulate material.

103. The method according to claim 102, wherein the mechanical property is wear resistance.

104. A system for printing, a. An intermediate transfer member including the surface of the release layer, b. The aqueous formulation according to any one of claims 1 to 82, c. A processing station for applying the aqueous formulation to the surface of the ITM and forming a wet layer having a maximum thickness of approximately 1.0 μm thereon, d. An image forming station for forming an ink image on an ITM by adhering droplets of aqueous ink onto the surface of the ITM after the wet layer has dried to become a dry thin film, wherein the dry thin film layer is optionally having a thickness of at least about 20 nm and a maximum of about 200 nm. e. A transfer station for transferring the ink image from the ITM to a substrate. A system that includes these features.

105. The system according to claim 104, wherein the dry thin film layer has a thickness of at least about 20 nm and a maximum of about 200 nm.

106. A printing system, a. An intermediate transfer member including a flexible endless belt mounted on multiple guide rollers, b. An image forming station configured to form an ink image on the surface of the ITM, wherein the first and second guide rollers are positioned upstream and downstream of the image forming station to define an upper run and a lower run passing through the image forming station, c. A printing station through which the lower run of the ITM passes, located downstream of the image forming station, and configured to transfer the ink image from the surface of the ITM to the substrate, d. A processing station located downstream of the printing station and upstream of the image forming station, for forming a uniform thin layer of liquid composition on the ITM surface in its lower run, e. A coating apparatus for coating the ITM with the aqueous treatment compound according to any one of claims 1 to 82, f. A coating thickness adjustment assembly for removing excess liquid to leave only a desired uniform wet thin layer of the formulation, wherein the layer has a maximum thickness of approximately 1.0 μm, and the coating thickness adjustment assembly includes a rounded tip facing the ITM surface in the lower run. Including processing stations and A system that includes these features.

107. The system according to any one of claims 104 to 106, wherein the ITM is a hydrophobic ITM.

108. The ITM includes a silicone-based release layer surface, and the silicone-based release layer surface has the following characteristics: (i) The receding contact angle of the distilled water droplets adhering to the surface of the silicone-based release layer is a maximum of 60°, and (ii) The 10-second dynamic contact angle (DCA) of distilled water droplets adhering to the surface of the silicone-based release layer is a maximum of 108°. The system according to any one of claims 104 to 107, which is sufficiently hydrophilic to satisfy at least one of the following conditions.

109. A method for improving at least one mechanical property of a printed ink image (on a substrate), a. To provide an intermediate transfer member including a release layer surface. b. To provide an aqueous formulation according to any one of claims 1 to 82, c. Applying the aqueous compound onto the surface of the ITM release layer and forming a wet (treated) layer having a maximum thickness of approximately 1.0 μm thereon, d. Optionally, the wetted (treated) layer of (c) is subjected to a drying process to form a dried (treated) thin film layer on the surface of the ITM peel layer, wherein the dried thin film layer optionally has a thickness of at least about 20 nm and a maximum of about 200 nm. e. Deposition of droplets of aqueous ink onto the thin film that has been dried (treated) in the manner described above to form an ink image on the surface of the ITM release layer, f. Drying the ink image to leave ink image residue on the surface of the ITM release layer, g. Transferring the ink image residue onto the printing substrate by pressurized contact between the ITM and the printing substrate. A method comprising, thereby generating a printed ink image on a substrate, wherein the printed ink image is the aqueous formulation but does not contain the particulate material, and has at least one improved mechanical property compared to an ink image generated using the aqueous formulation.

110. The method according to claim 109, wherein the dry thin film layer has a thickness of at least about 20 nm and a maximum of about 200 nm.

111. The method according to claim 109 or 110, wherein the mechanical property is wear resistance.

112. A kit for printing with an indirect printing system, a. An intermediate transfer member including the surface of the release layer, b. The aqueous treatment compound according to any one of claims 1 to 82 A kit that includes this.

113. Printed products, (i) Substrate and (ii) One or more ink dots firmly attached to at least one area of ​​the surface of the substrate, wherein the ink dots are continuous and can form an ink thin film on the substrate, or may be spaced apart from each other. Includes, The one or more ink dots and the at least one region of the surface of the substrate are covered with a substantially dry thin film layer having an optional thickness of at least about 20 nm and up to about 200 nm, wherein the substantially dry thin film layer comprises one or more of (i) at least one thermoplastic polymer particle material and (ii) at least one thermosetting polymer particle material. printed products.

114. The printed product according to claim 113, wherein the substrate is selected from the group consisting of an uncoated fiber printing substrate, a product-coated fiber printing substrate, plastic, polyethylene terephthalate (PET), polyethylene (PE), biaxially oriented polypropylene (BOPP), aluminum, and any combination thereof.

115. The printed product according to claim 114, wherein the substrate is paper, and optionally selected from the group of papers consisting of bonded paper, uncoated offset paper, coated offset paper, copy paper, newsprint, coated newsprint, free sheet paper, coated free sheet paper, and laser printer paper.

116. The printed product according to any one of claims 113 to 115, wherein the particle material has a particle size between approximately 1 nm and approximately 500 nm.

117. The printed product according to any one of claims 113 to 116, wherein the particle material has a substantially two-dimensional disc shape, the diameter of which constitutes the longest access point of the particle material.

118. The printed product according to any one of claims 113 to 117, wherein the diameter or longest axis of the particle material is substantially parallel to the surface of the substrate.

119. The printed product according to any one of claims 113 to 118, wherein the substantially dry thin film layer has a thickness of at least about 20 nm and a maximum of about 200 nm.

120. The printed product according to claim 119, wherein the thickness of the dried thin film layer is a maximum of 200 nm, a maximum of 120 nm, a maximum of 100 nm, a maximum of 80 nm, a maximum of 70 nm, a maximum of 60 nm, a maximum of 50 nm, a maximum of 45 nm, or a maximum of 40 nm.

121. The printed product according to any one of claims 113 to 120, wherein the thickness of the dried thin film layer is at least 15 nm, at least 20 nm, at least 25 nm, or at least 30 nm.

122. The printed product according to any one of claims 113 to 121, wherein the thickness of the dried thin film is a maximum of about 50 nm.

123. The printed product according to any one of claims 113 to 121, wherein the thickness of the dried thin film is a maximum of about 100 nm.

124. The printed product according to any one of claims 113 to 121, wherein the thickness of the dried thin film is a maximum of approximately 120 nm.

125. The printed product according to any one of claims 113 to 121, wherein the thickness of the dried thin film is a maximum of approximately 150 nm.

126. The printed product according to any one of claims 113 to 125, wherein the dried thin film continuously covers the entire surface of the substrate.

127. The printed product according to any one of claims 113 to 126, wherein the dried thin film layer covers at least 50%, at least 75%, at least 90%, at least 95%, at least 95%, at least 99%, or 100% of the surface.

128. The printed product according to any one of claims 113 to 127, wherein the thermosetting polymer particle material is a hydrophobic particle material.

129. The printed product according to claim 128, wherein the hydrophobic particle material is a polymer selected from polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), or fluorinated ethylene propylene (FEP).

130. The printed product according to claim 129, wherein the hydrophobic particle material is PTFE.

131. The printed product according to claim 130, wherein the PTFE particle material has a size between approximately 1 and approximately 500 nm.

132. The printed product according to claim 131, wherein the PTFE particle material has a size between approximately 50 nm and approximately 200 nm.

133. The printed product according to any one of claims 113 to 132, wherein the thermoplastic polymer particle material is a wax particle material.

134. The printed product according to claim 133, wherein the wax particle material is an oxidized polyethylene wax particle material.

135. The printed product according to claim 134, wherein the granular oxidized polyethylene wax has a size between approximately 1 nm and approximately 500 nm.

136. The printed product according to claim 134 or 135, wherein the granular oxidized polyethylene wax has a glass transition temperature (Tg) value of approximately 130°C.

137. The printed product according to any one of claims 113 to 136, wherein the thermoplastic polymer particle material is a coating wax particle material.

138. The printed product according to claim 137, wherein the coating wax particle material is a wax particle material coated with silicon dioxide.

139. The printed product according to claim 138, wherein the coating wax particle material has a size of about 100 nm.

140. The printed product according to claim 138 or 139, wherein the coating wax particle material has a glass transition temperature (Tg) value of about 125°C.

141. The printed product according to any one of claims 113 to 140, wherein the thin film layer further comprises one or more of (i) at least one modified polysaccharide, (ii) at least one surfactant, (iii) at least one water-retaining agent, (iv) at least one wetting agent, and (v) at least one antimicrobial agent.

142. The printed product according to any one of claims 113 to 141, wherein the thin film layer further comprises at least one modified polysaccharide.

143. The printed product according to any one of claims 113 to 142, wherein the product has one or more improved mechanical properties compared to a printed product lacking the particle material.

144. The printed product according to claim 143, wherein the improved mechanical properties are exhibited in the region containing ink on the substrate.

145. The printed product according to claim 143 or 144, wherein the improved mechanical properties are exhibited in the area of ​​the surface of the substrate that is coated with the substantially dry thin film layer and is ink-free.

146. The printed product according to any one of claims 143 to 145, wherein the mechanical properties are selected from one or more of abrasion resistance, coefficient of friction, scratch resistance, and surface adhesion.

147. The printed product according to claim 146, wherein the aforementioned mechanical property is abrasion resistance.

148. The printed product according to claim 146, wherein the aforementioned mechanical property is the coefficient of friction.

149. The printed product according to any one of claims 113 to 148, wherein the particulate material is embedded in the dry thin film layer without substantially protruding from the surface of the layer, and the surface is a surface distal to the surface of the substrate.

150. The printed product according to any one of claims 113 to 149, wherein the one or more ink dots form a continuous thin film of ink on the substrate.

151. A printed product according to any one of claims 113 to 150, manufactured according to the method of any one of claims 85 to 103.

152. An intermediate transfer member including a release layer surface, wherein the surface is substantially covered with a substantially dry continuous thin film layer comprising one or more of (i) at least one thermoplastic polymer particulate material and (ii) at least one thermosetting polymer particulate material, the thickness of the substantially dry continuous thin film layer being at least about 20 nm and up to about 200 nm.

153. The intermediate transfer member according to claim 152, wherein the substantially dry thin film layer covers at least 50%, at least 75%, at least 90%, at least 95%, at least 95%, at least 99%, or 100% of the surface of the intermediate transfer member release layer.

154. The intermediate transfer member according to claim 152 or 153, wherein the substantially dry thin film layer further comprises one or more of (i) at least one modified polysaccharide, (ii) at least one surfactant, (iii) at least one water-retaining agent, (iv) at least one wetting agent, and (v) at least one antimicrobial agent.

155. The intermediate transfer member according to any one of claims 152 to 154, wherein the substantially dry thin film layer further comprises at least one modified polysaccharide.

156. The intermediate transfer member according to any one of claims 152 to 155, wherein the particle material is embedded in the substantially dry thin film layer without substantially protruding from the surface of the layer.

157. The intermediate transfer member according to any one of claims 152 to 156, wherein the intermediate transfer member is a hydrophobic intermediate transfer member.

158. The surface of the release layer is a silicone-based release layer surface, and the silicone-based release layer surface has the following characteristics: (i) The receding contact angle of the distilled water droplets adhering to the surface of the silicone-based release layer is a maximum of 60°, and (ii) The 10-second dynamic contact angle (DCA) of distilled water droplets adhering to the surface of the silicone-based release layer is a maximum of 108°. An intermediate transfer member according to any one of claims 152 to 157, which is sufficiently hydrophilic to satisfy at least one of the following conditions.

Images