Inkjet printing method, ink set for inkjet printing, and inkjet printing device

Abstract

To provide an inkjet printing method which enables formation of an image excellent in image density and wet friction fastness on a fabric.SOLUTION: An inkjet printing method coats first treatment liquid, pigment ink, and second treatment liquid on a fabric in this order by an inkjet head, and coats the first treatment liquid, the pigment ink and the second treatment liquid to the same part in an undried manner, wherein the first treatment liquid makes at least one of the pigment ink and the second treatment liquid remaining on the fabric surface, the first treatment liquid contains a water-soluble cationic coagulant, the second treatment liquid contains a silicone acrylic resin, the pigment ink contains a pigment, an anionic pigment dispersant, anionic resin particles having film elongation of 600 to 1,600%, and a nonionic surface active agent, and a value of a ratio of the nonionic surface active agent to the total amount of the pigment, the anionic pigment dispersant and the anionic resin particles is 0.022 or more and 0.096 or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an inkjet textile printing method, an inkjet textile printing ink set, and an inkjet textile printing apparatus. In particular, the present invention relates to an inkjet textile printing method, an inkjet textile printing ink set, and an inkjet textile printing apparatus that are capable of forming an image on a fabric that has excellent image density and wet rub fastness. [Background technology]

[0002] Conventionally, inkjet textile printing methods using inkjet recording devices (printing devices) have been used as methods for forming images such as letters, pictures, and designs on fabrics such as woven fabrics and nonwoven fabrics (see, for example, Patent Documents 1 to 3). In such inkjet textile printing methods, a pretreatment liquid is typically used to aggregate the pigment ink, thereby retaining the ink on the surface of the fabric, thereby improving color density. Hereinafter, the "pigment ink" used in inkjet textile printing methods will also be simply referred to as "ink."

[0003] Patent Document 1 discloses an inkjet printing method in which a pretreatment liquid, ink, and a posttreatment liquid are ejected onto an object to be printed. The pretreatment liquid contains binder resin particles containing a cationic resin, the ink contains a pigment and an anionic dispersion, and the posttreatment liquid contains a lubricant. As a result, the invention described in Patent Document 1 aims to produce a printed item with excellent image density and wet fastness, and to prevent deterioration in the feel of the printed item.

[0004] D2 describes an inkjet textile printing recording method having a step of applying a pretreatment liquid to a fabric and a step of forming an image. The image-forming step is a step of applying a colored ink composition and a clear ink composition to a fabric while they are both wet. The pretreatment liquid contains a reactant, and the colored ink composition contains a resin that exhibits aggregating properties due to the reactant. The clear ink composition contains a resin that does not exhibit aggregating properties due to the reactant. In this way, the invention described in D2 avoids nozzle clogging and a decrease in ink storage stability that are associated with increased viscosity of the ink composition, and improves the adhesion and color development of the image.

[0005] D3 describes an image forming method (textile printing method) that includes a step of applying ink onto a fabric by an inkjet method and a step of applying a post-treatment liquid onto the ink applied to the fabric. The ink contains a pigment and resin particles, and the post-treatment liquid contains a lubricant. The resin constituting the resin particles and the lubricant each have a specific solubility parameter relationship. This allows the invention described in D3 to maintain high abrasion resistance over a long period of time without impairing the texture of the fabric. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2022-3175 [Patent Document 2] Japanese Patent Application Publication No. 2017-132946 [Patent Document 3] Japanese Patent Application Publication No. 2023-179259 Summary of the Invention [Problem to be solved by the invention]

[0007] However, the above-mentioned conventional textile printing methods have been required to be further improved in terms of image density and wet rub fastness of the resulting printed textiles.

[0008] The present invention has been made in view of the above problems and circumstances, and an object of the present invention is to provide an inkjet textile printing method, an ink set for inkjet textile printing, and an inkjet textile printing apparatus that are capable of forming an image on a fabric that is excellent in image density and wet rub fastness. [Means for solving the problem]

[0009] In order to solve the above-mentioned problems, the present inventors conducted extensive research, focusing on the physical properties and compositions of the pigment ink and treatment liquid. Here, "treatment liquid" is a general term for the first treatment liquid and the second treatment liquid. As a result, the present inventors discovered that by adding anionic resin particles with a specific film elongation to the pigment ink and adding a silicone acrylic resin to the second treatment liquid, it is possible to form an image on fabric that is excellent in wet rub fastness and image density, and thus arrived at the present invention. That is, the above-mentioned problems of the present invention are solved by the following means.

[0010] 1. An inkjet textile printing method comprising ejecting a pigment ink, a first treatment liquid, and a second treatment liquid onto a fabric using an inkjet head in the order of the first treatment liquid, the pigment ink, and the second treatment liquid, and adhering the first treatment liquid, the pigment ink, and the second treatment liquid to the same location without drying, the first treatment liquid is for fixing at least one of the pigment ink and the second treatment liquid on the surface of the fabric, the first treatment liquid contains a water-soluble cationic flocculant, the second treatment liquid contains a silicone acrylic resin, The pigment ink contains a pigment, an anionic pigment dispersant, anionic resin particles having a film elongation of 600 to 1600%, and a nonionic surfactant; an ink-jet printing method, wherein the ratio of the amount of the nonionic surfactant to the total amount of the pigment, the anionic pigment dispersant, and the anionic resin particles is 0.022 or more and 0.096 or less;

[0011] 2. The ink-jet printing method described in item 1, wherein the nonionic surfactant is an acetylene surfactant.

[0012] 3. The ink-jet printing method according to item 1 or 2, wherein the cationic flocculant is a cationic polymer.

[0013] 4. The ink-jet printing method described in item 1 or 2, wherein the pigment ink contains a silicone acrylic resin.

[0014] 5. The anionic pigment dispersant comprises a block copolymer; The block copolymer includes an ABA block copolymer having two hydrophilic blocks A arranged at both ends of the molecule and a hydrophobic block B arranged between the two hydrophilic blocks, 3. The ink-jet printing method according to item 1 or 2, wherein the hydrophilic block A interacts or reacts with the cationic flocculant.

[0015] 6. The ink-jet printing method according to item 1 or 2, wherein the anionic resin particles are made of a urethane resin.

[0016] 7. The ink-jet printing method described in item 1 or 2, wherein the pigment ink contains a crosslinking agent.

[0017] 8. The ink-jet printing method described in item 3, wherein the cationic polymer is a compound having a quaternary ammonium salt group.

[0018] 9. An inkjet printing ink set comprising a pigment ink, a first treatment liquid, and a second treatment liquid, the pigment ink, the first treatment liquid, and the second treatment liquid are ejected onto a recording medium by an inkjet head in this order, and the first treatment liquid, the pigment ink, and the second treatment liquid are adhered to the same location before drying; the first treatment liquid is for fixing at least one of the pigment ink and the second treatment liquid on the surface of the fabric, an anionic pigment dispersant, an anionic resin particle having a film elongation of 600 to 1600%, and a nonionic surfactant; and a ratio of the nonionic surfactant to the total amount of the pigment, the anionic pigment dispersant, and the anionic resin particle is 0.022 or more and 0.096 or less.

[0019] 10. An inkjet unit that ejects pigment ink onto the fabric while scanning in the main scanning direction; a first treatment liquid ejection head that scans together with the inkjet unit in the main scanning direction and ejects a first treatment liquid onto the fabric; a second treatment liquid ejection head that scans together with the inkjet unit in the main scanning direction and ejects the second treatment liquid onto the fabric, the first treatment liquid ejection head and the second treatment liquid ejection head are disposed on both sides of the inkjet unit in the main scanning direction, an inkjet head including the inkjet unit, the ejection head for the first treatment liquid, and the ejection head for the second treatment liquid; the pigment ink, the first treatment liquid, and the second treatment liquid are ejected onto the fabric by an inkjet head in the order of the first treatment liquid, the pigment ink, and the second treatment liquid, so that the first treatment liquid, the pigment ink, and the second treatment liquid are adhered to the same location before drying; the first treatment liquid is for fixing at least one of the pigment ink and the second treatment liquid on the surface of the fabric, an anionic pigment dispersant, an anionic resin particle having a film elongation of 600 to 1600%, and a nonionic surfactant; and a ratio of the nonionic surfactant to the total amount of the pigment, the anionic pigment dispersant, and the anionic resin particle is 0.022 or more and 0.096 or less. [Effects of the Invention]

[0020] The above-described means of the present invention can provide an inkjet textile printing method capable of forming an image on a fabric that is excellent in image density and wet rub fastness, and also provide an inkjet textile printing ink set and an inkjet textile printing apparatus that can be used in such an inkjet textile printing method.

[0021] The mechanism by which the effects of the present invention are manifested or the mechanism of action is not clear, but is speculated as follows.

[0022] By including anionic resin particles with a film elongation of 600 to 1600% in the pigment ink, the coating film deforms so as to elongate even when force is applied to the interface between the fabric and the "coating film formed by printing." Anionic resin particles with a film elongation of 600 to 1600% are relatively soft particles. This is presumably why peeling of the coating film from the fabric is suppressed and wet rubbing fastness is improved. Hereinafter, the "coating film formed by printing" refers to a film formed on the fabric by ejecting the first treatment liquid, pigment ink, and second treatment liquid onto the fabric, and is a film on which an image is formed. Hereinafter, it will also be simply referred to as the "coating film."

[0023] The first treatment liquid, the pigment ink, and the second treatment liquid are ejected onto the fabric in this order. Therefore, first, aggregates are formed by mixing the first treatment liquid and the pigment ink. Then, the second treatment liquid containing a silicone acrylic resin is applied to the formed aggregates. The silicone acrylic resin then spreads onto the fabric surface, carrying the aggregates with it. It is presumed that the aggregates that spread onto the fabric surface fill areas of the fabric where the pigment ink is not attached, thereby improving image density. Furthermore, the silicone acrylic resin spreads onto the fabric surface, carrying the aggregates with it, increasing the contact area between the coating film formed on the fabric and the fabric. Hereinafter, the "contact area between the coating film formed on the fabric and the fabric" may be simply referred to as the "contact area." It is presumed that this increased contact area between the coating film and the fabric improves wet rub fastness. Furthermore, it is presumed that wet rub fastness is improved by the silicone acrylic resin and the anionic resin particles becoming compatible with each other after heating.

[0024] The following effects are presumed to be achieved by setting the ratio of nonionic surfactant to the "total amount of pigment, anionic pigment dispersant, and anionic resin particles" to 0.022 or more and 0.096 or less. Hereinafter, the "ratio of nonionic surfactant to the total amount of pigment, anionic pigment dispersant, and anionic resin particles" is also referred to as the "nonionic surfactant ratio." Setting the nonionic surfactant ratio to 0.022 or more and 0.096 or less is presumed to improve ejectability, i.e., ejectability from an inkjet head, even when anionic resin particles with a film elongation of 600 to 1600% are used. Furthermore, by setting the "ratio of nonionic surfactant" within the above range, the nonionic surfactant does not inhibit ionic bonding between the anionic resin particles and the cationic flocculant, thereby presumably maintaining good wet friction fastness. [Brief explanation of the drawings]

[0025] [Figure 1] FIG. 1 is a schematic diagram illustrating an embodiment of an inkjet textile printing apparatus. [Figure 2]FIG. 2 is a plan view schematically showing an inkjet unit, a first treatment liquid ejection head, and a second treatment liquid ejection head mounted on a carriage. [Figure 3] 4 is a flowchart showing an example of a process for applying a treatment liquid and a pigment ink in the inkjet textile printing method of the present embodiment. [Figure 4] FIG. 1 is a diagram showing a schematic configuration of an inkjet printing apparatus in which a fabric is attached to a conveying belt and conveyed. DETAILED DESCRIPTION OF THE INVENTION

[0026] One embodiment of the inkjet textile printing method of the present invention is an inkjet textile printing method in which a pigment ink, a first treatment liquid, and a second treatment liquid are ejected onto fabric using an inkjet head in the following order: first treatment liquid, pigment ink, second treatment liquid. The inkjet textile printing method of this embodiment is an inkjet textile printing method in which the first treatment liquid, pigment ink, and second treatment liquid are applied to the same location without drying. Hereinafter, the inkjet textile printing method will also be simply referred to as the "textile printing method."

[0027] In the textile printing method of this embodiment, the first treatment liquid is used to retain at least one of the pigment ink and the second treatment liquid on the fabric surface. It is preferable that the first treatment liquid retains at least the pigment ink on the fabric surface. The first treatment liquid contains a water-soluble cationic flocculant, and the second treatment liquid contains a silicone acrylic resin. The pigment ink contains a pigment, an anionic pigment dispersant, "anionic resin particles having a film elongation of 600 to 1600%," and a nonionic surfactant. Furthermore, the ratio of the nonionic surfactant to the "total amount of the pigment, anionic pigment dispersant, and anionic resin particles" is 0.022 or more and 0.096 or less. This feature is a technical feature common to or corresponding to each of the following embodiments.

[0028] According to the textile printing method of this embodiment, an image with excellent image density and wet rub fastness can be formed on a fabric. That is, as described above, the first treatment liquid, the pigment ink, and the second treatment liquid are ejected onto the fabric in this order. Therefore, first, aggregates are formed by mixing the first treatment liquid and the pigment ink. Then, the second treatment liquid containing a silicone acrylic resin is applied to the formed aggregates. The silicone acrylic resin then spreads onto the fabric surface, wetting it along with the aggregates. The aggregates that spread on the fabric surface fill in areas of the fabric where the pigment ink is not attached, allowing an image with excellent image density to be formed on the fabric. Furthermore, as described above, the pigment ink contains anionic resin particles with a film elongation of 600 to 1600%, so that the coating film stretches and deforms even when force is applied to the interface between the fabric and the "coating film formed by textile printing." Therefore, peeling of the coating film from the fabric is suppressed, and an image with excellent wet rub fastness can be formed on the fabric. Furthermore, as described above, the silicone acrylic resin wets and spreads on the fabric surface, accompanied by aggregates, thereby increasing the contact area between the coating film formed on the fabric and the fabric. This increased contact area between the coating film and the fabric allows an image with excellent wet rub fastness to be formed on the fabric. Furthermore, the silicone acrylic resin and the anionic resin particles become compatible after heating, allowing an image with excellent wet rub fastness to be formed on the fabric. Furthermore, as described above, by setting the "nonionic surfactant ratio value" to 0.022 or more and 0.096 or less, ejection performance from an inkjet head can be improved even when anionic resin particles with a film elongation of 600 to 1600% are used. Furthermore, by setting the "ratio of nonionic surfactants" to 0.022 or more and 0.096 or less, the ionic bonding between anionic resin particles and cationic flocculants is not inhibited, and an image with excellent wet friction fastness can be formed on the fabric.

[0029] In the textile printing method of this embodiment, the nonionic surfactant is preferably an acetylene-based surfactant. This configuration has the advantage of improving ejection properties (ejection from an inkjet head) and forming an image on a fabric with excellent image density and wet friction fastness. This is thought to be because the particles have good re-adsorption even after ejection, so the fabric is filled with the surfactant by wetting and spreading in the X and Y directions, improving density. Furthermore, the increased contact area between the fabric and the coating film is thought to improve wet friction.

[0030] In the textile printing method of this embodiment, the cationic flocculant is preferably a cationic polymer. This configuration has the advantage of enabling the formation of an image on the fabric with excellent image density and wet rub fastness. If the cationic property is too strong, wetting and spreading in the X and Y directions may be suppressed, resulting in a deterioration in density and wet rub fastness. If the cationic property is too weak, the ink may easily penetrate in the Z direction. However, if the cationic property is a polymer, a certain degree of aggregate diameter is easily formed, which is thought to improve image density.

[0031] In the textile printing method of this embodiment, the pigment ink preferably contains a silicone acrylic resin. This configuration has the advantage of enabling the formation of an image on fabric with excellent image density and wet rub fastness. This is thought to be because the ink maintains wet spread in the X and Y directions even after injection, filling the fabric and improving density, and increasing the contact area between the fabric and the coating film, thereby improving wet rub fastness. Furthermore, it is thought that the silicone acrylic resin particles and the anionic resin particles become compatible after heating, thereby improving wet rub fastness.

[0032] The anionic pigment dispersant preferably contains a block copolymer, an ABA block copolymer consisting of two hydrophilic blocks A at both ends of the molecule and a hydrophobic block B located between the two hydrophilic blocks, and the hydrophilic block A interacts or reacts with the cationic flocculant. This configuration offers the advantage of enabling the formation of images on fabrics with excellent image density and wet rub fastness. This is because the block contains many sites that interact or react with the flocculant, making it easier for interaction or reaction with the flocculant to occur, resulting in higher wet rub fastness.

[0033] In the textile printing method of this embodiment, the anionic resin particles are preferably urethane resin. This configuration has the advantage of enabling the formation of an image on fabric with excellent image density and wet rub fastness. This is because polyurethane resins have excellent adhesion to substrates and high wet rub fastness. Furthermore, it is preferable that the average particle size of the resin particles be 130 nm or less. This allows the formation of a coating film that fills the gaps between the pigment and the media, and between the pigments, thereby achieving even higher wet rub fastness.

[0034] It is more preferable that the pigment ink contains a crosslinking agent. This composition has the advantage of enabling the formation of an image on fabric with superior image density and wet rub fastness. This is because crosslinking reactions between crosslinking agents, crosslinking reactions with resin particles and dispersants contained in the ink composition, and crosslinking reactions with reactive sites such as hydroxyl groups in the fabric proceed, improving the wet rub fastness of the printed material.

[0035] The cationic polymer is preferably a compound having a quaternary ammonium salt group. The compound is a polymer. This configuration has the advantage of enabling the formation of an image on the fabric with superior image density and wet rub fastness. Furthermore, if the cationic polymer has less than quaternary salt groups, the fabric may turn yellow during heat drying.

[0036] Next, one embodiment of the inkjet printing ink set of the present invention is an inkjet printing ink set containing a pigment ink, a first treatment liquid, and a second treatment liquid. Hereinafter, this may be simply referred to as the "ink set." The ink set of this embodiment is used in inkjet printing, in which the pigment ink, the first treatment liquid, and the second treatment liquid are ejected onto fabric from an inkjet head in the order of first treatment liquid, pigment ink, and second treatment liquid. The ink set is used in inkjet printing, in which the first treatment liquid, pigment ink, and second treatment liquid are applied to the same location before drying. Here, the first treatment liquid serves to retain at least one of the pigment ink and the second treatment liquid on the fabric surface. Treatment liquid 1 contains a water-soluble cationic flocculant, and treatment liquid 2 contains a silicone acrylic resin. The pigment ink contains a pigment, an anionic pigment dispersant, "anionic resin particles having a film elongation of 600 to 1600%," and a nonionic surfactant. Furthermore, the ratio of the nonionic surfactant to the "total amount of pigment, anionic pigment dispersant, and anionic resin particles" is 0.022 or more and 0.096 or less. By configuring the ink set in this manner, the effects of the textile printing method of this embodiment can be obtained when used in the textile printing method of this embodiment.

[0037] Next, one embodiment of the inkjet textile printing apparatus of the present invention includes an inkjet unit, a discharge head for a first treatment liquid, and a discharge head for a second treatment liquid. The inkjet unit is a unit that discharges pigment ink onto fabric while scanning in the main scanning direction. The discharge head for the first treatment liquid is a discharge head that scans together with the inkjet unit in the main scanning direction and discharges the first treatment liquid onto the fabric. The discharge head for the second treatment liquid is a discharge head that scans together with the inkjet unit in the main scanning direction and discharges the second treatment liquid onto the fabric. The discharge head for the first treatment liquid and the discharge head for the second treatment liquid are disposed on both sides of the inkjet unit in the main scanning direction. The inkjet textile printing apparatus of this embodiment includes an inkjet head that has an inkjet unit, a discharge head for the first treatment liquid, and a discharge head for the second treatment liquid. The inkjet textile printing apparatus of this embodiment discharges the pigment ink, the first treatment liquid, and the second treatment liquid onto the fabric using the inkjet head in the order of the first treatment liquid, the pigment ink, and the second treatment liquid. The first treatment liquid, pigment ink, and second treatment liquid are then applied to the same location while still wet. The first treatment liquid is used to retain at least one of the pigment ink and the second treatment liquid on the fabric surface. The first treatment liquid contains a water-soluble cationic coagulant, and the second treatment liquid contains a silicone acrylic resin. The pigment ink contains a pigment, an anionic pigment dispersant, anionic resin particles with a film elongation of 600 to 1600%, and a nonionic surfactant. The ratio of the nonionic surfactant to the "total amount of pigment, anionic pigment dispersant, and anionic resin particles" is 0.022 or more and 0.096 or less. By configuring the inkjet textile printing device in this manner, the effects of the textile printing method of this embodiment can be obtained when used in the textile printing method of this embodiment.

[0038] The present invention, its components, and modes and aspects for carrying out the present invention will be described in detail below. In this application, the symbol "to" indicating a range of values ​​is used to mean that the values ​​before and after it are included as the lower limit and upper limit.

[0039] [Inkjet printing method] Next, the inkjet printing method of this embodiment will be described in more detail. The printing method of this embodiment is a printing method in which a first treatment liquid, a second treatment liquid, and a pigment ink are applied using an inkjet head. Hereinafter, the first treatment liquid and the second treatment liquid may be collectively referred to simply as "treatment liquids."

[0040] As described above, the inkjet printing method of this embodiment is a printing method in which the first treatment liquid, pigment ink, and second treatment liquid are ejected onto fabric in this order using an inkjet head, and the first treatment liquid, pigment ink, and second treatment liquid are adhered to the same location before drying. The method is characterized by the pigment ink, first treatment liquid, and second treatment liquid.

[0041] The steps of applying the treatment liquid and the pigment ink include, for example, a first treatment liquid application step S01, a pigment ink application step S02, and a second treatment liquid application step S03, as shown in the flowchart of FIG. 3. Here, the first treatment liquid application step is a step of ejecting and adhering a first treatment liquid to the fabric. The second treatment liquid application step is a step of ejecting and adhering a second treatment liquid to the fabric. The pigment ink application step is a step of ejecting and adhering a pigment ink to the fabric. Thereafter, a fabric transport step S04 is performed in which the fabric is transported in the transport direction Y, and then the above steps S01, S02, S03, and S04 are repeated to form an image on the fabric. Here, FIG. 3 is a flowchart showing an example of the steps of applying the treatment liquid and the pigment ink in the inkjet printing method of this embodiment.

[0042] The first treatment liquid, the second treatment liquid, the pigment ink, and the like used in the textile printing method of this embodiment will be described below.

[0043] <First processing liquid> The first treatment liquid contains a water-soluble cationic flocculant.

[0044] (Water-soluble cationic flocculant) Water-soluble cationic flocculants aggregate pigments and other particles contained in ink. Aggregation by water-soluble cationic flocculants utilizes electrical action. Hereinafter, water-soluble cationic flocculants may also be simply referred to as cationic flocculants.

[0045] Cationic flocculants that cause aggregation by electrical action include compounds having cationic groups and polyvalent metal salts. These cationic flocculants can interact or react with the anionic pigment dispersant contained in the pigment ink.

[0046] Examples of the cationic group in the compound having a cationic group include a secondary amino group, a tertiary amino group, and a quaternary ammonium base. Examples of the compound having a cationic group include a cationic resin and a cationic surfactant, and preferably a cationic resin. A cationic resin can also be called a cationic polymer.

[0047] Examples of cationic resins include cationic urethane resins, cationic olefin resins, and cationic alkylamine resins. Examples of commercially available products include MPT-60 (manufactured by Mitsubishi Pencil Co., Ltd.), Unisense KHE100L (manufactured by Senka Co., Ltd.), and MZ477 (urethane resin, manufactured by Takamatsu Oil & Fat Co., Ltd.). Among these, cationic alkylamine resins MPT-60 and Unisense KHE100L (manufactured by Senka Co., Ltd.) are preferred as cationic resins. This makes it easier for the cationic resin to interact or react with the block copolymer.

[0048] Polyvalent metal salts can be water-soluble compounds having a divalent or higher polyvalent metal ion and an associated anion. Examples of polyvalent metal ions include Ca 2+ , Cu 2+ , Ni 2+ , Mg 2+ , Zn 2+ , Ba 2+ Divalent metal ions such as Al 3+ , Fe 3+ , Cr 3+ Examples of anions include trivalent metal ions such as Cl- , I - , Br - , SO4 2- , ClO 3- , NO 3- , and HCOO - , CH3COO - Examples of such polyvalent metal salts include metal salts of organic acids such as calcium salts, magnesium salts, nickel salts, and aluminum salts, such as zinc acetate dihydrate, magnesium nitrate, calcium chloride, magnesium chloride, aluminum chloride, magnesium sulfate, and acetic acid. Of these, calcium salts and magnesium salts are preferred, and calcium nitrate and calcium chloride are more preferred.

[0049] Among these, compounds having a cationic group or organic acids are preferred, and compounds having a cationic group are more preferred.

[0050] The content of the cationic flocculant in the first treatment liquid is not particularly limited, but is preferably 0.1 to 15% by mass, and more preferably 0.5 to 8% by mass, relative to the first treatment liquid.

[0051] <Second processing liquid> The second treatment liquid contains a silicone acrylic resin.

[0052] (Silicone acrylic resin) The silicone acrylic resin is a silicone acrylic resin that exists in a dispersed state as resin particles in an aqueous medium. The second treatment liquid is an aqueous treatment liquid containing water and any water-soluble organic solvent. Therefore, the silicone acrylic resin is also contained as resin particles in the second treatment liquid. Whether the silicone acrylic resin exists as resin particles can be confirmed by whether or not a peak corresponding to the silicone acrylic resin is present when the dispersed particle size (Z average) of the second treatment liquid is measured using a particle size measuring device. An example of a particle size measuring device is the "Zataizer Nano S90" manufactured by Melvern.

[0053] The silicone acrylic resin is a copolymer containing structural units derived from polyorganosiloxane and structural units derived from other polymerizable monomers (including macromonomers) copolymerizable therewith.

[0054] The copolymer may be, for example, a graft copolymer in which a structural unit derived from polyorganosiloxane is graft-polymerized with a polymerizable monomer such as a (meth)acrylic acid ester. The copolymer may also be, for example, a copolymer in which the side chains or ends of a (meth)acrylic resin or the like are modified with a polyorganosiloxane. Among these, a graft copolymer in which a (meth)acrylic acid ester or the like is graft-polymerized with a polymer containing a structural unit derived from polyorganosiloxane is preferred. Such a graft copolymer has a structure in which the polyorganosiloxane portion forms the trunk and the (meth)acrylic acid ester or the like forms the branches, making it more compatible with the binder resin contained in the ink layer and therefore preferred. The form of copolymerization is not limited to graft copolymerization, and may be random copolymerization or block copolymerization.

[0055] The silicone acrylic resin may also have an ionic group. The ionic group of the silicone acrylic resin may be an ionic group that forms a pair with the ionic group of the fabric (or the ionic group of the flocculant attached to the fabric). For example, since cationic flocculants usually have cationic groups, the silicone acrylic resin may be an anionic silicone acrylic resin that has an anionic group. Examples of the anionic group include a carboxy group, a sulfonic acid group, and a phosphonic acid group.

[0056] That is, the silicone acrylic resin preferably contains a structural unit derived from a polyorganosiloxane having a radical polymerizable group and a structural unit derived from another polymerizable monomer copolymerizable therewith.

[0057] Examples of polyorganosiloxanes having a radical polymerizable group include polyorganosiloxanes represented by the following formula (1).

[0058] [ka]

[0059] In the above formula (1), R 1 , R 2 and R 3 are each independently a hydrocarbon group having 1 to 10 carbon atoms.

[0060] In the above formula (1), Y is a radical polymerizable group selected from the group consisting of a vinyl group, an allyl group, and a γ-(meth)acryloxypropyl group.

[0061] In the above formula (1), X 1 and X 2 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group represented by the formula (2): SiR 4 R 5 R 6 It is a group represented by the formula: m is an integer of 1 to 10000. n is an integer of 1 or more. The siloxane chain may be branched.

[0062] In addition, the above formula (2): SiR 4 R 5 R 6 In R 4 and R 5 are each independently a hydrocarbon group having 1 to 10 carbon atoms. 6 is a radical polymerizable group selected from the group consisting of a vinyl group, an allyl group, and a γ-(meth)acryloxypropyl group, or a hydrocarbon group having 1 to 10 carbon atoms.

[0063] Other polymerizable monomers include (meth)acrylic acid esters. In this specification, (meth)acrylic refers to acrylic, methacrylic, or both.

[0064] The (meth)acrylic acid ester is an alkyl ester, hydroxyalkyl ester, or alkoxyalkyl ester of (meth)acrylic acid. Examples of the (meth)acrylic acid ester include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate. Other examples of the (meth)acrylic acid ester include 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2-methoxyethyl (meth)acrylate. Among these, methyl methacrylate and 2-hydroxyethyl methacrylate are preferred.

[0065] The content of structural units derived from polyorganosiloxane in the silicone acrylic resin is preferably 50% by mass or more, more preferably 60% by mass or more and 95% by mass or less, based on the total amount of structural units constituting the silicone resin. When the content of structural units derived from polyorganosiloxane is 50% by mass or more, the effect of reducing the friction coefficient derived from polysiloxane is more easily achieved, and wet rubbing fastness can be further improved. When the content of structural units derived from polyorganosiloxane is 95% by mass or less, affinity with other compounds and other resins is more likely to be improved.

[0066] The silicone acrylic resin may further contain structural units derived from other polymerizable monomers than those mentioned above. Examples of other polymerizable monomers than those mentioned above include ethylenically unsaturated carboxylic acids such as (meth)acrylic acid, styrenes, etc. For example, from the viewpoint of exhibiting anionic properties, the silicone acrylic resin may further contain structural units derived from ethylenically unsaturated carboxylic acids such as (meth)acrylic acid.

[0067] The graft copolymerization can be carried out by a known method, for example, by emulsifying and dispersing the polyorganosiloxane represented by the above formula (1) and a copolymerizable compound such as a (meth)acrylic acid ester in water, and polymerizing them in the presence of a radical polymerization initiator.

[0068] Examples of commercially available silicone (meth)acrylic copolymers include Charine LC190, Charine R-170, R170S, Charine FE-230N, FE-502, and R-170BX (manufactured by Nissin Chemical Industry Co., Ltd.).

[0069] The second treatment liquid contains the silicone acrylic resin described above, but if, for example, the amount of surfactant is increased in place of the silicone acrylic resin in the second treatment liquid, the ionic bond between anions and cations may be inhibited, resulting in poor wet friction. Furthermore, if the amount of surfactant is increased, the surface friction coefficient may also increase, resulting in poor dry friction.

[0070] There are no particular restrictions on the content of the silicone acrylic resin in the second treatment liquid. For example, the content of the silicone acrylic resin in the second treatment liquid is preferably 0.1 to 2.0% by mass, and more preferably 0.3 to 1.0% by mass, relative to the second treatment liquid. If it is less than 0.1% by mass, it may be difficult to obtain the effects of the silicone acrylic resin. If it is more than 2.0% by mass, wet rub fastness may be impaired.

[0071] <Pigment ink> The pigment ink contains a pigment, an anionic pigment dispersant, anionic resin particles with a film elongation of 600 to 1600%, and a nonionic surfactant. The pigment ink preferably also contains water. Furthermore, the ratio of the nonionic surfactant (by mass) to the "total amount (by mass) of the pigment, anionic pigment dispersant, and anionic resin particles" is 0.022 or more and 0.096 or less.

[0072] (pigment) The pigment is not particularly limited, but examples thereof include organic pigments or inorganic pigments having the following numbers listed in the Color Index.

[0073] Examples of red or magenta pigments include Pigment Red 3, 5, 19, 22, 31, 38, 43, 48:1, 48:2, 48:3, 48:4, 48:5, 49:1, 53:1, 57:1, 57:2, 58:4, 63:1, 81, 81:1, 81:2, 81:3, 81:4, 88, 104, 108, 112, 122, 123, 144, 146, 149, 166, 168, 169, 170, 177, 178, 179, 184, 185, 208, 216, 226, 254, and 257; Pigment Violet 3, 19, 23, 29, 30, 37, 50, and 88; and Pigment Orange. 13, 16, 20, 34, 36, and 43. The red or magenta pigment may be a mixed crystal.

[0074] Examples of blue or cyan pigments include Pigment Blue 1, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17-1, 22, 27, 28, 29, 36, 60.

[0075] Examples of green pigments include Pigment Green 7, 26, 36, and 50.

[0076] Examples of yellow pigments include Pigment Yellow 1, 3, 12, 13, 14, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, 137, 138, 139, 153, 154, 155, 157, 166, 167, 168, 180, 185, and 193.

[0077] Examples of black pigments include Pigment Black 7, 28, and 26.

[0078] Commercially available examples of pigments include Cromofine Yellow 2080, 5900, 5930, AF-1300, 2700L, Cromofine Orange 3700L, 6730, Cromofine Scarlet 6750, Cromofine Magenta 6880, 6886, 6891N, 6790, 6887, Cromofine Violet RE, Cromofine Red 6820, 6830, Cromofine Blue HS-3, 5187, 5108, 5197, 5085N, SR-5020, 5026, 5050, 4920, 4927, 4937, 4824, 4933GN-EP, 4940, 4973, 5205, 5208, 5214, 5221, 5000P, Chrome Fine Green 2GN, 2GO, 2G-550D, 5310, 5370, 6830, Chrome Fine Black A-1103, Seika Fast Yellow 10GH, A-3, 2035, 2054, 2200, 2270, 2300, 2400(B), 2500, 2600, ZAY-260, 2700(B), 2770, Se Squidfast Red 8040, C405(F), CA120, LR-116, 1531B, 8060R, 1547, ZAW-262, 1537B, GY, 4R-4016, 3820, 3891, ZA-215, Seikafast Carmine 6B1476T-7, 1483LT, 3840, 3870, Seikafast Bordeaux 10B-430, Seikalite Rose R40, Seikalite Violet B800, 7805, Seikafast Maroon 460N, Seikafast Orange 900, 2900, Seikalite Blue C718, A612, Cyanine Blue 4933M, 4933GN-EP, 4940, 4973 (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.); KET Yellow 401, 402, 403, 404, 405, 406, 416, 424, KET Orange 501, KET Red 301, 302, 303, 304, 305, 306, 307, 308, 309, 310, 336, 337, 338, 346, KET Blue 101, 102, 103, 104, 105, 106, 111, 118, 124, KET Green 201 (manufactured by Dainippon Ink and Chemicals Co., Ltd.);Colortex Yellow 301, 314, 315, 316, P-624, 314, U10GN, U3GN, UNN, UA-414, U263, Finecol Yellow T-13, T-05, Pigment Yellow1705, Colortex Orange 202, Colortex Red101, 103, 115, 116, D3B, P-625, 102, H-1024, 105C, UFN, UCN, UBN, U3BN, URN, UGN, UG276, U456, U457, 105C, USN, Colortex Maroon601, Colortex BrownB610N, Colortex Violet600, Pigment Red 122, Colortex Blue516, 517, 518, 519, A818, P-908, 510, Colortex Green 402, 403, Colortex Black 702, U905 (manufactured by Sanyo Dye Co., Ltd.); Lionol Yellow 1405G, Lionol Blue FG7330, FG7350, FG7400G, FG7405G, ES, ESP-S (manufactured by Toyo Ink Co., Ltd.); Toner Magenta E02, Permanent Rubin F6B, Toner Yellow HG, Permanent Yellow GG-02, Hostapearm Blue B2G (manufactured by Hoechst Industrie); Novoperm P-HG, Hostaperm Pink E, Hostaperm Blue B2G (manufactured by Clariant); carbon black #2600, #2400, #2350, #2200, #1000, #990, #980, #970, #960, #950, #850, MCF88, #750, #650, MA600, MA7, MA8, MA11, MA100, MA100R, MA77, #52, #50, #47, #45, #45L, #40, #33, #32, #30, #25, #20, #10, #5, #44, and CF9 (manufactured by Mitsubishi Chemical Corporation).

[0079] (self-dispersing pigment) The pigment may be a self-dispersing pigment. A self-dispersing pigment is a pigment particle whose surface is modified with a group having a hydrophilic group. A self-dispersing pigment has pigment particles and hydrophilic groups bonded to the surface of the pigment particles.

[0080] Examples of hydrophilic groups include carboxy groups, sulfonic acid groups, and phosphorus-containing groups, and examples of phosphorus-containing groups include phosphoric acid groups, phosphonic acid groups, phosphinic acid groups, phosphite groups, and phosphate groups.

[0081] Commercially available examples of self-dispersing pigments include Cabot's Cab-0-Jet® 200K, 250C, 260M, and 270V (sulfonic acid group-containing self-dispersing pigments). Other commercially available examples of self-dispersing pigments include Cabot's Cab-0-Jet® 300K (carboxylic acid group-containing self-dispersing pigments) and Cab-0-Jet® 400K, 450C, 465M, 470V, and 480V (phosphate group-containing self-dispersing pigments).

[0082] The pigment content is not particularly limited, but is preferably within the range of 1.5 to 15% by mass of the pigment ink. This makes it easy to adjust the viscosity of the pigment ink within the above range and enables the formation of high-density images. When the pigment content is 1.5% by mass or more, high-density images are easily formed. When the pigment content is 15% by mass or less, the ink viscosity does not become too high, and ejection stability is less likely to be impaired. For the same reason, the pigment content is more preferably within the range of 5 to 15% by mass of the pigment ink.

[0083] (Water dispersible resin) The pigment ink may further contain a water-dispersible resin. The water-dispersible resin has the function of fixing the pigment and the like to the fabric. The water-dispersible resin may be contained in the ink as resin particles (second resin particles).

[0084] Examples of water-dispersible resins include urethane resins, butadiene resins, acrylic resins, polystyrene, and ester resins. Examples of butadiene resins include styrene-butadiene copolymers and acrylonitrile-butadiene copolymers. Examples of acrylic resins include acrylic ester copolymers, styrene-acrylic copolymers, silicone-acrylic copolymers, and acrylic-modified fluororesins. Among these, urethane resins and acrylic ester copolymers and styrene-acrylic copolymers are preferred. These are thought to bond with the block copolymer through intermolecular hydrogen bonds, which makes it easier to improve the adhesion of the pigment to fabrics and the wet rub fastness.

[0085] Examples of styrene-acrylic copolymers include styrene-(meth)acrylic acid copolymers and styrene-(meth)acrylic acid-(meth)acrylic acid ester copolymers. Examples of (meth)acrylic acid esters include benzyl (meth)acrylate, cyclohexyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylhexyl carbitol (meth)acrylate, phenol EO-modified (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate.

[0086] Urethane resins are polymers obtained by reacting polyols with polyisocyanates. Examples of polyols include polypropylene glycol, polyethylene glycol, polytetramethylene glycol, poly(ethylene adipate), poly(diethylene adipate), poly(propylene adipate), poly(tetramethylene adipate), poly(hexamethylene adipate), poly-ε-caprolactone, poly(hexamethylene carbonate), and silicone polyols. Examples of isocyanates include tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, and hexamethylene diisocyanate. Other examples of isocyanates include hydrogenated tolylene diisocyanate, hydrogenated 4,4-diphenylmethane diisocyanate, isophorone diisocyanate, and tetramethylxylylene diisocyanate.

[0087] The average particle size of the water-dispersible resin is not particularly limited, but from the viewpoint of preventing nozzle clogging of the inkjet head, it is preferably 300 nm or less, and more preferably 130 nm or less. The average particle size of the water-dispersible resin can be measured by laser diffraction / scattering particle size distribution measurement.

[0088] The content of the water-dispersible resin is preferably 1 to 15% by mass relative to the pigment ink. When the content of the water-dispersible resin is 1% by mass or more, it is easy to increase the viscosity of the pigment ink appropriately, which not only improves the ejection stability but also makes it easy to improve the adhesion to the fabric and the abrasion resistance of the resulting image. When the content of the water-dispersible resin is 15% by mass or less, the viscosity of the pigment ink does not become too high, making it less likely to cause nozzle clogging and the like. For the same reason, the content of the water-dispersible resin is more preferably 2 to 10% by mass relative to the pigment ink.

[0089] (Silicone acrylic resin) The pigment ink may further contain a silicone acrylic resin. The silicone acrylic resin may be one having the same composition as the silicone acrylic resin contained in the second treatment liquid described above. This has the effect of making the first treatment liquid more easily wettable and spreadable.

[0090] (anionic pigment dispersant) Pigment ink contains an anionic pigment dispersant. The anionic pigment dispersant adheres to the surface of the pigment, making it easier to disperse the pigment in water. A pigment with an anionic pigment dispersant attached thereto dispersed in a dispersion medium (such as water) is called an anionic pigment dispersion. Anionic pigment dispersions are also simply called pigment dispersions. Anionic pigment dispersions include "a pigment with an anionic pigment dispersant attached thereto" and "a dispersion medium in which the "pigment with an anionic pigment dispersant attached thereto" is dispersed." Anionic pigment dispersions may also contain other ingredients.

[0091] The anionic pigment dispersant may be a random copolymer, a block copolymer, or a graft copolymer, and one type may be used alone, or two or more types may be used in combination.

[0092] The anionic pigment dispersant is not particularly limited, but examples thereof include acrylic resins, urethane resins, polyester resins, polyamide resins, and polyimide resins. Among these, acrylic resins and urethane resins are preferred. Use of such an anionic pigment dispersant tends to further improve abrasion resistance.

[0093] The acrylic resin is a resin obtained by polymerizing a monomer containing at least an acrylate or acrylic acid, and an acrylic resin obtained by polymerizing at least one of an acrylate or acrylic acid with another monomer is preferred. Examples of other monomers include styrene-acrylic resins using styrene. The acrylic resin may be a commercially available product or may be produced by a known method.

[0094] Urethane resin is a general term for resins having urethane bonds. In addition to polyurethane bonds, urethane resins may include polyol-type urethane resins containing hydroxy groups in the main chain, polyester-type urethane resins containing ester bonds in the main chain, and polycarbonate-type urethane resins containing carbonate bonds in the main chain. The urethane resin may be a commercially available product or one produced by a known method.

[0095] (Block copolymer) The block copolymer serving as the anionic pigment dispersant is preferably an ABA block copolymer consisting of two hydrophilic blocks A located at both ends of the molecule and a hydrophobic block B located between the two hydrophilic blocks A. The hydrophilic block A interacts or reacts with the cationic flocculant. Here, interaction includes electrical bonding, bonding by hydrogen bonding, etc.

[0096] Conventionally, the pigment dispersant contained in pigment inks has been, for example, a random copolymer or an AB block copolymer. For example, a random copolymer is a copolymer that randomly contains sites that interact or react with a flocculant. For example, an AB block copolymer is a copolymer that has a block (usually a hydrophilic block A) that contains many sites that interact or react with a flocculant at only one end of the molecule.

[0097] Random copolymers do not have blocks containing many sites that interact or react with flocculants, making them less likely to interact or react with flocculants. AB-type block copolymers have blocks containing many sites that interact or react with flocculants. However, because the block is located at only one end of the molecule, there may be fewer bonding points available for bonding to the fabric. This may make it difficult to obtain adhesion of the copolymer to the fabric, resulting in poor wet and dry friction fastness. Furthermore, because the copolymer can bond continuously (film-like) to the fabric at one bonding point, the fabric may also tend to become hard.

[0098] In contrast, the above-mentioned block copolymers, such as ABA type, contain blocks at both ends of the molecule that contain many sites that interact or react with the flocculant. Because these blocks are present at at least two locations on both ends of the molecule, there are many bonding points available for bonding with the fabric, making the bond with the fabric stronger. This improves adhesion to the fabric and increases wet friction resistance. Furthermore, because the copolymer can bond intermittently with the fabric at multiple bonding points, the fabric is less likely to become hard than if the copolymer were continuously bonded at a single bonding point. The block containing many sites that interact or react with the flocculant is a hydrophilic block.

[0099] That is, the block copolymer preferably contains two hydrophilic blocks A arranged at both ends of the molecule and a hydrophobic block B arranged between the two hydrophilic blocks A.

[0100] The "hydrophilic block A" is a block that enhances affinity with the aqueous solvent contained in the pigment ink and contains a site that interacts or reacts with the flocculant attached to the fabric. The "hydrophilic block A" refers to the block that has the highest affinity with water among the blocks constituting the copolymer. The number of hydrophilic blocks is preferably two.

[0101] The hydrophilic block A contains structural units derived from a monomer having a hydrophilic functional group (hereinafter referred to as a "hydrophilic monomer"), such as a hydroxyl group, a carboxyl group, and a sulfonic acid group.

[0102] Examples of the hydrophilic monomer constituting the hydrophilic block A include vinyl-based monomers containing a hydrophilic functional group. Examples of such vinyl-based monomers include unsaturated polycarboxylic acids such as (meth)acrylic acid and maleic acid, and monomers containing a carboxy group or an acid anhydride group such as maleic anhydride. Other examples include monomers containing a sulfonic acid group such as styrenesulfonic acid and 4-(methacryloyloxy)butylsulfonic acid. Still other examples include ethylene oxide-modified (meth)acrylic acid ester monomers such as ethylene oxide-modified (meth)acrylic acid alkyl ester. Of these, the hydrophilic monomer is preferably (meth)acrylic acid from the viewpoint of imparting appropriate water solubility to the hydrophilic block A.

[0103] The content of the structural units derived from hydrophilic monomers in the hydrophilic block A should be higher than the content of the structural units derived from hydrophilic monomers in the hydrophobic block B. Specifically, the content of the structural units derived from hydrophilic monomers in the hydrophilic block A is preferably 5% by mass or more relative to 100% by mass of the hydrophilic block A. When the content of the structural units derived from hydrophilic monomers is 5% by mass or more, not only is the dispersibility in aqueous solvents more likely to be improved, but the interaction or reaction with the flocculant is also more likely to be enhanced, which makes it easier to improve adhesion to fabrics. From the same viewpoint, the content is more preferably 10 to 40% by mass.

[0104] The hydrophilic block A may further contain structural units derived from other monomers besides the hydrophilic monomer. Examples of other monomers include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate and tert-butyl (meth)acrylate. Among these, alkyl esters having two or more carbon atoms, such as butyl (meth)acrylate, are preferred. This is because the glass transition temperature (Tg) of the block copolymer is low, and the fabric is less likely to become stiff. However, the other monomers do not include hydrophobic monomers, which will be described later.

[0105] The "hydrophobic block B" is a portion that adsorbs to the pigment, and is the block that has the lowest affinity for the aqueous solvent contained in the ink among the blocks that make up the copolymer. The number of hydrophobic blocks B is preferably one.

[0106] The hydrophobic block B contains structural units derived from a monomer having a hydrophobic functional group (hereinafter referred to as "hydrophobic monomer"). Examples of the monomer having a hydrophobic functional group include vinyl monomers containing an aromatic ring group or an alicyclic hydrocarbon group.

[0107] Examples of vinyl monomers containing an aromatic ring group include (meth)acrylates having an aromatic ring group, such as benzyl (meth)acrylate, phenyl (meth)acrylate, and phenoxyethyl (meth)acrylate. Other examples include aromatic vinyl monomers such as styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene, and 1-vinylnaphthalene. Among these vinyl monomers containing an aromatic ring group, preferred are, but are not limited to, vinyl monomers having an aromatic ring group with 6 to 15 carbon atoms.

[0108] Examples of vinyl monomers having an alicyclic alkyl group include (meth)acrylates having an alicyclic alkyl group. Examples of such (meth)acrylates include cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, and cyclododecyl (meth)acrylate. Other examples include bornyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate. Although not particularly limited, among these vinyl monomers having an alicyclic alkyl group, vinyl monomers having an alicyclic alkyl group having 6 to 15 carbon atoms are preferred.

[0109] Of these, from the viewpoint of improving the adsorption onto the pigment, the hydrophobic monomer is preferably a vinyl monomer having an aromatic ring group with 6 to 15 carbon atoms, such as styrene.

[0110] The content of structural units derived from hydrophobic monomers in the hydrophobic block B is preferably 80% by mass or more relative to the hydrophobic block B. When the content is 80% by mass or more, the adsorption to pigments is likely to be enhanced. From the same viewpoint, the content is more preferably more than 90% by mass, and even more preferably 95% by mass or more.

[0111] The hydrophobic block B may further contain structural units derived from monomers other than hydrophobic monomers. Examples of the other monomers include the above-mentioned other monomers and hydrophilic monomers. However, when the hydrophobic block B contains structural units derived from hydrophilic monomers, the content of the structural units derived from hydrophilic monomers in the hydrophobic block B is lower than that in the hydrophilic block A. Specifically, the content of the structural units derived from hydrophilic monomers is preferably 20% by mass or less, more preferably less than 10% by mass, and even more preferably 5% by mass or less, relative to the hydrophobic block B. In other words, of the two hydrophilic blocks A and B, the content of the structural units derived from hydrophilic monomers (molar number of hydrophilic functional groups) in the hydrophobic block B is the lowest.

[0112] The content of the hydrophobic block B in the ABA block copolymer is preferably 20% by mass or more and 80% by mass or less, and more preferably 20% by mass or more and 50% by mass or less, based on the total mass of the block copolymer. When the content is 20% by mass or more, the content of the hydrophilic block A is low (or the molecular weight is small), which makes it easier to suppress crosslinking aggregation. On the other hand, when the content is 80% by mass or less, the content of the hydrophilic block A is high (or the molecular weight is large), which makes it easier to increase affinity for aqueous solvents.

[0113] When the hydrophilic block is A and the hydrophobic block is B, examples of the structure of the block copolymer include an ABA type, an ABABA type, etc. Among these, the block copolymer is preferably an ABA type block copolymer consisting of two hydrophilic blocks A located at both ends of the molecule and a hydrophobic block B located between them.

[0114] The types and compositional ratios of monomers in the multiple blocks A contained in the block copolymer may be the same or different from one another. Furthermore, when the block copolymer contains multiple blocks B, the types and compositional ratios of monomers in the multiple blocks B may be the same or different from one another. In particular, it is preferable that the two hydrophilic blocks A have the same monomer composition.

[0115] The weight-average molecular weight of the block copolymer is preferably 5,000 to 70,000, and more preferably 7,000 to 30,000. The larger the weight-average molecular weight, the easier it is to increase the dispersibility of the pigment in an aqueous solvent, and the smaller the weight-average molecular weight, the easier it is to suppress crosslinking and aggregation between pigments to which anionic pigment dispersants are attached (which can also be referred to as pigments themselves). The weight-average molecular weight of the block copolymer can be measured in polystyrene equivalent terms by gel permeation chromatography.

[0116] The molecular weight distribution (PDI) (weight average molecular weight (Mw) of the block copolymer) / (number average molecular weight (Mn) of the block copolymer) is preferably 2.0 or less, and more preferably 1.8 or less. A lower PDI means a narrower and more uniform molecular weight distribution, resulting in better dispersibility.

[0117] The acid value of the block copolymer is, for example, preferably 40 to 400 mgKOH / g, more preferably 40 to 300 mgKOH / g, and even more preferably 40 to 190 mgKOH / g. An acid value of 40 mgKOH / g or higher can enhance the hydrophilicity of the pigment dispersant and further improve the dispersibility of the pigment. Furthermore, an acid value of 400 mgKOH / g or lower can further prevent the hydrophilicity of the pigment dispersant from becoming excessively high, thereby further improving the water resistance of the resulting image-formed product. The acid value can be measured in accordance with the measurement method of JIS K0070:1992.

[0118] The content of the block copolymer is preferably 10 to 50% by mass, more preferably 20 to 40% by mass, relative to the pigment. A content of 10% by mass or more can further enhance the dispersibility of the pigment in the pigment dispersion. Furthermore, a content of the pigment dispersant of 50% by mass or less can further suppress an increase in the viscosity of the pigment dispersion due to an excessive amount of pigment dispersant.

[0119] The method for synthesizing the block copolymer is not particularly limited, but for example, it can be obtained by sequentially polymerizing vinyl monomers that constitute the blocks by living radical polymerization.

[0120] The pigment ink contains anionic resin particles with a film elongation of 600 to 1600%.

[0121] (Anionic resin particles with a film elongation of 600 to 1600%) Anionic resin particles having a film elongation of 600 to 1600% exist in a dispersed state in an aqueous medium. Hereinafter, anionic resin particles having a film elongation of 600 to 1600% may be simply referred to as "anionic resin particles."

[0122] The anionic resin particles are not particularly limited in type as long as they are anionic resin particles having a film elongation of 600 to 1600%, but examples thereof include urethane resins, acrylic resins, and ester resins. The resin constituting the anionic resin particles preferably contains a urethane resin or an acrylic resin, and more preferably a urethane resin. The inclusion of a urethane resin or an acrylic resin is advantageous in that an image having excellent image density and wet rub fastness can be formed on the fabric.

[0123] The film elongation of anionic resin particles was measured as follows. First, the resin was applied to a polytetrafluoroethylene sheet so that the dried film thickness was 500 μm. The resin was then dried for 15 hours at room temperature and atmospheric pressure, i.e., 20°C and 65% RH, followed by 6 hours at 80°C and 20 minutes at 120°C. The resin was then peeled off from the sheet to create a resin film. The film elongation of the resulting resin film was measured using a tensile tester at a temperature of 20°C and a measurement speed of 200 mm / min. The film elongation was measured by stretching the resin film and measuring the length it extended until it broke. This ratio was expressed as a percentage, representing the film elongation. The tensile tester used may be, for example, the "Tensilon Universal Tester RTC-1225A" manufactured by Orientec Co., Ltd., or a similar device.

[0124] The film elongation of the anionic resin particles is preferably 600 to 1600%. If the film elongation of the anionic resin particles is less than 600%, the ink film will have difficulty following the expansion and contraction of the fabric, and may detach, resulting in poor wet rubbing fastness. If the film elongation of the anionic resin particles is more than 1600%, the fastness of the coating film itself will be poor.

[0125] The content of anionic resin particles with a film elongation of 600 to 1600% is preferably 5.0 to 15.0% by mass, and particularly preferably 7.5 to 12.5% ​​by mass, based on the total pigment ink. If it is less than 5.0% by mass, there is a problem of poor wet rub fastness. If it is more than 15.0% by mass, there is a problem of poor ejection stability.

[0126] The pigment ink contains a nonionic surfactant.

[0127] Examples of nonionic surfactants contained in pigment inks include acetylene-based surfactants, ether-based surfactants, silicone-based surfactants, and fluorine-based surfactants. Among these, acetylene-based surfactants are preferred. The use of acetylene-based surfactants as the nonionic surfactant offers the advantage of enabling images with excellent image density and wet friction fastness to be formed on fabric. This is thought to be because the particles have good re-adsorption even after ejection, allowing the fabric to be filled with the ink as it spreads in the X and Y directions, improving density. Furthermore, the increased contact area between the fabric and the coating film is thought to improve wet friction resistance.

[0128] The content of the nonionic surfactant is preferably 0.05 to 1.0% by mass, more preferably 0.08 to 0.75% by mass, and particularly preferably 0.1 to 0.5% by mass, based on the total pigment ink. If the content is less than 0.05% by mass, the ink will adhere more to the nozzle surface, resulting in problems with ejection stability. If the content is more than 1.0% by mass, the ink will increase in viscosity, resulting in problems with ejection stability.

[0129] (Water-soluble organic solvent) The pigment ink, first treatment liquid, and second treatment liquid preferably further contain a water-soluble organic solvent, which can further improve ejection stability by inkjet printing.

[0130] The water-soluble organic solvent is not particularly limited as long as it is compatible with water, and examples thereof include polyhydric alcohols (for example, dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and polypropylene glycol, and trihydric or higher alcohols such as glycerin, trimethylolpropane, and hexanetriol); polyhydric alcohol ethers (for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and diethylene glycol dimethyl ether); ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether); monohydric alcohols (e.g., methanol, ethanol, propanol, pentanol, hexanol, cyclohexanol, benzyl alcohol); amines (e.g., ethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, triethylenetetramine); amides (e.g., formamide, N,N-dimethylformamide, N,N-dimethylacetamide); heterocycles (e.g., 2-pyrrolidone, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidine), sulfoxides (e.g., dimethyl sulfoxide); and sulfones (e.g., sulfolane).

[0131] Furthermore, from the viewpoint of further improving ejection stability by inkjet printing, the water-soluble organic solvent preferably contains a water-soluble organic solvent having a boiling point of 180°C or higher, preferably 190°C or higher, and more preferably 200°C or higher. Examples of water-soluble organic solvents having a boiling point of 180°C or higher include dihydric alcohols and trihydric or higher alcohols. Examples of dihydric alcohols include ethylene glycol (boiling point 197°C), 1,3-butanediol (boiling point 208°C), 1,6-hexanediol (boiling point 223°C), and polypropylene glycol. Examples of trihydric or higher alcohols include glycerin (boiling point 290°C) and trimethylolpropane (boiling point 295°C).

[0132] The content of the water-soluble organic solvent contained in the first treatment liquid is preferably, for example, 10% to 65% by mass, and more preferably 20% to 45% by mass, relative to the first treatment liquid. The content of the water-soluble organic solvent contained in the second treatment liquid is preferably, for example, 10% to 65% by mass, and more preferably 20% to 45% by mass, relative to the second treatment liquid. The content of the water-soluble organic solvent contained in the pigment ink is preferably, for example, 10% to 65% by mass, and more preferably 20% to 45% by mass, relative to the pigment ink.

[0133] The water content of the first treatment liquid is preferably 30% to 85% by mass, and more preferably 50% to 75% by mass, relative to the first treatment liquid. The water content of the second treatment liquid is preferably 30% to 85% by mass, and more preferably 50% to 75% by mass. The water content of the pigment ink is preferably 30% to 85% by mass, and more preferably 50% to 75% by mass, relative to the pigment ink.

[0134] (Other ingredients) The pigment ink, the first treatment liquid, and the second treatment liquid may further contain other components in addition to those described above, as necessary. Examples of other components include surfactants, preservatives, etc. The pigment ink may contain surfactants other than nonionic surfactants.

[0135] The surfactant can reduce the surface tension of the pigment ink, the first treatment liquid, and the second treatment liquid, thereby increasing the wettability of the pigment ink, the first treatment liquid, and the second treatment liquid to the fabric. The type of surfactant is not particularly limited, but can be, for example, an acetylene glycol surfactant, a silicone surfactant, a fluorine surfactant, or the like.

[0136] Examples of the preservative or antifungal agent include aromatic halogen compounds (eg, Preventol CMK), methylene dithiocyanate, halogen-containing nitrogen-sulfur compounds, 1,2-benzisothiazolin-3-one (eg, PROXEL GXL), and the like.

[0137] The pigment ink may further contain a crosslinking agent for crosslinking the resin that constitutes the resin particles. The crosslinking agent is preferably a compound having at least two functional groups in the molecule that react with the crosslinkable groups (hydroxyl groups, carboxyl groups, and ketone groups) of the resin particles. Examples of crosslinking groups that react with hydroxyl groups include isocyanate groups and blocked isocyanate groups. Examples of crosslinking groups that react with carboxyl groups include oxazolyl groups, aziridine groups, and carbodiimide groups. Examples of crosslinking groups that react with ketone groups include hydrazide groups.

[0138] Specifically, examples of crosslinking agents that react with hydroxyl groups include Fixer N (a blocked isocyanate-based crosslinking agent, manufactured by Matsui Pigment Chemical Industry Co., Ltd.). Examples of crosslinking agents that react with carboxyl groups include Fixer F (an aziridine-based crosslinking agent, manufactured by Matsui Pigment Chemical Industry Co., Ltd.). Examples of crosslinking agents that react with ketone groups include adipic acid dihydrazide (ADH, a hydrazine-based crosslinking agent).

[0139] For example, the most preferred crosslinking agent contained in pigment ink is adipic acid dihydrazide, and the most preferred combination is with diacetone acrylamide (DAAM), a crosslinking monomer that reacts with adipic acid dihydrazide. By using this crosslinking agent in pigment ink, the ink can be stored for long periods at room temperature and can be crosslinked at room temperature. There are no particular restrictions on the amount of crosslinking agent contained in pigment ink.

[0140] <Preparation of pigment ink, first treatment liquid, and second treatment liquid> The pigment ink, first treatment liquid, and second treatment liquid can be prepared by any method so as to contain the components described above. For example, the pigment ink can be produced by mixing the pigment, water, any dispersant, and the like.

[0141] [Inkjet textile printing ink set] Next, one embodiment of the inkjet textile printing ink set of the present invention will be described. The inkjet textile printing ink set of this embodiment is an inkjet textile printing ink set including a pigment ink, a first treatment liquid, and a second treatment liquid, and is characterized in that the pigment ink, the first treatment liquid, and the second treatment liquid are the pigment ink, the first treatment liquid, and the second treatment liquid used in the inkjet textile printing method of this embodiment described above. Such an inkjet textile printing ink set has the advantage that it can be used in the inkjet textile printing method of this embodiment described above, and can form an image on fabric that has excellent image density and wet rub fastness.

[0142] [Inkjet printing device] Hereinafter, one embodiment of the inkjet textile printing apparatus of the present invention will be described with reference to the drawings, but the present invention is not limited thereto. Fig. 1 is a schematic diagram showing an embodiment of the inkjet textile printing apparatus 1. Fig. 2 is a plan view showing an inkjet unit 11, a first treatment liquid ejection head 13, and a second treatment liquid ejection head 14 mounted on a carriage 10. The XYZ three-dimensional coordinate system shown in Fig. 1 is a coordinate system in which the XY plane is the horizontal plane and the Z direction is the vertical direction, and is a coordinate system common to the coordinate system shown in Fig. 2. The X direction is the main scanning direction, and the Y direction is the direction in which the fabric is transported.

[0143] The inkjet textile printing apparatus 1 includes an inkjet unit 11, a first treatment liquid ejection head 13, and a second treatment liquid ejection head 14. The inkjet unit 11 ejects pigment ink onto the fabric 3 while scanning in the main scanning direction X. The first treatment liquid ejection head 13 scans together with the inkjet unit 11 in the main scanning direction X and ejects the first treatment liquid onto the fabric 3. The second treatment liquid ejection head 14 scans together with the inkjet unit 11 in the main scanning direction X and ejects the second treatment liquid onto the fabric 3. The first treatment liquid ejection head 13 and the second treatment liquid ejection head 14 are disposed on either side of the inkjet unit 11 in the main scanning direction X. The inkjet unit 11 also includes a yellow ink head 11y, a magenta ink head 11m, a cyan ink head 11c, and a black ink head 11k. Furthermore, the inkjet printing apparatus 1 is equipped with an inkjet head 15 having an inkjet unit 11, a first treatment liquid ejection head 13, and a second treatment liquid ejection head 14. In the inkjet printing apparatus 1 of this embodiment, the inkjet head 15 is made up of the inkjet unit 11, the first treatment liquid ejection head 13, and the second treatment liquid ejection head 14. Note that the inkjet unit 11 may be configured to have additional inkjet heads of the same color or different colors, or may have several rows of the inkjet heads 15.

[0144] The inkjet printing apparatus 1 of this embodiment is capable of inkjet printing that satisfies each of the requirements of the inkjet printing method of this embodiment. Specifically, the pigment ink, first treatment liquid, and second treatment liquid are ejected onto the fabric 3 using the inkjet head 15 in the following order: first treatment liquid, pigment ink, second treatment liquid. The first treatment liquid, pigment ink, and second treatment liquid are then applied to the same location before drying. The first treatment liquid contains a water-soluble cationic coagulant, and the second treatment liquid contains a silicone acrylic resin. The pigment ink contains a pigment, an anionic pigment dispersant, anionic resin particles having a film elongation of 600 to 1600%, and a nonionic surfactant. The ratio of the nonionic surfactant to the total amount of the pigment, anionic pigment dispersant, and anionic resin particles is 0.022 or more and 0.096 or less. The first treatment liquid is used to retain at least one of the pigment ink and the second treatment liquid on the fabric surface. The first treatment liquid preferably serves to at least retain the pigment ink on the surface of the fabric.

[0145] The inkjet printing apparatus 1 of this embodiment is a printing apparatus that forms an image by ejecting ink onto a fabric 3 that is transported along a predetermined transport direction. As shown in Fig. 1, this inkjet printing apparatus 1 includes a transport section 2 that transports the fabric 3, an image forming section 4, and a control section 30. A drying section 5 and the like may also be provided separately.

[0146] (Transportation section) The conveying unit 2 conveys the fabric 3 along a predetermined conveying direction (the Y direction in FIG. 1). The conveying unit 2 includes a pair of conveying rollers 2a and 2b and a platen 2c. The pair of conveying rollers 2a and 2b rotate about a rotation axis parallel to the X direction in FIG. 1 by driving a conveying motor (not shown). This conveys the fabric 3 stretched over the pair of conveying rollers 2a and 2b in the conveying direction (the Y direction). The platen 2c is a plate-shaped member disposed between the pair of conveying rollers 2a and 2b so that its upper surface is substantially horizontal. The platen 2c supports the fabric 3 on its upper surface. Alternatively, the platen 2c may be provided with an air vent to suck air from the side opposite the fabric 3, thereby adsorbing the fabric 3 to the upper surface of the platen 2c. In this case, the fabric 3 is conveyed in the predetermined conveying direction while adsorbed to the upper surface of the platen 2c. The configuration of the conveying section 2 is not limited to the above, and may be configured, for example, such that an endless conveying belt is stretched between a pair of conveying rollers 2a and 2b, and the fabric 3 is conveyed in the conveying direction by the conveying belt which moves in a circular motion in accordance with the rotation of the conveying rollers 2a and 2b.

[0147] In FIG. 1, the conveying section 2 is configured to convey the fabric 3 by the conveying rollers 2a and 2b, but it may also be configured to convey the fabric 3 by attaching it to a conveying belt, for example.

[0148] In the case of a configuration in which the fabric is attached to a conveyor belt and conveyed, the following cleaning process is performed. FIG. 4 is a diagram showing the schematic configuration of an inkjet printing apparatus in which the fabric is attached to a conveyor belt and conveyed. In the case of a configuration in which the fabric is attached to a conveyor belt and conveyed, as shown in FIG. 4, a conveyor belt cleaning unit 104 is disposed below the belt conveying unit 102. The conveyor belt cleaning unit 104 is provided with a plurality of cleaning means and the like arranged in order along the moving direction of the conveyor belt 223. In the belt conveying unit 102, the drive roller 221 is rotated at a predetermined speed in the counterclockwise direction (see the arrow) in FIG. 4 by the rotational drive of the sub-scanning motor, thereby rotating the conveyor belt 223 stretched between the drive roller 221 and the driven roller 222. As a result, the fabric T2 placed on the surface of the conveyor belt 223 is conveyed in the sub-scanning direction, indicated by arrow A in the figure. In FIG. 4, reference numeral 103 denotes an image forming unit serving as an inkjet coating device.

[0149] The conveyor belt cleaning unit 104 includes a water sprinkler pipe 141 , a brush roller 142 , a cleaning blade 143 , a cleaning sponge 144 , and a heating unit 145 .

[0150] The sprinkler pipe 141 is suspended across the entire width of the conveyor belt 223. A large number of nozzles are arranged along the length of the sprinkler pipe 141 at a position facing the surface of the conveyor belt 223. A cleaning liquid is supplied to the sprinkler pipe 141 via a sprinkler tube 141a by driving a sprinkler pump. The sprinkler pipe 141 sprays the supplied cleaning liquid from the nozzles onto the surface of the conveyor belt 223, thereby cleaning foreign matter adhering to the surface of the conveyor belt 223.

[0151] The brush roller 142 is formed in a roller shape by burying multiple brush bundles, each consisting of a bundle of brush bristles, around a rotating shaft that spans the entire width of the conveyor belt 223. The tips of the brush bundles are constantly in contact with the surface of the conveyor belt 223 downstream of the water sprinkling position of the sprinkler pipe 141 in the direction of rotation of the conveyor belt 223. The brush roller 142 rotatably contacts the surface of the conveyor belt 223 and removes foreign matter such as aggregates remaining on the surface of the conveyor belt 223. Specifically, the brush roller 142 rotates at a predetermined speed in the same direction as the rotation direction of the drive roller 221 based on the power of a brush drive unit (not shown). As a result, the brush roller 142 moves in a direction opposite to the direction of movement of the conveyor belt 223, rubbing the tips of the brush bundles against the surface of the conveyor belt 223. As a result, the brush roller 142 removes foreign matter that has been washed away by the spraying of cleaning liquid from the sprinkler pipe 141, which is located upstream of the direction of movement of the conveyor belt 223.

[0152] A cleaning tub for storing cleaning liquid may be provided below brush roller 142. In this case, the lower part of brush roller 142 is partially immersed in this cleaning liquid, and the cleaning liquid is stirred up as brush roller 142 rotates, thereby enhancing the effect of removing foreign matter. Furthermore, the cleaning liquid in this cleaning tub may be supplied to sprinkler pipe 141 via sprinkler tube 141a. In this case, the cleaning liquid sprayed onto the surface of conveyor belt 223 and dripping thereon is collected again in the cleaning tub and reused.

[0153] The cleaning blade 143 is provided downstream of the brush roller 42 in the rotation direction of the conveyor belt 223. The cleaning blade 143 is formed in a flat plate shape using, for example, an elastic material such as rubber, a PET sheet, or a straight brush, and is stretched across the entire width of the conveyor belt 223. The cleaning blade 143 is configured so that its tip can come into contact with or be separated from the surface of the conveyor belt 223. The cleaning blade 143 comes into contact with the surface of the conveyor belt 223 and removes foreign matter and cleaning liquid remaining on the surface of the conveyor belt 223 by scraping it off.

[0154] The cleaning sponge 144 is a porous body having water absorption properties, such as a sponge, and is stretched across the entire width of the conveyor belt 223. The surface of the cleaning sponge 144 is configured to be able to come into contact with or separate from the surface of the conveyor belt 223, downstream of the cleaning blade 143 in the rotation direction of the conveyor belt 223. By coming into contact with the surface of the conveyor belt 223, the cleaning sponge 144 absorbs and wipes away cleaning liquid remaining on the surface of the conveyor belt 223.

[0155] The heating unit 145 is a belt heater, and is provided downstream of the cleaning sponge 144 and upstream of the driven roller 222 in the rotation direction of the conveyor belt 223. The heating unit 145 heats and evaporates the cleaning liquid remaining on the surface of the conveyor belt 223.

[0156] 1, the conveying unit 2 intermittently conveys the fabric 3 along the conveying direction (Y direction). That is, the conveying unit 2 conveys the fabric 3 a predetermined amount in the conveying direction and then stops the conveying operation of the fabric 3. Then, after an image of a predetermined width is formed on the fabric 3 by the image forming unit 4, the conveying unit 2 conveys the fabric 3 again a predetermined amount in the conveying direction and then stops the conveying operation of the fabric 3. In this way, the conveying unit 2 repeats the operation of conveying the fabric 3 a predetermined amount in the conveying direction and then stopping the conveying.

[0157] (Image forming section) As shown in FIG. 1 , the image forming unit 4 is disposed above the fabric 3 being conveyed by the conveying unit 2, so as to cross in a direction (X direction) perpendicular to the conveying direction (Y direction). The image forming unit 4 forms an image on the fabric 3 by ejecting ink onto the fabric 3 while the conveying unit 2 is stopped. The image forming unit 4 includes an inkjet unit 11 and a carriage 10 that holds the inkjet unit 11. The inkjet unit 11 is an inkjet unit that ejects ink of four colors, for example, yellow (Y), magenta (M), cyan (C), and black (K). The carriage 10 is attached to a rail member 5 that crosses above the fabric 3, and is driven by a motor (not shown) to reciprocate along the extension direction (X direction) of the rail member 5. The moving direction (X direction) of the carriage 10 is the main scanning direction in which the inkjet unit 11 scans when forming an image on the fabric 3. That is, while the transport of the fabric 3 is stopped, the image forming unit 4 forms an image by causing the inkjet unit 11 to scan in the main scanning direction and ejecting ink from the inkjet unit 11 onto the fabric 3. At this time, the inkjet unit 11 ejects ink onto the fabric 3 based on image data to be printed (textile printed). Therefore, while moving in the main scanning direction, the inkjet unit 11 ejects ink onto image areas that contain valid image components in the image data to be printed. The inkjet unit 11 does not eject ink into margin areas that do not contain valid image components.

[0158] The inkjet unit 11 is provided at the center of the carriage 10 in the main scanning direction. The carriage 10 is also equipped with treatment liquid ejection heads 12a and 12b on both sides of the inkjet unit 11 in the main scanning direction. That is, in the main scanning direction, the treatment liquid ejection head 12a is arranged on one side of the inkjet unit 11, and the treatment liquid ejection head 12b is arranged on the other side. These treatment liquid ejection heads 12a and 12b are arranged alongside the inkjet unit 11 in the main scanning direction of the carriage 10. The treatment liquid ejection heads 12a and 12b move in the main scanning direction together with the inkjet unit 11. The treatment liquid ejection heads 12a and 12b eject a predetermined treatment liquid onto the fabric 3 before or after the inkjet unit 11 ejects ink onto the fabric 3.

[0159] At least one end of a rail member 5 provided in the image forming unit 4 extends further outward than the transport path along which the fabric 3 is transported. Therefore, the carriage 10 can move further outward than the transport path along which the rail member 5 extends. A purge tub 6 and a drainage tank 8 are provided at the extended end of the rail member 5. A cleaning unit 20 is also provided adjacent to the purge tub 6 and the drainage tank 8. The purge tub 6 and the drainage tank 8 are used to collect ink and treatment liquid purged from the inkjet unit 11 and the treatment liquid ejection heads 12a and 12b, respectively. The cleaning unit 20 is used to clean the ink ejection surface of the inkjet unit 11 and the nozzles provided on the treatment liquid ejection surfaces of the treatment liquid ejection heads 12a and 12b. The cleaning unit 20 is disposed on a cleaning unit rail member 21 that is arranged along a direction (Y direction) parallel to the transport direction of the fabric 3. The cleaning unit 20 is movable in the Y direction along the cleaning unit rail member 21.

[0160] (Drying section) The inkjet textile printing apparatus of this embodiment may also include a drying section (not shown) that dries the first treatment liquid, pigment ink, and second treatment liquid applied in the image forming section 4. The drying means used in the drying section is not particularly limited, and is preferably hot air, a hot plate, a heat roller, or heating by infrared drying. From the viewpoint of sufficiently removing the solvent component in a short time, heated drying is more preferable. The drying temperature is preferably within the range of 100 to 200°C.

[0161] (Control unit) The control unit 30 controls the operation of each of the above-mentioned units, for example, as follows. For example, when forming an image on the fabric 3, the control unit 30 intermittently transports the fabric 3 in the transport direction, and moves the carriage 10 along the main scanning direction while stopping the transport of the fabric 3. For example, while moving the carriage 10 forward from the start position, the control unit 30 drives the inkjet unit 11 to form a one-line image on the fabric 3 in the main scanning direction. At this time, the width of the one-line image formed on the fabric 3 corresponds to the printing width of the inkjet unit 11 in the transport direction of the fabric 3. Then, after the one-line image is formed, the control unit 30 intermittently transports the fabric 3. The transport amount of the fabric 3 at this time corresponds to the width of the one-line image formed by the inkjet unit 11. When the fabric 3 has been transported by the width of the one-line image, the control unit 30 stops the transport of the fabric 3 and moves the carriage 10 along the main scanning direction again. After the forward movement, the carriage 10 moves in the backward direction, which is the opposite direction. The control unit 30 does not drive the inkjet unit 11 while the carriage 10 is moving in the backward direction. After returning the carriage 10 to its original start position, the control unit 30 moves the carriage 10 in the forward direction again and drives the inkjet unit 11. By repeating this intermittent operation, the control unit 30 forms an image on the fabric 3.

[0162] Furthermore, when cleaning the nozzles of the inkjet unit 11, the control unit 30 moves the carriage 10 to a position above the purge tub 6 or to a position above the cleaning unit 20. When the carriage 10 is moved to a position above the purge tub 6, the control unit 30 drives the inkjet unit 11 and the treatment liquid ejection heads 12a and 12b to purge and discharge the ink and treatment liquid from the nozzles. This makes it possible to prevent nozzle clogging. When the carriage 10 is moved to a position above the cleaning unit 20, the control unit 30 drives the cleaning unit 20 to move it along the Y direction. This allows the cleaning unit 20 to clean the nozzles of the inkjet unit 11 and the treatment liquid ejection heads 12a and 12b.

[0163] (inkjet unit, treatment liquid ejection head) Next, the inkjet unit 11 and the treatment liquid ejection heads 12a and 12b mounted on the carriage 10 will be described in detail.

[0164] As shown in FIG. 2, the inkjet unit 11 includes a yellow ink head 11y, a magenta ink head 11m, a cyan ink head 11c, and a black ink head 11k, which eject inks of four colors: Y, M, C, and K. The yellow ink head 11y, the magenta ink head 11m, the cyan ink head 11c, and the black ink head 11k may be simply referred to as "ink heads 11y, 11m, 11c, and 11k." The ink heads 11y, 11m, 11c, and 11k are arranged at predetermined intervals along the main scanning direction. Each of the ink heads 11y, 11m, 11c, and 11k has a number of nozzles on the ejection surface facing the fabric 3. The nozzles are arranged along the transport direction of the fabric 3, which is perpendicular to the main scanning direction, and define the printing width when forming an image on the fabric 3. For example, the ink ejected from each of the ink heads 11c, 11m, 11y, and 11k contains at least a pigment.

[0165] The treatment liquid ejection heads 12a and 12b are arranged in the same row as the ink heads 11c, 11m, 11y, and 11k in the main scanning direction. That is, the ink heads 11c, 11m, 11y, and 11k are arranged so that they are sandwiched between the treatment liquid ejection heads 12a and 12b on both sides in the main scanning direction.

[0166] The treatment liquid ejection head 12a includes a first treatment liquid ejection head 13. The first treatment liquid ejection head 13 is arranged adjacent to the outer side of the cyan ink head 11c at a distance greater than the distance between the ink heads 11c, 11m, 11y, and 11k.

[0167] The treatment liquid ejection head 12b is equipped with a second treatment liquid ejection head 14. The second treatment liquid ejection head 14 of the treatment liquid ejection head 12b is arranged adjacent to the outer side of the black ink head 11k at a distance greater than the distance between the ink heads 11c, 11m, 11y, and 11k.

[0168] As described above, the inkjet printing apparatus 1 of this embodiment includes one ejection head 13 for the first treatment liquid and one ejection head 14 for the second treatment liquid, which are arranged on both sides of the inkjet unit 11 in the main scanning direction.

[0169] The first treatment liquid ejection head 13 ejects the first treatment liquid onto the fabric 3. The first treatment liquid is a liquid that is ejected onto the fabric 3 before the pigment ink is ejected onto the fabric 3. It is used as a pre-treatment liquid. The first treatment liquid contains a water-soluble cationic flocculant that aggregates the pigment ink. The first treatment liquid containing a water-soluble cationic flocculant aggregates the pigment ink ejected onto the fabric 3, thereby making the color of the pigment ink stand out and suppressing color unevenness.

[0170] The first treatment liquid ejection head 13 mounted on the carriage 10 ejects the first treatment liquid onto the fabric 3 when the inkjet unit 11 is moving in the main scanning direction, before pigment ink is ejected from the ink heads 11c, 11m, 11y and 11k.

[0171] When the inkjet unit 11 is moving in the main scanning direction, the second treatment liquid ejection head 14 ejects the second treatment liquid onto the fabric 3 after the pigment inks have been ejected from the ink heads 11c, 11m, 11y, and 11k.

[0172] (fabric) The types of fibers that make up the fabric include natural fibers (hydrophilic fibers) such as cotton, linen, wool, or silk, and chemical fibers such as rayon, vinylon, nylon, acrylic, polyurethane, polyester, or acetate. [Example]

[0173] The present invention will be specifically described below using examples, but the present invention is not limited thereto. In the following examples, unless otherwise specified, operations were performed at room temperature (25°C). Furthermore, unless otherwise specified, "%", "ppm", and "parts" mean "% by mass", "ppm by mass", and "parts by mass", respectively. Furthermore, in the following examples, "dispersion" refers to a dispersion in which resin particles, pigments, etc. are dispersed in a dispersion medium.

[0174] 1. Preparation of the First Treatment Solution <Preparation of First Treatment Solution A-1> The following components were mixed in 100% by mass to prepare a first treatment liquid A-1. MPT-60 (Mitsubishi Pencil Co., Ltd., flocculant): 3 parts by mass Glycerin: 10 parts by mass Propylene glycol: 30 parts by mass Proxel GXL(S) (preservative): 0.05 parts by weight Olfine E1010 (manufactured by Nissin Chemical Industry Co., Ltd., surfactant): 0.1 parts by mass Ion-exchanged water: 55.85 parts by mass

[0175] <Preparation of first treatment solutions A-2 and A-3> First treatment liquids A-2 and A-3 were prepared in the same manner, except that the type and content of the flocculant were changed as shown in Table 1 and the amount of ion-exchanged water was adjusted so that the total amount was 100 parts by mass.

[0176] Table 1 shows the compositions of the first treatment liquids A-1 to A-3.

[0177] [Table 1]

[0178] MPT-60: Alkylamine epichlorohydrin adduct quaternary salt PAS-M-1L: Methyldiallylamine hydrochloride polymer (Nittobo Medical Co., Ltd.)

[0179] 2. Pigment Ink Preparation 2-1. Preparation of polymers for dispersants <Preparation of Block Copolymer P-1> A flask equipped with an argon gas inlet tube and a stirring blade was charged with 138.8 g of n-butyl methacrylate (hereinafter referred to as "BMA"), 73.5 g of methyl methacrylate (hereinafter referred to as "MMA"), 59.6 g of methacrylic acid (hereinafter referred to as "MAA"), 23.3 g of ethyl 2-methyl-2-n-butyltellanyl propionate (hereinafter referred to as "BTEE"), 14.3 g of dibutyl ditelluride (hereinafter referred to as "DBDT"), 2.6 g of 2,2'-azobisisobutyronitrile (hereinafter referred to as "AIBN"), 166.1 g of methyl ethyl ketone, and 166.1 g of acetonitrile, and the mixture was reacted at 60°C for 18 hours to obtain Reaction Solution A. This produced a prepolymer (hydrophilic block A, weight-average molecular weight (Mw): 6920).

[0180] A mixed solution of 233 g of benzyl methacrylate (hereinafter referred to as "BzMA"), 23.3 g of MAA, 2.6 g of AIBN, 98.0 g of methyl ethyl ketone, and 98.0 g of acetonitrile, which had been previously purged with argon, was added to the reaction solution A, and the mixture was reacted at 60°C for 9 hours to obtain reaction solution AB. As a result, a prepolymer (weight average molecular weight (Mw): 9910) containing a hydrophilic block A and a hydrophobic block B was obtained.

[0181] A mixed solution of 138.8 g of BMA, 73.5 g of MMA, 59.6 g of MAA, 1.3 g of AIBN, 61.1 g of methyl ethyl ketone, and 388.5 g of acetonitrile, which had been previously purged with argon, was added to the reaction solution AB and reacted at 60°C for 23 hours to obtain reaction solution ABA. This yielded block copolymer P-1 (weight average molecular weight (Mw): 13,800, acid value: 100) containing hydrophilic block A, hydrophobic block B, and hydrophilic block A.

[0182] After the reaction was completed, 3.6 kg of methyl ethyl ketone was added to the reaction solution ABA, and the mixture was poured into 21 L of heptane with stirring. The precipitated polymer was filtered by suction and dried to obtain a block copolymer P-1.

[0183] <Preparation of Random Copolymer P-2> A random copolymer P-2 (weight average molecular weight (Mw): 15,500, acid value: 96) having a monomer composition of BMA / BzMA / MMA / MAA=36 / 30 / 19 / 15 was obtained by known radical polymerization.

[0184] 2-2. Preparation of pigment dispersion (anionic pigment dispersion) <Preparation of Pigment Dispersion O-1> A pigment dispersion precursor was obtained by mixing 20.0 parts by weight of magenta pigment with 30% by weight of block copolymer P-1 as a pigment dispersant, 20 parts by weight of propylene glycol (PG), 5 parts by weight of 1,2-hexanediol (1,2-HD), and ion-exchanged water. The resulting pigment dispersion precursor was an aqueous pigment dispersion with a pigment concentration of 20.0%. The magenta pigment was Firstgen Super Magenta RY (CI Pigment Red 122, manufactured by Dainippon Ink and Chemicals, Inc.).

[0185] The pigment dispersion precursor was dispersed using a horizontal media disperser to prepare Pigment Dispersion O-1 (average particle size: 120 nm) with a pigment concentration of 20.0%. The volume-based average particle size of the pigment particles was measured using a particle size distribution analyzer (Zeta Nanosizer 1000HS, manufactured by Malvern Instruments). The horizontal media disperser was a Labostar Mini LMZ015 (zirconia bead diameter 0.3 mm, manufactured by Ashizawa Finetech Co., Ltd.).

[0186] <Preparation of Pigment Dispersion O-2> In the preparation of the above pigment dispersion O-1, a pigment dispersion O-2 (average particle size: 120 nm) with a pigment concentration of 20.0% was prepared using the same method, except that the block copolymer P-1 was changed to the random copolymer P-2.

[0187] <Preparation of Pigment Dispersion O-3> Pigment Dispersion O-3 was prepared in the same manner as in the preparation of Pigment Dispersion O-1, except that Cabo-Jet-4637M (manufactured by Cabot Corporation, pigment concentration 23% by mass) was used as the pigment dispersion.

[0188] 2-3. Preparation of resin dispersion <Synthesis of Resin Dispersion Q-1> A separable flask equipped with a stirrer, temperature sensor, condenser, and argon gas inlet was prepared. An activator solution was prepared by dissolving 2.52 g of anionic activator (sodium dodecylbenzenesulfonate: SDS) and 0.58 g of sodium carbonate in 553 g of ion-exchanged water. The activator solution was then added to the separable flask, and the internal temperature was raised to 80°C while stirring at 330 rpm under an argon gas flow. Meanwhile, a monomer solution was prepared by dissolving 162 g of n-butyl acrylate (BA), 54 g of methyl methacrylate (MMA), 12 g of diacetone acrylamide (DAAM), and 12 g of methacrylic acid (MAA). Next, a solution was prepared by dissolving 0.16 g of polymerization initiator (potassium persulfate: KPS) in 3.06 g of ion-exchanged water, and added to the solution in the separable flask, which had been heated to 80°C. The monomer solution prepared above was added dropwise to this solution over 60 minutes with stirring to produce a dispersion of anionic resin particles. After the dropwise addition was completed, the mixture was heated and stirred for 120 minutes. A solution of 0.16 g of polymerization initiator (potassium persulfate: KPS) dissolved in 3.06 g of ion-exchanged water was then added, and the mixture was stirred for 60 minutes. The mixture was then cooled to 40°C to obtain anionic resin particle dispersion Q-1 (resin concentration 20% by mass). The film elongation was 700%. The "anionic resin particle dispersion" is also referred to as a "resin dispersion."

[0189] <Resin dispersion Q-2~Q-7> Table 2 shows the product names and film elongations of resin dispersions Q-2 to Q-7.

[0190] [Table 2]

[0191] Superflex 460: Daiichi Kogyo Seiyaku Co., Ltd. Impranil DLP-R: manufactured by Sumika Covestro Urethane Co., Ltd. Impranil DLH: manufactured by Sumika Covestro Urethane Co., Ltd. Takelac W-6061: Mitsui Chemicals Superflex 420: Daiichi Kogyo Seiyaku Co., Ltd. Takelac W-6010: Mitsui Chemicals

[0192] 2-4. Preparation of pigment ink <Preparation of Pigment Ink B-1> The following components were mixed in 100% by mass to prepare pigment ink B-1. Anionic pigment dispersion O-1: 4.5 parts by mass Anionic resin particles Q-2: 10 parts by mass Chaline E-370 (manufactured by Nissin Chemical Industry Co., Ltd., silicone acrylic resin): 0.5 parts by mass Glycerin: 10 parts by mass Propylene glycol: 20 parts by mass Proxel GXL(S) (preservative): 0.1 parts by weight Olfine E1010 (manufactured by Nissin Chemical Industry Co., Ltd., nonionic surfactant): 0.5 parts by mass TEGO WET 250 (manufactured by Evonik, nonionic surfactant): 0.1 parts by mass Ion-exchanged water: 54.3 parts by mass

[0193] <Preparation of Pigment Inks B-2 to B-12> Pigment inks B-2 to B-12 were prepared in the same manner as B-1, except that the type of pigment dispersion, the type and mass parts of anionic resin particles, and the type and mass parts of nonionic surfactant were changed as shown in Table 3, and the amount of ion-exchanged water was adjusted so that the total amount was 100 mass parts.

[0194] [Table 3]

[0195] <Preparation of Pigment Ink B-13> Pigment ink B-13 was prepared in the same manner as pigment ink B-2, except that the silicone acrylic resin was omitted and the amount of ion-exchanged water was adjusted so that the total amount was 100 parts by mass.

[0196] <Preparation of Pigment Ink B-14> Pigment ink B-14 was prepared in the same manner as pigment ink B-2, except that a crosslinking agent (Meikanate NS-1) was added and the amount of ion-exchanged water was adjusted so that the total amount was 100 parts by mass.

[0197] 3. Preparation of the second processing solution <Preparation of second treatment liquid C-1> The following components were mixed in 100% by mass to prepare a second treatment liquid C-1. Resin dispersion Q-2: 10 parts by mass Chaline E-370 (manufactured by Nissin Chemical Industry Co., Ltd., silicone acrylic resin): 0.5 parts by mass Glycerin: 10 parts by mass Propylene glycol: 20 parts by mass Proxel GXL(S) (preservative): 0.1 parts by weight Olfine E1010 (manufactured by Nissin Chemical Industry Co., Ltd., surfactant): 0.1 parts by mass Ion-exchanged water: 59.30 parts by mass

[0198] <Preparation of second treatment solutions C-2 to C-6> The type of resin dispersion, and the types and parts by mass of the silicone acrylic resin and nonionic surfactant were changed as shown in Table 4. The amount of ion-exchanged water was adjusted so that the total amount was 100 parts by mass. Otherwise, second treatment liquids C-2 to C-6 were prepared in the same manner as C-1. The nonionic surfactant refers to a nonionic surfactant.

[0199] Table 4 shows the compositions of the second treatment liquids C-1 to C-6.

[0200] [Table 4]

[0201] 4. Imaging and Evaluation 4-1. Inkjet textile printing image formation Cotton satin (100% cotton: product name 60 Cotton Satin, manufactured by Okadaya Co., Ltd.) was prepared as the fabric. The inkjet head printing method in the inkjet printing device was a scan type, and a Konica Minolta Pro120 equipped with an inkjet head KM1024i (Konica Minolta, Inc.) was used. A first treatment liquid head filled with first treatment liquid A, a pigment ink C head, and a second treatment liquid head filled with second treatment liquid B were used. The liquids were applied to the fabric by inkjet printing, followed by drying, to obtain an inkjet-printed image. The first treatment liquid, pigment ink, and second treatment liquid were ejected from the inkjet head at a main scanning speed of 540 dpi and a sub-scanning speed of 720 dpi. dpi refers to the number of ink droplets (dots) per 2.54 cm. The ejection frequency was 22.4 kHz. The image was produced using four passes (four scans). The substrate was then dried in a belt-conveying dryer at 150°C for 3 minutes to obtain a 200mm x 200mm 100% solid printed image. The deposition amounts of the first treatment liquid, the pigment ink, and the second treatment liquid were each 15g / m 2 , 15g / m 2 and 15 g / m 2 These adhesion amounts were each determined from the amount of treatment liquid ejected.

[0202] [Evaluation of color development] The surface reflectance of the printed solid image was measured using a spectrophotometer CM-25d (Konica Minolta, Inc.), and the K / S value at 540 nm was calculated. The K / S value is an index of surface color density defined by the following formula: Kubelka-Munk equation: K / S=(1-R)2 / 2R (K: light absorption coefficient, S: light scattering coefficient, R: surface reflectance) The higher the K / S value, the higher the color density, and the lower the K / S value, the lower the color density. Based on the calculated K / S value, the color development was evaluated according to the following criteria. In the following criteria, A and B were considered to be within the acceptable range.

[0203] Evaluation criteria A: K / S value is 5.0 or more B: K / S value is 4.0 or more and less than 5.0 C:K / S value is 3.0 or more and less than 4.0 D:K / S value is less than 3.0

[0204] [Evaluation of wet rubbing fastness] The wet rub fastness of the image formed on the fabric was evaluated using a crock meter (rubbing tester type I) in accordance with the wet test of JIS L 0849.

[0205] Specifically, a 100 mm x 100 mm area of ​​the formed image was rubbed back and forth 100 times with a white cotton rubbing cloth under a load of 200 g. The white cotton rubbing cloth was wetted with water to a moisture content of approximately 100%. After rubbing, color transfer to the white cotton rubbing cloth was observed, and the wet rubbing fastness was evaluated according to the following criteria. The results are shown in Table 5. According to the following criteria, A and B were considered acceptable. The criteria for color change were based on a staining gray scale, with "Grade 1" indicating the greatest degree of staining.

[0206] Evaluation criteria A: Color change is grade 3 or higher. B: Color change is grade 2-3 (grades 2 and 3 are not included). C: Color change is grade 2. D: Color change is grade 1-2 (grade 2 not included).

[0207] [Injection stability (injection properties)] The prepared pigment ink was ejected using a fixed Konica Minolta KM1024iMHE printer at 25°C and 50% RH using a line method with a droplet volume of 13 pL. After confirming that the filled pigment ink was being ejected from all 60 nozzles at the start of ejection, the printer continued to eject the ink for 60 minutes. After the 60 minutes of continuous ejection, the number of nozzles that had been able to eject ink to the end (the number of nozzles ejecting ink after the 60 minutes of continuous ejection) was counted. The evaluation criteria were as follows. The results are shown in Table 5. Based on the following criteria, A and B were considered to be within the acceptable range.

[0208] Evaluation criteria A: The number of nozzles after 60 minutes of continuous discharge is 60 B: The number of nozzles ejecting after 60 minutes of continuous ejection is 55 or more but less than 60 C: The number of nozzles discharging after 60 minutes of continuous discharging is 50 or more but less than 55 D: The number of nozzles discharged after 60 minutes of continuous discharge is less than 50

[0209] The evaluation results of the ejection properties of the image-formed products and pigment inks of Examples 1 to 12 and Comparative Examples 1 to 5 are shown in Table 5. In Table 5, "ratio (active agent / pigment+resin)" means "the ratio of the nonionic surfactant to the total amount of the pigment, anionic pigment dispersant, and anionic resin particles."

[0210] [Table 5] [Industrial Applicability]

[0211] According to the present invention, it is possible to provide an inkjet printing method capable of forming an image on a fabric that is excellent in image density and wet rub fastness. [Explanation of symbols]

[0212] 1. Inkjet printing equipment 2. Conveyor section 3 Fabric 4 Image forming unit 5 Rail components 6 Purging Tub 8 Drainage tank 10 Carriage 11 Inkjet unit 11y Yellow ink head 11m magenta ink head 11c Cyan ink head 11k black ink head 12a, 12b Treatment liquid ejection head 13 First processing liquid ejection head 14 Second processing liquid ejection head 15 Inkjet head 20 Cleaning Department 21 Cleaning unit rail member 30 Control Unit 102 Belt conveyor 103 Image forming unit 104 Conveyor belt cleaning section 141 Sprinkler Pipe 141a Watering tube 142 Brush Roller 143 Cleaning Blade 144 Cleaning Sponge 145 Heating section 221 Drive roller 222 driven roller 223 Conveyor Belt T1 fabric

Claims

1. an inkjet textile printing method comprising ejecting a pigment ink, a first treatment liquid, and a second treatment liquid onto a fabric from an inkjet head in the order of the first treatment liquid, the pigment ink, and the second treatment liquid, and adhering the first treatment liquid, the pigment ink, and the second treatment liquid to the same location without drying, the first treatment liquid is for fixing at least one of the pigment ink and the second treatment liquid on the surface of the fabric, the first treatment liquid contains a water-soluble cationic flocculant, the second treatment liquid contains a silicone acrylic resin, the pigment ink contains a pigment, an anionic pigment dispersant, anionic resin particles having a film elongation of 600 to 1600%, and a nonionic surfactant; an ink-jet printing method, wherein a ratio of the amount of the nonionic surfactant to the total amount of the pigment, the anionic pigment dispersant, and the anionic resin particles is 0.022 or more and 0.096 or less;

2. 2. The ink-jet printing method according to claim 1, wherein the nonionic surfactant is an acetylene surfactant.

3. 3. The ink-jet printing method according to claim 1, wherein the cationic flocculant is a cationic polymer.

4. 3. The ink-jet printing method according to claim 1, wherein the pigment ink contains a silicone acrylic resin.

5. the anionic pigment dispersant comprises a block copolymer; the block copolymer comprises an ABA type block copolymer consisting of two hydrophilic blocks A arranged at both ends of the molecule and a hydrophobic block B arranged between the two hydrophilic blocks, 3. The ink-jet printing method according to claim 1, wherein the hydrophilic block A interacts or reacts with the cationic flocculant.

6. 3. The ink-jet printing method according to claim 1, wherein the anionic resin particles are made of a urethane resin.

7. 3. The ink-jet printing method according to claim 1, wherein the pigment ink contains a crosslinking agent.

8. 4. The ink-jet printing method according to claim 3, wherein the cationic polymer is a compound having a quaternary ammonium salt group.

9. An inkjet printing ink set comprising a pigment ink, a first treatment liquid, and a second treatment liquid, the pigment ink, the first treatment liquid, and the second treatment liquid are ejected onto a fabric by an inkjet head in this order, and the first treatment liquid, the pigment ink, and the second treatment liquid are adhered to the same location before drying, the first treatment liquid is for fixing at least one of the pigment ink and the second treatment liquid on the surface of the fabric, an anionic pigment dispersant, an anionic resin particle having a film elongation of 600 to 1600%, and a nonionic surfactant; and a ratio of the nonionic surfactant to the total amount of the pigment, the anionic pigment dispersant, and the anionic resin particle is 0.022 or more and 0.096 or less.

10. an inkjet unit that ejects pigment ink onto the fabric while scanning in a main scanning direction; a first treatment liquid ejection head that scans together with the inkjet unit in the main scanning direction and ejects a first treatment liquid onto the fabric; a second treatment liquid ejection head that scans together with the inkjet unit in the main scanning direction and ejects a second treatment liquid onto the fabric, the first treatment liquid ejection head and the second treatment liquid ejection head are disposed on both sides of the inkjet unit in the main scanning direction, an inkjet head including the inkjet unit, the ejection head for the first treatment liquid, and the ejection head for the second treatment liquid; the pigment ink, the first treatment liquid, and the second treatment liquid are ejected onto the fabric by an inkjet head in the order of the first treatment liquid, the pigment ink, and the second treatment liquid, so that the first treatment liquid, the pigment ink, and the second treatment liquid are adhered to the same location before drying; the first treatment liquid is for fixing at least one of the pigment ink and the second treatment liquid on the surface of the fabric, an anionic pigment dispersant, an anionic resin particle having a film elongation of 600 to 1600%, and a nonionic surfactant; and a ratio of the nonionic surfactant to the total amount of the pigment, the anionic pigment dispersant, and the anionic resin particle is 0.022 or more and 0.096 or less.

Images