Transfer medium and production method for same

Abstract

The present invention addresses the problem of providing a transfer medium that makes it possible to easily reuse a peeled base material in transfer printing. A transfer medium according to the present disclosure is produced by a production method comprising an ink receiving part formation step for forming a peelable ink receiving part on the surface of a base material via printing and a first ink printing step for printing a first ink on the peelable ink receiving part. A transfer medium according to the present disclosure is characterized by comprising: a base material; an ink-receptive printing part that is formed on a surface of the base material in such a manner as to be peelable from the base material; and a first ink that is received by the printing part.

Description

Transfer Medium and Method for Manufacturing the Same

[0001] The present disclosure relates to a transfer medium used for transfer printing and a method for manufacturing the same.

[0002] There is known a transfer printing method in which a transfer medium having an image formed thereon is overlaid on a transfer target medium and heat treatment or the like is performed to transfer the image to the transfer target medium. In the base material of the transfer medium, an ink receiving layer for imparting absorbency of ink printed on the base material is generally provided.

[0003] For example, Patent Document 1 describes that an ink receiving layer having releasability is formed by coating a polyester resin film with an ink receiving layer forming treatment agent containing silica, silicone oil, polyurethane resin, and silicone wax. Then, an ink image layer for representing a required image is formed on this ink receiving layer by inkjet printing, and further, a hot melt resin powder layer is formed on the ink image layer to produce a transfer medium, and it is disclosed that a required image is transferred to a transfer target medium using this.

[0004] Japanese Patent Application Laid-Open No. 2022-147673

[0005] However, in the method of Patent Document 1, among the ink receiving layers formed on the base material, the ink receiving layer at the transfer portion (the portion where the ink image layer and the hot melt resin powder layer are formed) is transferred to the transfer target medium, but the ink receiving layers formed on the other portions remain on the base material, so the base material after transfer printing has been discarded. Therefore, an object of the present disclosure is to provide a transfer medium in which the base material peeled off in transfer printing can be easily reused.

[0006] As a result of intensive studies to solve the above problems, the present inventor has formed a peelable ink receiving portion on the surface of the base material at a desired position, specifically, at the position where an image to be transferred is formed, by printing, and by printing ink for forming a target image on this ink receiving portion, it has been found that the ink receiving portion can be prevented from remaining on the base material after transfer printing, and the content of the present disclosure has been completed.

[0007] In other words, the gist of this disclosure is as follows: [1] A method for manufacturing a transfer medium, comprising: an ink receiving portion forming step of forming a releaseable ink receiving portion on the surface of a substrate by printing; and a first ink printing step of printing a first ink onto the releaseable ink receiving portion. [2] The method for manufacturing a transfer medium according to [1], wherein the printing is by inkjet printing or jet dispenser printing. [3] The method for manufacturing a transfer medium according to [1] or [2], wherein the first ink is a color ink containing a colorant. [4] The method for manufacturing a transfer medium according to any one of [1] to [3], further comprising a second ink printing step of printing a second ink onto the printed surface of the first ink, wherein the second ink is a white ink containing a white pigment. [5] The method for manufacturing a transfer medium according to any one of [1] to [4], further comprising an adhesive portion forming step of forming an adhesive portion on the printed surface of the first ink directly or via another member. [6] The method for manufacturing a transfer medium according to [5], wherein the adhesive portion is formed by printing an adhesive resin-containing liquid or by coating with adhesive resin powder. [7] A method for manufacturing a transfer medium according to [5] or [6], wherein a heat treatment is performed after the adhesive portion forming step. [8] A method for manufacturing a transfer medium according to any one of [1] to [7], wherein the transfer medium is used for heat transfer to a transfer medium. [9] A method for manufacturing a transfer medium according to any one of [1] to [8], wherein the transfer medium is used for transfer to a cloth.

[10] A method for manufacturing a transfer print, comprising a contact step of bringing a transfer medium into contact with an ink-receiving portion forming surface of a transfer medium obtained by the manufacturing method according to any one of [1] to [9], and a peeling step of peeling the substrate from the transfer medium.

[11] A method for manufacturing a transfer print according to

[10] , wherein in the peeling step, the peeling is performed so that the ink-receiving portion does not remain on the substrate.

[12] A transfer medium comprising a substrate, an ink-receiving printing portion formed on the surface of the substrate so as to be peelable from the substrate, and a first ink portion formed from a first ink received in the printing portion.

[13] A transfer medium according to

[12] , wherein the ink-receiving printing portion is partially formed on the surface of the substrate.

[14] The transfer medium according to

[12] or

[13] , wherein all of the ink-receptive printing portion and the first ink portion can be transferred onto the surface of the transfer medium.

[15] The transfer medium according to any one of

[12] to

[14] , which is used for thermal transfer onto a transfer medium.

[16] The transfer medium according to any one of

[12] to

[15] , which is used for transfer onto a fabric.

[17] The transfer medium according to any one of

[12] to

[16] , wherein the first ink portion is substantially absent on a substrate on which the ink-receptive printing portion is not formed.

[18] The transfer medium according to any one of

[12] to

[17] , wherein the first ink portion contains a coloring material.

[19] The transfer medium according to any one of

[12] to

[18] , which has a second ink portion directly laminated on the first ink portion, and the second ink portion contains a white pigment.

[20] The transfer medium according to any one of

[12] to

[19] , which further has an adhesive portion containing an adhesive resin laminated directly or via another member on the first ink portion.

[0008] According to the present disclosure, it is possible to prevent an ink-receiving portion from remaining on a substrate peeled off in transfer printing. Therefore, the substrate can be easily reused without being discarded, and transfer printing can be performed again.

[0009] FIG. 1 is a schematic cross-sectional view showing an example of the transfer medium of the present disclosure. FIG. 2 is a schematic cross-sectional view showing another example of the transfer medium of the present disclosure. FIG. 3 is a schematic cross-sectional view showing still another example of the transfer medium of the present disclosure. FIG. 4 is a diagram schematically showing a method for manufacturing a transfer printed matter using the transfer medium of the present disclosure. FIG. 5 is a diagram schematically showing a method for manufacturing a transfer printed matter in a comparative example.

[0010] One embodiment of this disclosure will be described below, but the contents of this disclosure are not limited thereto. Unless otherwise specified in this specification, "A to B" representing a numerical range means "A or more, B or less". Also, "(meth)acrylic acid" means acrylic acid or methacrylic acid, and "(meth)acrylate" means acrylate or methacrylate. The same applies to terms such as "(meth)acryloxy" and "(meth)acryloyl". Furthermore, "structural unit derived from ~" corresponds to a structure in which the carbon-carbon double bond of each monomer component is replaced by a carbon-carbon single bond and two bonds attached to each carbon.

[0011] 1. Manufacturing of the Transfer Medium The manufacturing method of the transfer medium according to this disclosure is characterized by comprising an ink receiving portion formation step of forming a releaseable ink receiving portion on the surface of a substrate by printing, and a first ink printing step of printing a first ink onto the releaseable ink receiving portion. Unlike conventional methods in which ink receiving portions are formed on the entire surface of the substrate by coating, by forming the ink receiving portion by printing at the position where the image to be transferred is formed, it is possible to prevent ink receiving portions from remaining on the substrate after transfer printing. Each step will be described below.

[0012] 1-1. Ink Receptor Formation Process The ink receptor formation process is a process of forming a peelable ink receptor on the surface of the substrate by printing, and can also be described as a process of forming a peelable ink-receptor printed area on the surface of the substrate.

[0013] 1-1-1. The substrate used in the substrate ink receiving section formation process is not particularly limited, but a material that does not shrink easily due to the heat treatment applied before transfer printing is preferred. Specifically, examples of substrate materials include metal, wood, plastic, or paper.

[0014] Examples of the aforementioned metals include aluminum and copper, with aluminum being preferred from a cost standpoint. Examples of the aforementioned plastics include polyolefin resin, polyester resin, polyamide resin, and polycarbonate resin, with polyester resin being preferred from a cost standpoint, and aromatic polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate being more preferred. Examples of the aforementioned paper include plain paper, fine paper, and coated paper. These may have a single-layer structure or a laminated structure. In the case of a laminated structure, the materials of each layer may be the same or different.

[0015] In particular, the base material is preferably plastic from the viewpoint of cost and release properties of the ink receiving area, and more preferably polyester resin, even more preferably aromatic polyester, and especially preferably polyethylene terephthalate from the viewpoint of good heat resistance.

[0016] The substrate may further include a release layer. If the substrate has a release layer, the release layer may be formed on the surface where the ink receiving portion is formed, or on the opposite side of the surface where the ink receiving portion is formed. By providing a release layer on the surface where the ink receiving portion is formed, the interface between the substrate and the ink receiving portion becomes easier to peel off, that is, the peelability of the ink receiving portion is improved. Also, by providing a release layer on the opposite side of the surface where the ink receiving portion is formed, blocking between substrates can be suppressed when the substrates are stacked or rolled up.

[0017] Furthermore, if a release layer is present on the surface where the ink receiving portion is formed, the surface of the release layer may be smooth or it may have an uneven shape. As described later, when peeling the substrate from the transfer medium in transfer printing, delamination occurs at the interface between the ink receiving portion and the substrate (in the embodiment with a release layer, the interface between the ink receiving portion and the release layer). If the surface of the release layer has an uneven shape, the unevenness originating from the release layer is transferred to the printed surface of the resulting transfer print (more specifically, the surface of the ink receiving portion), thereby giving the image in the transfer print a matte finish (a non-glossy effect).

[0018] As the release layer, a known release layer can be used, and among these, a layer obtained by coating with a release agent is preferred. Examples of the release agent include polyethylene wax-based release agents, silicone-based release agents, and fluorine-based release agents.

[0019] If the substrate has a release layer, the thickness of the release layer is not particularly limited, but from the viewpoint of further improving the release properties of the ink receiving portion, it is preferably 10 nm or more, more preferably 30 nm or more, and from the viewpoint of suppressing bulkiness when used as a roll-shaped substrate or transfer medium, it is preferably 2 μm or less.

[0020] The thickness of the substrate is not particularly limited, but is, for example, 10 to 500 μm, and preferably 30 to 200 μm.

[0021] 1-1-2. Printing Method 1 The printing method for forming the peelable ink receiving portion can be any printing method that can selectively form an ink receiving portion at the transfer position (specifically, the position where at least one of the first ink portion, the second ink portion, and the adhesive portion described later is laminated), and can be flexographic printing, offset printing, lithographic printing, gravure printing, screen printing, jet dispenser printing, inkjet printing, etc. In particular, digital printing is preferred because it is plateless, resource-saving, and energy-saving, and among these, jet dispenser printing and inkjet printing are more preferred, and inkjet printing is even more preferred.

[0022] The printing is preferably carried out by applying an ink-receiving area-forming composition to the desired location on the surface of the substrate. The amount of ink-receiving area-forming composition applied per unit area is 5 to 80 g / m². 2 Preferably, 10 to 60 g / m 2 More preferably, 15 to 45 g / m 2 That is particularly preferable.

[0023] The releaseable ink receiving portion may be formed by printing only on the surface to which the first ink, described later, is printed, or it may be formed by printing on a wider surface including the surface to which the first ink is printed. By forming the releaseable ink receiving portion on a wider surface including the surface to which the first ink is printed, quality defects such as deterioration of image quality and transfer failure due to slight misalignment of the printing position of the first ink can be suppressed. The releaseable ink receiving portion is preferably printed so as to extend 0 to 3.0 mm beyond the outer edge of the surface to which the first ink is printed, more preferably so as to extend 0.05 to 2.0 mm, and even more preferably so as to extend 0.10 to 1.5 mm. When performing the adhesive portion formation process described later in the manufacturing of the transfer medium, it is preferable to adjust the width by which the releaseable ink receiving portion extends from the outer edge of the adhesive portion formation surface to within the above range.

[0024] The ink-receiving portion forming composition preferably contains, for example, known components for forming an ink-receiving portion, and more specifically, particles and resin.

[0025] 1-1-2a. Particles The particles contained in the ink-receiving portion forming composition are preferably particles that can maintain their particle shape even in the ink-receiving portion, and are more preferably particles that satisfy at least one of the following requirements (1) to (3). By using such particles, irregularities are given to the surface of the ink-receiving portion, and the absorption of ink into the ink-receiving portion can be increased. In particular, in cases where a large amount of white ink is used as the second ink described later to enhance the color development of the image, even in such cases, it is possible to prevent the white ink from spilling out of the image. (1) Has no glass transition temperature (2) Has a glass transition temperature of 50°C or higher (3) Has a melting point of 80°C or higher

[0026] The glass transition temperature (Tg) in requirement (2) above is preferably 60°C or higher, more preferably 80°C or higher, and there is no particular upper limit, but for example it is 200°C or lower. If the particles satisfy requirement (3), they may or may not have a Tg, and if they do, their Tg may be less than 50°C.

[0027] The melting point in requirement (3) is preferably 90°C or higher, more preferably 100°C or higher, and there is no particular upper limit, but for example it is 200°C or lower. If the particles satisfy requirement (1) or (2), the melting point of the particles may be less than 80°C, or they may not have a melting point at all.

[0028] The glass transition temperature and melting point of the aforementioned particles can be measured by differential scanning calorimetry (DSC) under the following measurement conditions. Measuring instrument: DSC 3500 (product name, manufactured by NETZSCH) Sample container: Sealed aluminum container Sample weight: 10 mg ± 2 mg Measurement method: Thermal analysis is performed in an N2 atmosphere according to the following temperature programs (1) to (5). (1) Increase temperature from 20°C to 200°C at 10°C / min (2) Hold at 200°C for 5 minutes (3) Decrease temperature from 200°C to 20°C at 10°C / min (4) Hold at 20°C for 5 minutes (5) Increase temperature from 20°C to 350°C at 10°C / min After measurement, the glass transition temperature and melting point are analyzed from the DSC curve chart during the temperature increase in (5) using the analysis software proteus Analysis. The value of the midpoint glass transition temperature is adopted as the glass transition temperature, and the top temperature of the endothermic peak is adopted as the melting point. Furthermore, if the particles are organic particles or organic-inorganic composite particles, if a glass transition point cannot be confirmed under the above measurement conditions, or if the thermal decomposition start temperature of the particles is lower than the glass transition temperature, then it is determined that the particles do not have a glass transition point. The thermal decomposition start temperature can be determined using a thermal analyzer (TG-DTA-2000S, manufactured by MacScience) under the conditions of a sample (particle) amount of 10 mg, a heating rate of 10 °C / min (maximum temperature reached 500 °C), and an air flow rate of 20 ml / min. The intersection of the extension of the baseline (horizontal line) of the obtained TG curve (temperature-weight) and the tangent to the weight loss portion (downward-sloping shaded area) can be determined as the thermal decomposition start temperature. In the case of inorganic particles, since a glass transition does not occur, it is determined that the particles do not have a glass transition point.

[0029] The particles are preferably water-insoluble, and more specifically, particles that dissolve in 100 mL of water at 25°C in an amount of 1 g or less are preferred.

[0030] The average particle diameter of the particles is preferably 0.1 to 1 μm, more preferably 0.15 to 0.9 μm, and even more preferably 0.2 to 0.8 μm. By adjusting the average particle diameter of the particles to be above the lower limit, ink absorption and release properties from the substrate (hereinafter sometimes referred to as transfer properties) can be improved, and by adjusting it to be below the upper limit, particle shedding from the ink receiving area can be suppressed and ejection properties during inkjet printing can be improved. The average particle diameter of the particles can be measured, for example, by the following method: Using a particle size distribution analyzer (Multisizer 4e manufactured by Beckman Coulter, Inc.) based on the Coulter counter method, the particle size distribution is measured at 25°C, and the value of D50 in the particle size distribution (volume basis) is calculated. If the calculated value of D50 is 1 μm or more, the value of D50 may be adopted as the average particle diameter. On the other hand, if the calculated D50 value is less than 1 μm, the particle size distribution can be measured separately using a dynamic light scattering particle size distribution analyzer (manufactured by Otsuka Electronics Co., Ltd., model number: FPAR-1000) at 25°C, and the value obtained using cumulant analysis can be adopted as the average particle size.

[0031] The shape of the particles is not particularly limited and may be spherical or have an irregular, non-spherical shape, but it is preferable that they be spherical.

[0032] The material of the aforementioned particles is not particularly limited and may be organic particles, inorganic particles, or organic-inorganic composite particles.

[0033] Examples of organic materials constituting the organic particles include (meth)acrylic resins, urethane resins, polyester resins, olefin resins, silicone resins, melamine resins, urea resins, styrene resins, polycarbonate resins, benzoguanamine resins, styrene-butadiene rubber, acrylonitrile-butadiene rubber, or composite materials of two or more of these. (Meth)acrylic resins, urethane resins, polyester resins, silicone resins, melamine resins, urea resins, styrene resins, polycarbonate resins, benzoguanamine resins, styrene-butadiene rubber, acrylonitrile-butadiene rubber, or composite materials of two or more of these are preferred. In particular, the organic materials constituting the organic particles preferably have a crosslinked structure, and (meth)acrylic resins having a crosslinked structure such as crosslinked polymethyl methacrylate are more preferred.

[0034] Examples of inorganic materials constituting the inorganic particles include metals such as Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; oxides of the metals; hydroxides of the metals; carbides of the metals; nitrides of the metals; sulfides of the metals; carbonates of the metals; and composite materials of two or more of these. In particular, preferred inorganic materials constituting the inorganic particles include silica, metal oxides such as aluminum oxide, titanium oxide, and zirconium oxide, and metal carbonates such as magnesium carbonate, calcium carbonate, strontium carbonate, and barium carbonate.

[0035] Examples of the aforementioned organic-inorganic composite particles include: particles in which inorganic particles are dispersed in an organic substance; particles in which the surface of inorganic particles is coated with an organic substance; polymerizable monomers having hydrolyzable silyl groups such as (meth)acryloxypropyltrimethoxysilane, or (co)polymers of monomers that are hydrolysis condensates of said monomers and other compounds having hydrolyzable silyl groups.

[0036] The ink receiving portion forming composition may contain one or more of the aforementioned particles.

[0037] The particle content is, for example, 20 to 80% by mass, preferably 30 to 65% by mass, and more preferably 35 to 55% by mass, based on 100% by mass of the solid content (non-volatile content) of the ink-receiving portion forming composition. By adjusting the particle content to be above the lower limit, ink absorption is further improved, and by adjusting it to be below the upper limit, a decrease in transferability can be suppressed. In this specification, solid content (non-volatile content) refers to the components excluding the solvent. Furthermore, the particle content is, for example, 20 to 300 parts by mass, preferably 50 to 230 parts by mass, and more preferably 70 to 180 parts by mass, based on 100 parts by mass of the resin described later.

[0038] 1-1-2b. Resin The resin is preferably a resin that functions as a binder in the ink receiving portion. Examples of the resin include vinyl resins, (meth)acrylic resins, polyester resins, olefin resins, urethane resins, fluororesins, silicone resins, epoxy resins, phenoxy resins, phenolic resins, xylene resins, etc., and at least one selected from vinyl resins, (meth)acrylic resins, polyester resins, urethane resins, fluororesins, silicone resins, epoxy resins, phenoxy resins, phenolic resins, and xylene resins is preferred. The ink receiving portion forming composition may contain one or more resins.

[0039] The resin preferably has a glass transition temperature. Preferably, the resin has a glass transition temperature (Tg) of -50°C or higher and less than 50°C, more preferably -30 to 40°C, even more preferably -10 to 30°C, and particularly preferably 0 to 20°C. If the resin has a Tg below the above upper limit, the ink receiving portion can be stretched appropriately, and the wash and tumble dry fastness of the resulting transfer print can be further improved. If the resin has a Tg above the above lower limit, the wet friction fastness of the resulting transfer print can be further improved. The Tg of the resin can be determined by differential scanning calorimetry (DSC).

[0040] In addition, when the resin contains two or more types of resin, or when the resin takes on a core-shell structure, multiple Tg values ​​may be observed. In this case, it is sufficient that at least one Tg value satisfies the above range, and it is preferable that all Tg values ​​satisfy the above range.

[0041] The acid value of the resin is preferably 50 mg KOH / g or less, more preferably 40 mg KOH / g or less, even more preferably 30 mg KOH / g or less, and may even be 0 mg KOH / g. By adjusting the acid value of the resin to the above range, the adhesion between the substrate (particularly a substrate made of polyester such as polyethylene terephthalate) and the ink receiving part tends to decrease, and the peelability from the substrate tends to increase. In addition, since aggregation between the resin and the flocculant described later can be suppressed, the storage stability of the ink receiving part forming composition can be improved. The acid value of the resin can be determined by calculating the number of mg of potassium hydroxide required to neutralize the acid groups (carboxyl groups, sulfo groups, phosphate groups, etc.) present in 1 g of the monomer components constituting the resin, and adopting the obtained value as the acid value of the resin.

[0042] The weight-average molecular weight (Mw) of the resin is, for example, 3,000 to 1,500,000, preferably 5,000 to 1,200,000, and more preferably 10,000 to 1,000,000. In this disclosure, the weight-average molecular weight and number-average molecular weight of the resin can be calculated by a standard polystyrene equivalent method using gel permeation chromatography (GPC).

[0043] When incorporating the resin into the ink-receiving portion-forming composition, it is preferable to add it as an emulsion; that is, in the ink-receiving portion-forming composition, it is preferable that the resin is included as emulsion particles.

[0044] The emulsion is preferably adjusted to a pH of 7 to 10 at 25°C, and more preferably to 7 to 9. The pH of the emulsion can be adjusted by adding pH adjusters such as alkali metal compounds such as sodium hydroxide and potassium hydroxide; alkaline earth metal compounds such as calcium hydroxide and calcium carbonate; ammonia; and water-soluble organic amines such as dimethylaminoethanol, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dimethylpropylamine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, and diethylenetriamine.

[0045] The shape of the emulsion particles is not particularly limited, but is usually spherical.

[0046] The emulsion particles may be resin particles having a single-phase structure or resin particles having a multi-phase structure. The emulsion particles may contain one or more single-phase resin particles, one or more multi-phase resin particles (preferably a core-shell structure), or a mixture of single-phase and multi-phase resin particles (preferably a core-shell structure).

[0047] The average particle size of the emulsion particles is, for example, 30 to 500 nm, preferably 80 to 300 nm, more preferably 100 to 300 nm, and even more preferably 150 to 250 nm. By adjusting the average particle size of the emulsion particles to the above range, it becomes easier to incorporate emulsion particles at a high concentration while maintaining the viscosity of the ink-receiving portion-forming composition within an appropriate range. The average particle size of the emulsion particles may be the cumulant average particle size measured by dynamic light scattering, as shown in the examples described later.

[0048] In particular, from the viewpoint of improving the wash and tumble-dry fastness of the resulting transfer print, it is preferable to use at least one resin selected from the group consisting of (meth)acrylic resins, urethane resins, and polyester resins. The total content of (meth)acrylic resins, urethane resins, and polyester resins in 100% by mass of the resin is preferably 50% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and may be 100% by mass.

[0049] The (meth)acrylic resin is a resin and its derivatives obtained by polymerizing or copolymerizing monomer components containing (meth)acrylic monomers having (meth)acryloyl groups. The total content of structural units derived from (meth)acrylic monomers is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 65% ​​by mass or more, even more preferably 80% by mass or more, particularly preferably 90% by mass or more, and may be 100% by mass, out of 100% by mass of structural units derived from all monomer components constituting the (meth)acrylic resin.

[0050] The (meth)acrylic resin preferably contains one or more structural units derived from alkyl (meth)acrylate. The alkyl (meth)acrylate may be an alkyl (meth)acrylate having a glass transition temperature (Tg) of -20°C or lower (hereinafter sometimes referred to as a low-Tg alkyl (meth)acrylate) and / or C methacrylate. 1-5 It is preferable that the material contains alkyl esters, and more preferably that it contains at least low-Tg alkyl (meth)acrylate esters. By appropriately adjusting the content of these monomer-derived structural units, the Tg of the (meth)acrylic resin can be easily adjusted.

[0051] In this specification, the "glass transition temperature of a homopolymer" may be the value listed in, for example, "Polymer Handbook Third Edition" (by J. Brandrup and E. H. Immergut, 1989, published by John Wiley & Sons, Inc., pp. VI / 209 to VI / 277) (if multiple Tg values ​​are listed, the lowest value may be used). Furthermore, for compounds not listed in "POLYMER HANDBOOK THIRD EDITION," you may use values ​​(calculated values) obtained by computer using commercially available glass transition temperature calculation software (for example, "MATERIALS STUDIO" from Accelrys Software Inc., version: 4.0.0.0, module: Synthia, conditions: calculation with an average polymerization molecular weight of 100,000).

[0052] The Tg of the low-Tg alkyl methacrylate is -20°C or lower, preferably -100 to -20°C, and more preferably -80 to -30°C. Examples of the low-Tg alkyl methacrylate include ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-octyl acrylate, 2-ethylhexyl acrylate, n-nonyl acrylate, isononyl acrylate, etc., and among these, at least one selected from n-butyl acrylate, 2-octyl acrylate, and 2-ethylhexyl acrylate is preferred.

[0053] The aforementioned methacrylic acid C 1-5 Alkyl esters refer to compounds in which the alkyl group constituting the alkyl methacrylate has 1 to 5 carbon atoms. Among these, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, and other C methacrylates are examples of alkyl methacrylates. 1-4 Chain-like alkyl esters are preferred, and methyl methacrylates are more preferred.

[0054] Furthermore, from the viewpoint of further improving transferability, it is preferable that the (meth)acrylic resin contains structural units derived from cyclic alkyl (meth)acrylic acid esters as structural units derived from alkyl (meth)acrylic acid esters. Among cyclic alkyl (meth)acrylic acid esters, cycloalkyl (meth)acrylate and / or isobornyl (meth)acrylate having 4 to 8 carbon atoms constituting the cycloalkyl group is preferred, and cyclohexyl (meth)acrylate and / or isobornyl (meth)acrylate is more preferred.

[0055] The content of structural units derived from alkyl (meth)acrylate is preferably 30 to 100% by mass, more preferably 50 to 98% by mass, and even more preferably 75 to 95% by mass, out of 100% by mass of structural units derived from all monomer components constituting the (meth)acrylic resin. In addition, structural units derived from low-Tg alkyl (meth)acrylate and C methacrylate are also included. 1-5 The total content of structural units derived from alkyl esters is preferably 20 to 100% by mass, more preferably 35 to 90% by mass, and even more preferably 45 to 80% by mass, out of 100% by mass of structural units derived from all monomer components constituting the (meth)acrylic resin. Furthermore, the content of structural units derived from cyclic alkyl (meth)acrylate is preferably 0 to 60% by mass, more preferably 5 to 50% by mass, and even more preferably 15 to 40% by mass, out of 100% by mass of structural units derived from all monomer components constituting the (meth)acrylic resin.

[0056] The (meth)acrylic resin preferably further contains one or more structural units derived from hydroxyl group-containing monomers. When the resin contains structural units derived from hydroxyl group-containing monomers, the dispersion stability of emulsion particles in the ink receiving portion forming composition can be improved if the composition contains an aqueous solvent.

[0057] A hydroxyl group-containing monomer is a monomer having at least one hydroxyl group and at least one polymerizable unsaturated group in its molecule. Examples of polymerizable unsaturated groups include vinyl groups and (meth)acryloyl groups, with (meth)acryloyl groups being preferred.

[0058] Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate; halogen-substituted hydroxyalkyl (meth)acrylates such as 3-chloro-2-hydroxypropyl (meth)acrylate; modified hydroxyalkyl (meth)acrylates such as caprolactone-modified 2-hydroxyethyl (meth)acrylate, 2-(meth)acryloyloxyethyl 2-hydroxyethyl phthalate; di- or polyalkylene glycol mono(meth)acrylates such as diethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate; etc. Among them, hydroxy C 1-10 alkyl (meth)acrylate is preferred, and hydroxy C 1-4 alkyl (meth)acrylate is more preferred.

[0059] The content of the structural unit derived from the hydroxyl group-containing monomer is, for example, 0 to 20% by mass, preferably 1 to 10% by mass, more preferably 3 to 8% by mass, in 100% by mass of the structural units derived from all the monomer components constituting the (meth)acrylic resin.

[0060] The (meth)acrylic resin may further contain one or more structural units derived from an acid group-containing monomer. By containing the structural unit derived from the acid group-containing monomer, the stability of the emulsion particles composed of the (meth)acrylic resin can be enhanced.

[0061] The acid group-containing monomer may be any monomer having at least one acid group and at least one polymerizable unsaturated group in the molecule. Examples of the acid group include a sulfo group, a phosphoric acid group, a carboxy group, etc., and among them, a carboxy group is preferred. Examples of the polymerizable unsaturated group include a vinyl group, a (meth)acryloyl group, etc., and among them, a (meth)acryloyl group is preferred.

[0062] Examples of acid group-containing monomers include unsaturated monocarboxylic acids such as (meth)acrylic acid, cinnamic acid, and crotonic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, and citraconic acid; monoesters of unsaturated dicarboxylic acids such as monomethyl maleic acid, monobutyl maleic acid, monomethyl itaconic acid, and monobutyl itaconic acid; anhydrides of unsaturated dicarboxylic acids such as maleic anhydride; and 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, and 2-acryloyloxyethyl hexahydrophthalic acid. Among these, unsaturated monocarboxylic acids are preferred as acid group-containing monomers, and (meth)acrylic acid is more preferred.

[0063] The content of structural units derived from acid group-containing monomers is, for example, 10.0% by mass or less, preferably 5.0% by mass or less, more preferably 3.5% by mass or less, even more preferably 2.5% by mass or less, and may be 0% by mass, based on 100% by mass of structural units derived from all monomer components constituting the (meth)acrylic resin. By adjusting the content of structural units derived from acid group-containing monomers to the above range, the adhesion between the substrate layer (especially a substrate layer made of polyester such as polyethylene terephthalate) and the ink receiving portion tends to decrease, and the peelability from the substrate tends to be further improved. In addition, since aggregation between the (meth)acrylic resin and the flocculant described later can be suppressed, the storage stability of the ink receiving portion forming composition can be improved. The content of structural units derived from acid group-containing monomers may be 0.5% by mass or more, 1.0% by mass or more, or 1.5% by mass or more, based on 100% by mass of structural units derived from all monomer components constituting the (meth)acrylic resin. By adjusting the content of structural units derived from acid group-containing monomers to the above range, the stability of emulsion particles can be further improved.

[0064] The (meth)acrylic resin may further contain one or more structural units derived from styrene monomers. The styrene monomers include styrene; halogen atoms (e.g., fluorine atoms, chlorine atoms, bromine atoms, iodine atoms); alkyl groups (e.g., methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, etc.). 1-4 Alkyl groups, vinyl groups, alkoxysilyl groups (e.g., trimethoxysilyl group, triethoxysilyl group, etc.) 1-4 Examples include styrene having one or more substituents such as alkoxysilyl groups. The substituent is preferably at least one selected from halogen atoms and alkyl groups. Specific examples of styrene monomers include styrene, vinyltoluene such as α-methylstyrene and p-methylstyrene, tert-butylstyrene, chlorostyrene, chloromethylstyrene, divinylbenzene, p-styryltrimethoxysilane, and 2-styrylethyltrimethoxysilane. Among the styrene monomers, styrene is preferred from the viewpoint of improving the water resistance of the resulting transfer print.

[0065] The content of structural units derived from styrene monomers is, for example, 30% by mass or less, preferably 15% by mass or less, more preferably 5% by mass or less, and even more preferably 0% by mass, out of 100% by mass of structural units derived from all monomer components constituting the (meth)acrylic resin. By adjusting the content of structural units derived from styrene monomers to the above range, the adhesion between the substrate (especially a substrate made of polyester such as polyethylene terephthalate) and the ink receiving portion tends to decrease, and the peelability from the substrate tends to be further improved.

[0066] In particular, the (meth)acrylic resin preferably contains structural units derived from alkyl (meth)acrylate esters and structural units derived from hydroxyl group-containing monomers. The total content of structural units derived from alkyl (meth)acrylate esters and structural units derived from hydroxyl group-containing monomers is preferably 50% by mass or more, more preferably 75% by mass or more, and even more preferably 90% by mass or more, and may be 100% by mass, based on 100% by mass of structural units derived from all monomer components constituting the (meth)acrylic resin.

[0067] Furthermore, the (meth)acrylic resin preferably contains structural units derived from low-Tg alkyl (meth)acrylate esters, and C methacrylate. 1-5 It is more preferable to include at least one structural unit selected from the group consisting of structural units derived from alkyl esters, structural units derived from cyclic alkyl (meth)acrylates, and structural units derived from hydroxyl group-containing monomers, and more preferably a structural unit derived from a low-Tg alkyl (meth)acrylate, a structural unit derived from a hydroxyl group-containing monomer, and C methacrylate. 1-5 It is even more preferable to include structural units derived from alkyl esters and / or structural units derived from cyclic alkyl (meth)acrylate esters.

[0068] (Meth)acrylic resins may have one or more structural units derived from alkyl (meth)acrylates, hydroxyl group-containing monomers, acid group-containing monomers, and monomers other than styrene monomers. Other monomers are not particularly limited and include, for example, other (meth)acrylic monomers such as alkoxyalkyl group-containing (meth)acrylates (e.g., methoxyethyl (meth)acrylate, methoxybutyl (meth)acrylate), piperidine group-containing (meth)acrylates (e.g., 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine); 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2- Examples include addition polymerizable oxazolines such as sopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, and 2-isopropenyl-5-ethyl-2-oxazoline; vinyl monomers such as vinyl acetate, vinyl chloride, and vinyl benzoate; acrylonitrile; (meth)acrylamide monomers such as (meth)acrylamide, N-monomethyl(meth)acrylamide, N-monoethyl(meth)acrylamide, and N,N-dimethyl(meth)acrylamide; olefin monomers such as ethylene and propylene; and the like.

[0069] The polyester resin is not particularly limited as long as it is a polymer having ester bonds in its main chain, and known polyester resins can be used. The polyester resin may be one that has been synthesized as appropriate, or a commercially available product may be used.

[0070] As the polyester resin, condensed polymers of dicarboxylic acids and diol compounds are preferred, such as condensed polymers of aromatic dicarboxylic acids and diol compounds, or condensed polymers of aliphatic dicarboxylic acids and diol compounds.

[0071] Examples of the aforementioned aromatic dicarboxylic acids include phthalic acid, isophthalic acid, and terephthalic acid.

[0072] Examples of the aliphatic dicarboxylic acid include saturated aliphatic dicarboxylic acids or their anhydrides, such as succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, and 1,4-cyclohexanedicarboxylic acid; and unsaturated aliphatic dicarboxylic acids or their anhydrides, such as fumaric acid, maleic acid, itaconic acid, and citraconic acid.

[0073] Examples of the diol compounds include aliphatic diols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, and neopentyl glycol; aromatic alcohols such as alkylene oxide adducts of bisphenol A, such as polyoxypropylene-2,2-bis(4-hydroxyphenyl)propane and polyoxyethylene-2,2-bis(4-hydroxyphenyl)propane; and hydrogenated bisphenol A or its alkylene oxide adducts.

[0074] The urethane resin is not particularly limited as long as it is a resin having a urethane skeleton, and known urethane resins can be used, for example, a reaction product of polyisocyanate and polyol. The urethane resin may be synthesized as appropriate, or a commercially available product may be used. When obtaining the urethane resin by synthesis, the reaction between polyisocyanate and polyol can be carried out by known methods.

[0075] The polyisocyanate is a compound containing at least two isocyanate groups in its molecule. Examples of the polyisocyanate include: chain-like aliphatic isocyanates such as tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate; cyclic aliphatic isocyanates such as 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and 3,3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate; and m- Aromatic isocyanates such as phenylenediisocyanate, p-phenylenediisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenylenediisocyanate, 3,3'-dimethoxy-4,4'-biphenylenediisocyanate, 3,3'-dichloro-4,4'-biphenylenediisocyanate, 1,5-naphthalenediisocyanate, 1,5-tetrahydronaphthalenediisocyanate, xylylenediisocyanate, and tetramethylxylylenediisocyanate; modified forms of these, such as isocyanurates and biuret compounds; and so on. In addition, so-called blocked isocyanates, obtained by reacting the isocyanate groups in these polyisocyanates with a masking agent containing active hydrogen to inactivate them, can also be used. These polyisocyanates may be used individually or in combination of two or more types.

[0076] Examples of the polyol include polyether polyols, polycarbonate polyols, and polyester polyols. Examples of polyether polyols include polyethylene glycol, polypropylene glycol, and polyalkylene glycols such as polytetramethylene glycol. Examples of polycarbonate polyols include reaction products of diols (preferably (poly)alkylene glycols) such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol with dialkyl carbonates such as phosgene and dimethyl carbonate, or cyclic carbonates such as ethylene carbonate. Examples of polyester polyols include condensation polymers of dicarboxylic acids such as aliphatic dicarboxylic acids and aromatic dicarboxylic acids and diol compounds. Specific examples of the aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and diol compounds include the specific examples of aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and diol compounds exemplified in the polyester resins mentioned above. These polyols may be used individually or in combination of two or more types.

[0077] Furthermore, acrylic urethane resin may be used as the urethane resin. In this specification, resins having a urethane skeleton are classified as urethane resins, meaning that acrylic urethane resins are classified as urethane resins and not acrylic resins.

[0078] Examples of acrylic urethane resins include copolymers of acrylic resins and urethane resins. More specifically, examples include copolymers obtained by polymerizing a urethane prepolymer and a (meth)acrylic monomer, in which structural units derived from the (meth)acrylic monomer or side chains of a poly(meth)acrylic structure are introduced into the urethane backbone. Examples of urethane prepolymers include those synthesized using the polyisocyanates and polyols mentioned above. Examples of (meth)acrylic monomers include, but are not limited to, alkyl (meth)acrylates, (meth)acrylic acid, and hydroxyalkyl (meth)acrylates, which were described as monomers constituting (meth)acrylic resins.

[0079] The resin content is, for example, 10 to 80% by mass, preferably 20 to 65% by mass, and more preferably 25 to 55% by mass, based on 100% by mass of the solid content (non-volatile content) of the ink-receiving portion forming composition. By adjusting the resin content to be above the lower limit, the wash and tumble-dry fastness can be further improved, and by adjusting it to be below the upper limit, the amount of particles can be increased, further improving ink absorption.

[0080] 1-1-2c. Coagulant The ink receiving portion forming composition preferably further contains a coagulant. Including a coagulant suppresses bleeding and unevenness of the color ink printed on the ink receiving portion, thereby improving image quality.

[0081] The aforementioned flocculant is preferably a component that floccates components such as colorants contained in color inks. Specifically, the flocculant is preferably a cationic compound, and more preferably a water-soluble cationic compound.

[0082] Examples of the cationic compound include metal salts and cationic polymers, with metal salts being particularly preferred. The ink receiving portion forming composition may contain one or more flocculants.

[0083] The metal salt is preferably a polyvalent metal salt composed of a divalent or higher metal ion and an anion. Examples of metals that constitute the divalent or higher metal ion include metals of Group 2 of the periodic table such as magnesium, calcium, strontium, and barium; and transition metals (preferably transition metals of the fourth period) such as titanium, chromium, copper, and zinc. Among these, metals of Group 2 of the periodic table are preferred, and calcium is more preferred, in terms of their excellent cohesive properties for pigments and the like. Examples of the anion include halide ions such as chloride ions, bromide ions, and iodide ions, as well as nitrate ions, sulfate ions, acetate ions, carbonate ions, and hydroxide ions. Among these, chloride ions, nitrate ions, and sulfate ions are preferred, and chloride ions and nitrate ions are more preferred. Specific examples of the polyvalent metal salt include metal salts of Group 2 of the periodic table such as calcium salts (calcium chloride, calcium nitrate, calcium acetate, etc.), magnesium salts (magnesium chloride, magnesium acetate, magnesium sulfate, etc.), and barium salts (barium chloride, etc.); and transition metal salts such as zinc salts (zinc chloride, zinc sulfate, etc.) and copper salts (copper nitrate, etc.).

[0084] The cationic polymer is preferably a water-soluble polymer having a cationic group. Examples of cationic groups in a cationic polymer include amino groups, ammonium groups, amide groups, imino groups, hydrazino groups, and -NHCONH2 groups. Examples of cationic polymers include polyallylamine, polyvinylamine, polyethyleneimine, and polydiallyldimethylammonium chloride.

[0085] The content of the flocculant is, for example, 0.1 to 20% by mass, preferably 0.5 to 10% by mass, and more preferably 1.0 to 5% by mass, based on 100% by mass of the solid content (non-volatile content) of the ink receiving portion forming composition. By adjusting the content of the flocculant to be above the lower limit, the image quality is further improved, and by adjusting it to be below the upper limit, the decrease in the water resistance of the resulting transfer print can be suppressed. Furthermore, the content of the flocculant is, for example, 0.1 to 50 parts by mass, preferably 1 to 30 parts by mass, and more preferably 3 to 15 parts by mass, based on 100 parts by mass of the resin.

[0086] The total content of the particles, resin, and flocculant is, for example, 50% by mass or more, preferably 70% by mass or more, and more preferably 80% by mass or more, based on 100% by mass of the solid content (non-volatile content) of the ink receiving portion forming composition.

[0087] 1-1-2d. Surfactants The ink-receiving portion forming composition may further contain a surfactant. By using a surfactant, the wettability of the ink-receiving portion forming composition to the substrate is improved.

[0088] As the surfactants mentioned above, it is preferable to use, for example, acetylene glycol-based surfactants, silicone-based surfactants, fluorine-based surfactants, etc. As the acetylene glycol-based surfactants, commercially available products may be used, specifically the Surfinol series (manufactured by Evonik), Olfin series (manufactured by Nisshin Chemical Industry Co., Ltd.), Acetyleneol series (manufactured by Kawaken Fine Chemical Co., Ltd.), etc. As the silicone-based surfactants, polyether-modified silicone-based surfactants are preferably used. As the silicone-based surfactants, commercially available products may be used, specifically the Silface series (manufactured by Nisshin Chemical Industry Co., Ltd.), KF series (manufactured by Nisshin Chemical Industry Co., Ltd.), BYK-345, 347, 348, 349, 3450, 3451, 3455, 3480 (all manufactured by BYK), etc. Examples of the fluorinated surfactants include perfluoroalkyl sulfonic acid compounds, perfluoroalkyl carboxylic acid compounds, perfluoroalkyl phosphate ester compounds, perfluoroalkyl ethylene oxide adducts, and polyoxyalkylene ether polymer compounds having perfluoroalkyl ether groups in their side chains. Commercially available products may be used as the fluorinated surfactants, specifically the Surflon series (manufactured by AGC Seikamika Co., Ltd.) and the Megafac F series (manufactured by DIC Corporation). These surfactants may be used individually or in combination of two or more.

[0089] The surfactants mentioned above are preferably acetylene glycol-based surfactants and silicone-based surfactants, more preferably silicone-based surfactants, and even more preferably polyether-modified silicone-based surfactants.

[0090] The surfactant content is, for example, 0 to 8% by mass based on 100% by mass of the solid content (non-volatile content) of the ink-receiving portion forming composition. However, from the viewpoint of improving wettability to the substrate, 0.1 to 8% by mass is preferred, more preferably 0.5 to 5% by mass, and even more preferably 1.0 to 3% by mass.

[0091] Furthermore, using two or more of the above-mentioned surfactants is preferable because it makes it easier to adjust the wettability of the ink-receiving portion-forming composition to the substrate. In particular, it is preferable to use a silicone-based surfactant and an acetylene glycol-based surfactant in combination, and more preferably to use a polyether-modified silicone-based surfactant and an acetylene glycol-based surfactant in combination. By using these in combination, the wettability of the ink-receiving portion-forming composition to the substrate can be further enhanced.

[0092] When using a silicone-based surfactant and an acetylene glycol-based surfactant in combination, the mass ratio (silicone-based surfactant / acetylene glycol-based surfactant) is preferably 0.1 to 5, and more preferably 0.5 to 2. In particular, it is preferable to adjust the mass ratio of the polyether-modified silicone-based surfactant to the acetylene glycol-based surfactant (polyether-modified silicone-based surfactant / acetylene glycol-based surfactant) to the above range.

[0093] 1-1-2e. Waxes The ink-receiving portion forming composition may contain various waxes, to the extent that the objectives of this disclosure are not hindered. By including waxes, the surface free energy of the ink-receiving portion can be adjusted to lower the wettability of the ink to the ink-receiving portion, thereby further suppressing the bleeding of the ink printed on the ink-receiving portion.

[0094] The waxes may be synthetic or natural waxes. Examples include hydrocarbon waxes such as paraffin wax and polyolefin wax (e.g., polyethylene wax, polypropylene wax, polyethylene / polypropylene wax); fatty acid waxes such as higher fatty acids; fatty acid amide waxes such as fatty acid amides and bis-fatty acid amides; fatty acid ester waxes such as lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids such as glycerides, polyglycol esters of fatty acids, and aliphatic alcohol esters of fatty acids; and modified versions thereof. The ink receiving portion forming composition may contain one or more types of waxes.

[0095] Examples of modified materials include known modified materials. For example, modified paraffin waxes include those obtained by modifying the properties of paraffin wax as a base material through oxidation, chlorination, adjustment of crystal structure, introduction of functional groups, or other chemical or physical treatments. Modified polyolefin waxes include those obtained by introducing polar or reactive groups by chemical modifications such as oxidation, maleic anhydride grafting, acrylic acid grafting, esterification, amidation, copolymerization, or terminal functionalization, using polyolefin wax as a base material.

[0096] Among the waxes, hydrocarbon waxes and / or modified versions thereof are preferred, at least one selected from paraffin wax, polyolefin wax, and their modified versions is more preferred, and at least one selected from paraffin wax, polyethylene wax, and their modified versions is even more preferred.

[0097] The melting point of the waxes is preferably 40°C or higher, and more preferably 40°C or higher and less than 80°C. The melting point of the waxes is also preferably 45 to 150°C, and more preferably 55 to 140°C.

[0098] The waxes are preferably added as an emulsion, that is, the waxes are preferably in the form of emulsion particles.

[0099] The content of the waxes is, for example, 0 to 30% by mass, preferably 5 to 20% by mass, of the solid content (non-volatile content) of the ink receiving portion forming composition. The content of the waxes is, for example, 0 to 100 parts by mass, preferably 30 to 80 parts by mass, per 100 parts by mass of the resin.

[0100] 1-1-2f. Solvent The ink-receiving portion forming composition preferably further contains a solvent. The solvent acts as a diluent to adjust the viscosity of the ink-receiving portion forming composition and improve handling properties such as discharge during printing. The solvent content in the ink-receiving portion forming composition can be set according to the desired viscosity of the ink-receiving portion forming composition and is not particularly limited, but is for example 40 to 95% by mass, preferably 55 to 90% by mass, and more preferably 70 to 88% by mass.

[0101] As the aforementioned solvent, an aqueous solvent is preferred from the viewpoint of reducing environmental impact. An aqueous solvent is a solvent whose main component is water, and the water content in the solvent is, for example, 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, and may be 100% by mass.

[0102] The aforementioned aqueous solvent may contain a water-soluble organic solvent along with water. A water-soluble organic solvent is an organic solvent that dissolves in water at a concentration of 0.01% by mass or more at 25°C and 1 atmosphere. By including a water-soluble organic solvent in the ink-receiving portion forming composition, the moisturizing properties and compatibility with the resin can be improved, and the film-forming properties can be enhanced. The water-soluble organic solvent may be used alone or in combination of two or more types. The content of the water-soluble organic solvent is preferably 15 to 55 parts by mass, more preferably 25 to 50 parts by mass, and even more preferably 30 to 45 parts by mass, per 100 parts by mass of water contained in the ink-receiving portion forming composition.

[0103] Examples of water-soluble organic solvents include lower alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, and tert-butyl alcohol (preferably C 1-4Alcohols; Glycols such as propylene glycol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol; Glycerin; Monoalkyl ethers of monoalkylene glycols (preferably mono-C) such as monoethylene glycol monomethyl ether, monoethylene glycol monoethyl ether, monoethylene glycol monopropyl ether, monoethylene glycol monoisopropyl ether, monoethylene glycol monobutyl ether, monoethylene glycol monoisobutyl ether, monopropylene glycol monomethyl ether, monopropylene glycol monoethyl ether, monopropylene glycol monopropyl ether, monopropylene glycol monoisopropyl ether, monopropylene glycol monobutyl ether, monopropylene glycol monoisobutyl ether, and monoalkyl ether. 2-3 Alkylene glycol mono C 1-4 Alkyl ethers); monoalkyl ethers of dialkylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monoisobutyl ether, etc. (preferably diC 2-3 Alkylene glycol mono C 1-4Alkyl ethers); Monoalkyl ethers of polyalkylene glycols (preferably polyC) such as monomethyl ether of polyethylene glycol, monoethyl ether of polyethylene glycol, monopropyl ether of polyethylene glycol, monoisopropyl ether of polyethylene glycol, monobutyl ether of polyethylene glycol, monoisobutyl ether of polyethylene glycol, monomethyl ether of polypropylene glycol, monoethyl ether of polypropylene glycol, monopropyl ether of polypropylene glycol, monoisopropyl ether of polypropylene glycol, monobutyl ether of polypropylene glycol, monoisobutyl ether of polypropylene glycol, etc. 2-3 Alkylene glycol mono C 1-4 Examples include alkyl ethers; heterocyclic compounds such as 2-pyrrolidone and N-methyl-2-pyrrolidone; ketones such as acetone and methyl ethyl ketone; and so on. The number of moles of alkylene oxide added to the monoalkyl ether of the polyalkylene glycol is preferably 2 to 10, and more preferably 2 to 4.

[0104] In particular, from the viewpoint of further enhancing moisturizing properties, among the water-soluble organic solvents, solvents with a boiling point of 150°C or higher are preferred, solvents with a boiling point of 180°C or higher are more preferred, and solvents with a boiling point of 200°C or higher are even more preferred. Examples of water-soluble organic solvents with a boiling point of 150°C or higher include propylene glycol, diethylene glycol, triethylene glycol, and glycerin. The content of the water-soluble organic solvent that further enhances moisturizing properties is preferably 10 to 50 parts by mass, and more preferably 20 to 40 parts by mass, per 100 parts by mass of water contained in the ink-receiving part forming composition.

[0105] Furthermore, from the viewpoint of further improving compatibility with the resin, the water-soluble organic solvent is preferably a water-soluble organic solvent having a hydrophobic group (e.g., alkyl group) and a hydroxyl group, and more preferably a monoalkyl ether of dialkylene glycol and / or a monoalkyl ether of polyalkylene glycol (number of alkylene oxide addition moles = 2 to 10, preferably 2 to 4), and diC 2-3Alkylene glycol mono C 1-4 Alkyl ethers and / or polycarbonates 2-3 Alkylene glycol mono C 1-4 Alkyl ethers (number of moles of alkylene oxide added = 2 to 10, preferably 2 to 4) are more preferred, and at least one selected from the group consisting of diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, triethylene glycol monobutyl ether, and tripropylene glycol monomethyl ether is even more preferred. The content of the water-soluble organic solvent that further enhances compatibility is preferably 1 to 15 parts by mass, and more preferably 2 to 8 parts by mass, per 100 parts by mass of water contained in the ink-receiving part forming composition.

[0106] 1-1-2 g. Additives The ink receiving portion forming composition may contain additives other than those described above, to the extent that the purpose of this disclosure is not hindered. For example, one or more of the following additives may be included in appropriate amounts: mold release agents, pH adjusters, dispersants, UV absorbers, UV stabilizers, thickeners, wetting agents, plasticizers, stabilizers, defoamers, antioxidants, crosslinking agents, crosslinking accelerators, preservatives, chain transfer agents, chelating agents, etc.

[0107] The ink-receiving portion forming composition preferably has a viscosity of 1 to 15 mPa·s at 25°C, and more preferably 2 to 10 mPa·s. By adjusting the viscosity of the ink-receiving portion forming composition to be above the lower limit, uneven drying can be reduced, and by adjusting it to be below the upper limit, workability such as inkjet ejection stability can be provided. The viscosity in this disclosure can be measured using an E-type viscometer.

[0108] The ink-receiving portion forming composition preferably has a static surface tension of 22 to 35 mN / m at 25°C, more preferably 23 to 32 mN / m, and even more preferably 24 to 30 mN / m. Leveling properties can be improved by adjusting the static surface tension of the ink-receiving portion forming composition to be above the lower limit, and uneven drying can be reduced by adjusting it to be below the upper limit. The static surface tension can be measured using a surface tension meter (manufactured by KYOWA Corporation, part number: DY-500) using the Wilhelmy method.

[0109] Furthermore, the ink receiving portion is formed to be removable from the surface of the substrate. For example, the ink receiving portion can be made removable by using a substrate having a release layer on the surface on which the ink receiving portion is formed, by including a release agent in the composition for forming the ink receiving portion, or by using a resin with low adhesion to the substrate (for example, a resin with a low acid value) as the resin contained in the composition for forming the ink receiving portion.

[0110] 1-1-3. Drying Treatment 1 In the ink receiving portion formation process, if necessary, a drying treatment (hereinafter referred to as drying treatment 1) may be performed to evaporate some or all of the components (i.e., solvent) of the printed ink receiving portion forming composition excluding the solid content. If the ink receiving portion forming composition contains a solvent, the drying treatment 1 can be performed to suppress the flow of the first ink printed on the ink receiving portion, thereby obtaining a clear image.

[0111] In drying treatment 1, of the 100% by mass of the components (i.e., solvent) of the ink-receiving portion forming composition excluding the solid content, preferably 30 to 100% by mass, more preferably 50 to 100% by mass, and even more preferably 80 to 100% by mass are evaporated. By adjusting the amount of evaporation to the above range, the flow of the first ink in the first ink printing process described later can be suppressed. The amount of evaporation can be calculated by dispensing a certain mass of the ink-receiving portion forming composition onto a substrate using an ink-receiving portion forming composition with a known solid content concentration in advance, and then measuring the total mass of the composition and substrate after drying, as well as the mass of the substrate alone, using a precision balance. Then, the drying conditions that result in the desired amount of evaporation can be determined, and the drying treatment described above can be performed under those conditions. The amount of evaporation for the first ink, second ink, and adhesive resin-containing liquid described later can also be determined by the same method.

[0112] The apparatus for performing drying process 1 is not particularly limited, but for example, heating means in various printing devices (e.g., platen heaters, hot air heaters, infrared heaters, etc.) can be used. Among these, a platen heater is preferable from the viewpoint of uniform drying. If the printing device used does not have a platen heater, a planar heating element such as a rubber heater can be installed on the platen of the printing device as an alternative to the platen heater.

[0113] For example, when using a platen heater or a planar heating element as an alternative, the drying process 1 can be performed by heating the substrate from the back surface with the platen heater or planar heating element. The heating temperature of the platen heater or planar heating element is preferably 30 to 80°C, more preferably 40 to 70°C, and even more preferably 40 to 60°C. By adjusting the heating temperature to above the lower limit, the heating time can be shortened, and by adjusting it to below the upper limit, for example, when performing inkjet printing, nozzle blockage due to heat transfer to the inkjet head can be suppressed.

[0114] The drying process 1 may be performed simultaneously with the printing of the ink receiving section, after the printing of the ink receiving section, or simultaneously with and after the printing of the ink receiving section. When the drying process 1 is performed simultaneously with the printing of the ink receiving section, it may be performed continuously from the start to the end of printing, or intermittently, but it is preferable to perform it continuously.

[0115] 1-2. First Ink Printing Process The first ink printing process is a process of printing the first ink onto the printing surface of the ink receiving portion.

[0116] 1-2-1. First Ink The first ink can be any known ink commonly used in this art. The first ink may be a color ink containing a colorant or a clear ink without a colorant, but it is preferable that it be a color ink containing a colorant for forming the desired image. That is, the first ink printing step is preferably an image forming step for printing the desired image.

[0117] If the first ink is a color ink, the hue of the color ink is not particularly limited and can be selected from black, white, and chromatic colors. Chromatic colors include the three primary colors of subtractive color mixing: magenta, yellow, and cyan, as well as colors of different densities such as light cyan, dark yellow, light magenta, and light black. Furthermore, one or more hues selected from red, blue, orange, green, and violet may also be used. In forming the desired image, the first ink printing process may be carried out using only one type of color ink, or it may be carried out using two or more color inks with different hues.

[0118] 1-2-1a. If the first ink is a color ink, the first ink contains a colorant. The colorant contained in the first ink is not particularly limited, but colorants used in ordinary inks can be used. The colorant may be a dye or a pigment, but from the viewpoint of further improving the fastness of the resulting transfer print, it is preferable that it be a pigment. Examples of the pigment include known organic pigments and inorganic pigments, which may be used individually or in combination of two or more types. In addition, if necessary, they may be used in combination with extender pigments.

[0119] Preferably, the pigment is dispersed and stabilized in the first ink with a dispersant. Examples of the dispersant include poly(meth)acrylic acid (salt) such as poly(meth)acrylic acid and poly(meth)acrylic acid salts; copolymers of (meth)acrylic acid (salt) with one or more of the monomer components other than (meth)acrylic acid (salt), such as alkyl (meth)acrylic acid esters, (meth)acrylamide, styrene, maleic acid, maleic anhydride, maleic acid esters, vinyl acetate; polyvinyl alcohol; and polyvinylpyrrolidone. The content of the dispersant is preferably 1 to 100 parts by mass, more preferably 2 to 50 parts by mass, and even more preferably 3 to 30 parts by mass, per 100 parts by mass of the colorant.

[0120] The content of the colorant in the solid content (non-volatile content) of the first ink may be 0% by mass in the case of clear ink, but in the case of color ink, it is preferably 1 to 80% by mass, and more preferably 10 to 60% by mass.

[0121] 1-2-1b. Resin The first ink preferably contains a resin.

[0122] The glass transition temperature (Tg) of the resin is preferably -50 to 10°C, more preferably -45 to 5°C, and even more preferably -40 to 3°C. By adjusting Tg to above the lower limit, the strength of the printed portion formed from the first ink can be improved, and by adjusting it to below the upper limit, the resulting transfer print can be more effectively protected from cracking and other damage even under harsh conditions such as washing and tumble drying.

[0123] The acid value of the resin is preferably 0 to 50 mg KOH / g, more preferably 2 to 40 mg KOH / g, and even more preferably 5 to 30 mg KOH / g.

[0124] The weight-average molecular weight (Mw) of the resin is preferably 50,000 or more, more preferably 200,000 or more, and even more preferably 400,000 or more, from the viewpoint of suppressing the flow of the first ink. Furthermore, the upper limit of the Mw of the resin is preferably 5,000,000 or less, from the viewpoint of film-forming properties and water resistance. In particular, when the resin is a (meth)acrylic resin, it is preferable to adjust the Mw to the above range.

[0125] When the resin is added to the first ink, it is preferable to add it as an emulsion; that is, in the first ink, the resin is preferably included as emulsion particles. The shape of the emulsion particles is not particularly limited, but is usually spherical. The emulsion particles may be resin particles having a single-phase structure, or resin particles having a multi-phase structure (preferably a core-shell structure). The average particle diameter of the emulsion particles is, for example, 30 to 500 nm, preferably 80 to 300 nm, more preferably 100 to 300 nm, and even more preferably 150 to 250 nm.

[0126] Examples of the resins include vinyl resins, (meth)acrylic resins, polyester resins, olefin resins, urethane resins, fluororesins, silicone resins, epoxy resins, phenoxy resins, phenolic resins, xylene resins, and the like. Among these, at least one selected from the group consisting of (meth)acrylic resins, polyester resins, and urethane resins is preferred, with (meth)acrylic resins being particularly preferred.

[0127] The (meth)acrylic resin comprises structural units derived from low-Tg alkyl (meth)acrylate and C methacrylate. 1-5It is preferable to include structural units derived from alkyl esters and / or styrene monomers (Aspect A), and more preferable to include structural units derived from low-Tg alkyl (meth)acrylate and structural units derived from styrene monomers (Aspect B) from the viewpoint of improving the water resistance of the resulting transfer print. Furthermore, it is preferable to include structural units derived from acid group-containing monomers in Aspects A and B (Aspect C) in addition to improving the stability of the (meth)acrylic resin and the durability of the resulting transfer print, such as wash and tumble dry fastness, tends to be further improved. Furthermore, it is preferable to include structural units derived from cyclic alkyl (meth)acrylate in Aspects A, B, and C (Aspect D), or to include structural units derived from hydroxyl group-containing monomers in Aspects A, B, and C (Aspect E), and more preferable to include structural units derived from cyclic alkyl (meth)acrylate and structural units derived from hydroxyl group-containing monomers in Aspects A, B, and C (Aspect F). The low-Tg alkyl (meth)acrylate, methacrylate C 1-5 Alkyl esters, styrene monomers, acid group-containing monomers, cyclic alkyl (meth)acrylates, and hydroxyl group-containing monomers include low-Tg alkyl (meth)acrylates and C methacrylates listed in the "1-1-2b. Resins" section. 1-5 The descriptions of alkyl esters, styrene monomers, acid group-containing monomers, cyclic alkyl (meth)acrylates, and hydroxyl group-containing monomers can be applied mutatis mutandis, including their preferred embodiments.

[0128] Low Tg alkyl methacrylate and C methacrylate in 100% by mass of (meth)acrylic resin. 1-5The total content of structural units derived from alkyl esters, styrene monomers, and acid group-containing monomers is preferably 60% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and may be 100% by mass. The content of structural units derived from low-Tg alkyl methacrylate in 100% by mass of (meth)acrylic resin may be adjusted as appropriate depending on the target Tg, but is preferably 20 to 95% by mass, more preferably 30 to 85% by mass, and even more preferably 40 to 70% by mass. C methacrylate 1-5 The total content of structural units derived from alkyl esters and styrene monomers is preferably 10 to 350 parts by mass, more preferably 25 to 200 parts by mass, and even more preferably 40 to 80 parts by mass, per 100 parts by mass of structural units derived from low-Tg alkyl (meth)acrylate. The content of structural units derived from acid group-containing monomers is low-Tg alkyl (meth)acrylate and C methacrylate. 1-5 The content of structural units derived from alkyl esters and styrene monomers is, for example, 0 to 8 parts by mass, preferably 0.5 to 5 parts by mass, and more preferably 1.0 to 3 parts by mass, per 100 parts by mass of the total structural units derived from alkyl esters and styrene monomers. The content of structural units derived from cyclic alkyl (meth)acrylates is low Tg alkyl (meth)acrylate and C methacrylate. 1-5 The content of structural units derived from alkyl esters and styrene monomers is, for example, 0 to 15 parts by mass, preferably 1 to 10 parts by mass, and more preferably 2 to 8 parts by mass, per 100 parts by mass of the total structural units derived from alkyl esters and styrene monomers. The content of structural units derived from hydroxyl group-containing monomers is low-Tg alkyl (meth)acrylate and C methacrylate. 1-5 For every 100 parts by mass of the total structural units derived from alkyl esters and styrene monomers, the amount is, for example, 0 to 15 parts by mass, preferably 1 to 10 parts by mass, and more preferably 2 to 8 parts by mass.

[0129] The (meth)acrylic resin is a low-Tg alkyl (meth)acrylate or C methacrylate. 1-5The (meth)acrylic resin may have structural units derived from monomers other than alkyl esters, styrene monomers, acid group-containing monomers, cyclic alkyl (meth)acrylic acid esters, and hydroxyl group-containing monomers. Examples of other monomers include those listed in the "1-1-2b. Resins" section. The content of structural units derived from other monomers in 100% by mass of the (meth)acrylic resin is preferably 40% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, and even more preferably 5% by mass or less, and may be 0% by mass.

[0130] The resin content in the solid content (non-volatile content) of the first ink is, for example, 20 to 99% by mass, preferably 30 to 90% by mass, and more preferably 40 to 85% by mass.

[0131] 1-2-1c. Solvent The first ink may further contain a solvent. Organic solvents and aqueous solvents can be suitably used as the solvent, but from the viewpoint of reducing environmental impact, it is preferable to use an aqueous solvent.

[0132] Examples of aqueous solvents include water, or a mixed solvent of water and a water-soluble organic solvent. From the viewpoint of improving moisture retention and compatibility with resin, it is preferable that the aqueous solvent contained in the first ink contains a water-soluble organic solvent along with water. Examples of water-soluble organic solvents contained in the first ink include the water-soluble organic solvents described in the "1-1-2e. Solvent" section, and the preferred embodiments thereof are also the same.

[0133] The content of the water-soluble organic solvent in the aqueous solvent is preferably 5 to 60% by mass, and more preferably 15 to 40% by mass.

[0134] The solvent content in the first ink can be set according to the desired viscosity of the first ink and is not particularly limited, but for example, it is 40 to 90% by mass, preferably 50 to 88% by mass, and more preferably 55 to 85% by mass.

[0135] 1-2-1d. Crosslinking Agent The first ink may further contain a crosslinking agent. It is presumed that the inclusion of a crosslinking agent in the first ink makes the first ink portion formed from the first ink more robust, thereby improving the durability of the resulting transfer print, such as its wash and tumble-dry fastness. Examples of the crosslinking agent include isocyanate compounds, epoxy compounds, melamine compounds, metal chelate compounds, aziridine compounds, mercapto compounds, oxazoline compounds, and the like, with oxazoline compounds being preferred. The crosslinking agent may be used alone or in combination of two or more. The content of the crosslinking agent is not particularly limited, but is, for example, 0 to 10 parts by mass, preferably 0.05 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, and even more preferably 0.2 to 5 parts by mass, per 100 parts by mass of resin contained in the first ink.

[0136] 1-2-1e. Surfactants The first ink may further contain surfactants. Examples of surfactants that can be used in the first ink include those described in the section "1-1-2d. Surfactants", and their preferred embodiments are also the same. The surfactant content in the solid content (non-volatile content) of the first ink is, for example, 0.1 to 4% by mass, preferably 0.5 to 3% by mass, and more preferably 1 to 2.5% by mass.

[0137] 1-2-1f. Additives The first ink may contain other components besides those described above, to the extent that the purpose of this disclosure is not hindered. For example, it may contain in appropriate amounts one or more of the following additives: leveling agents, UV absorbers, UV stabilizers, thickeners, wetting agents, plasticizers, stabilizers, defoamers, antioxidants, crosslinking accelerators, pH adjusters, preservatives, etc.

[0138] The first ink preferably has a viscosity of 2 to 10 mPa·s at 25°C, and more preferably 3 to 7 mPa·s. By adjusting the viscosity of the first ink to be above the lower limit, uneven ink drying can be reduced, and by adjusting it to be below the upper limit, workability such as inkjet ejection stability can be provided.

[0139] 1-2-2. Printing Method 2 The method for printing the first ink can be any printing method that can apply the first ink to the printing portion of the ink receiving portion, for example, flexographic printing, offset printing, lithographic printing, gravure printing, screen printing, inkjet printing, and printing by a jet dispenser can be used. Digital printing is particularly preferred, and among these, inkjet printing and printing by a jet dispenser are more preferred, with inkjet printing being even more preferred.

[0140] Furthermore, it is preferable that the first ink is printed only on the printing surface of the ink receiving portion, that is, it is preferable that the first ink is not printed on the substrate on which the ink receiving portion is not formed.

[0141] In printing with the first ink, the amount of the first ink applied per unit area is 1 to 30 g / m². 2 Preferably, 3 to 25 g / m 2 More preferably, 5 to 20 g / m 2 That is particularly preferable.

[0142] 1-2-3. Drying Treatment 2 In the first ink printing process, a drying treatment (hereinafter referred to as drying treatment 2) may be performed as needed. Drying treatment 2 is a process of evaporating some or all of the components (i.e., solvent) of the printed first ink or the ink receiving part forming composition excluding the solid content. In drying treatment 2, of 100% by mass of the components (i.e., solvent) of the first ink excluding the solid content, preferably 10 to 80% by mass, more preferably 15 to 70% by mass, even more preferably 20 to 60% by mass, and particularly preferably 20 to 50% by mass or 20 to 40% by mass is evaporated. By adjusting the amount of evaporation to be above the lower limit, the flow of the components printed on the printed surface of the first ink can be suppressed, and by adjusting the amount of evaporation to be below the upper limit, peeling at the interface between the first ink and the member laminated on the first ink (second ink or adhesive part) during transfer printing can be suppressed, thereby further improving transferability. If neither the second ink printing process nor the adhesive joint formation process is performed, the heat treatment 5 described later may be performed without performing the drying process 2, or both the drying process 2 and the heat treatment 5 may be performed. The apparatus and conditions for performing the drying process 2 may be the same as those described for performing the drying process 1, including preferred embodiments.

[0143] 1-3. Second Ink Printing Process A second ink printing process may be performed after the first ink printing process, in which the second ink is printed on the printed surface of the first ink.

[0144] 1-3-1. Second Ink While known inks such as color inks and clear inks can be used as the second ink, it is preferable that the second ink be white ink, especially when the first ink is a color ink. This allows the component formed from the second ink to function as a highly opaque base, thereby enhancing the color development of the image formed by the first ink.

[0145] 1-3-1a. The second white pigment ink is preferably a white ink as described above, and more preferably a white ink containing one or more white pigments as colorants. Known white pigments can be used as the white pigment, and among them, titanium dioxide is preferred from the viewpoint of having a high refractive index and excellent opacity, and titanium dioxide with a rutile crystal structure is more preferred.

[0146] Preferably, the white pigment is dispersed and stabilized in the second ink with a dispersant. Examples of the dispersant include those included as dispersants in the first ink. The amount of the dispersant is preferably 1 to 100 parts by mass, and more preferably 2 to 30 parts by mass, per 100 parts by mass of the white pigment.

[0147] The content of white pigment in the solid content (non-volatile content) of the second ink is preferably 20 to 80% by mass, and more preferably 40 to 60% by mass.

[0148] 1-3-1b. Resin The second ink preferably further contains one or more resins. Examples of resins used in the second ink include those listed in the "1-2-1b. Resin" section, and the preferred embodiments thereof are also the same. The resin content in the solid content (non-volatile content) of the white ink is, for example, 20 to 80% by mass, preferably 40 to 60% by mass.

[0149] 1-3-1c. Solvents The second ink preferably further contains one or more solvents. Examples of solvents that can be used in the second ink include those listed in the "1-2-1c. Solvents" section, and the preferred embodiments thereof are also the same. The solvent content in the second ink can be set according to the desired viscosity of the second ink and is not particularly limited, but for example it is 40 to 90% by mass, preferably 50 to 88% by mass, and more preferably 55 to 85% by mass.

[0150] 1-3-1d. Crosslinking Agent The second ink may further contain one or more crosslinking agents. It is presumed that the inclusion of a crosslinking agent in the second ink makes the second ink portion formed from the second ink more robust, thereby improving the durability of the resulting transfer print, such as its wash and tumble-dry fastness. Examples of crosslinking agents used in the second ink include those described in the "1-2-1d. Crosslinking Agent" section, and the preferred embodiments thereof are also the same. The content of the crosslinking agent is not particularly limited, but is, for example, 0 to 10 parts by mass, preferably 0.1 to 8 parts by mass, and more preferably 0.5 to 5 parts by mass, per 100 parts by mass of resin contained in the second ink.

[0151] 1-3-1e. Surfactants The second ink may further contain one or more surfactants. Examples of surfactants that can be used in the second ink include those listed in the "1-1-2d. Surfactants" section, and their preferred embodiments are similar. The surfactant content in the solid content (non-volatile content) of the second ink is, for example, 0.1 to 4% by mass, preferably 0.5 to 3% by mass, and more preferably 1 to 2.5% by mass.

[0152] 1-3-1f. Additives The second ink may contain other components besides those described above, to the extent that the purpose of this disclosure is not hindered. For example, one or more additives such as leveling agents, UV absorbers, UV stabilizers, thickeners, wetting agents, plasticizers, stabilizers, defoamers, antioxidants, crosslinking accelerators, pH adjusters, and preservatives may be included in appropriate amounts.

[0153] The second ink preferably has a viscosity of 2 to 10 mPa·s at 25°C, and more preferably 3 to 7 mPa·s. By adjusting the viscosity of the second ink to be above the lower limit, uneven drying can be reduced, and by adjusting it to be below the upper limit, workability such as inkjet ejection stability can be provided.

[0154] 1-3-2. Printing Method 3 The method for printing the second ink can be any printing method that can apply the second ink to the printing surface of the first ink, such as flexographic printing, offset printing, lithograph printing, gravure printing, screen printing, inkjet printing, or printing using a jet dispenser. Digital printing is particularly preferred, and among these, inkjet printing and printing using a jet dispenser are more preferred, with inkjet printing being even more preferred.

[0155] Furthermore, it is preferable that the second ink is not printed on a substrate in which no ink receiving portion is formed. Also, it is preferable that the printing of the second ink is carried out so as to cover the printed surface of the first ink. The printing of the second ink may be carried out only on the printed surface of the first ink, or it may be printed on the printed surface of the first ink as well as around it.

[0156] In printing with the second ink, the amount of second ink applied per unit area is 30 to 150 g / m². 2 Preferably, 40 to 110 g / m 2 More preferably, 50 to 90 g / m 2 That is particularly preferable.

[0157] 1-3-3. Drying Treatment 3 In the second ink printing process, a drying treatment (hereinafter referred to as drying treatment 3) may be performed as needed. Drying treatment 3 is a process that evaporates some or all of the components (i.e., solvents) of the printed first ink, second ink, and ink receiving part forming composition excluding solids. In drying treatment 3, of 100% by mass of the components of the second ink excluding solids, preferably 10 to 80% by mass, more preferably 15 to 70% by mass, even more preferably 20 to 60% by mass, and particularly preferably 20 to 50% by mass or 20 to 40% by mass is evaporated. By adjusting the amount of evaporation to be above the lower limit, when printing of the adhesive resin-containing liquid is performed in the adhesive part forming process described later, the flow of the adhesive resin-containing liquid can be suppressed. Furthermore, by adjusting the amount of evaporation to be below the upper limit, peeling at the interface between the second ink and the adhesive part during transfer printing can be suppressed, thereby further improving transferability. If the adhesive joint formation process is not performed, the heat treatment 5 described later may be performed without performing the drying treatment 3, or both the drying treatment 3 and the heat treatment 5 may be performed. The apparatus and conditions for performing the drying treatment 3 can be described by analogy to the apparatus and conditions for performing the drying treatment 1, including preferred embodiments.

[0158] 1-4. Adhesive Formation Step After the first ink printing step or after the second ink printing step, an adhesive formation step may be further performed to form an adhesive portion on the printed surface of the first ink, either directly or via another component. That is, if the second ink printing step is performed, the adhesive formation step can be said to be a step to form an adhesive portion on the printed surface of the first ink via a component formed from the second ink, and if the second ink printing step is not performed, it can be said to be a step to form an adhesive portion directly on the printed surface of the first ink. The adhesive portion formed by the adhesive formation step has the role of increasing adhesion to the transfer medium during transfer printing, and can increase the durability of the resulting transfer print, such as wet friction fastness and wash / tumble dry fastness.

[0159] The adhesive portion can be formed by attaching an adhesive resin to the printed surface of the first ink or the printed surface of the second ink, and, if necessary, by undergoing the heat treatment 5 described later. It is preferable that the adhesive resin (specifically, the adhesive resin-containing liquid or adhesive resin powder described later) be attached so as to cover the printed surface of the first ink (or the printed surface of the second ink if the second ink printing process is performed). The adhesive resin (specifically, the adhesive resin-containing liquid or adhesive resin powder described later) may be attached to the printed surface of the second ink if the second ink printing process is performed, or only to the printed surface of the first ink if the second ink printing process is not performed, or it may be attached to the printed surfaces of the first and second inks as well as their surroundings. However, it is preferable not to attach the adhesive resin to a substrate on which no ink receiving portion is formed.

[0160] Methods for adhering the adhesive resin to the printed surface of the first or second ink include printing an adhesive resin-containing liquid, or coating with adhesive resin powder.

[0161] 1-4-1. Printing of Adhesive Resin-Containing Liquids Printing methods for adhesive resin-containing liquids can include, for example, flexographic printing, offset printing, lithographic printing, gravure printing, screen printing, inkjet printing, and jet dispenser printing. Digital printing is particularly preferred, with inkjet printing and jet dispenser printing being more preferred, and inkjet printing being even more preferred.

[0162] In printing with adhesive resin-containing liquids, the amount of adhesive resin-containing liquid applied per unit area is 40 to 250 g / m². 2 Preferably, 70-200 g / m 2 More preferably, 110 to 160 g / m² 2 That is particularly preferable.

[0163] The glass transition temperature (Tg) of the adhesive resin contained in the adhesive resin-containing liquid is preferably -50 to 35°C, more preferably -25 to 20°C, and even more preferably -10 to 10°C. Having a Tg of the adhesive resin above the lower limit suppresses the flow of the adhesive resin-containing liquid during printing, and having a Tg of the adhesive resin below the upper limit allows the resin to soften quickly during transfer printing, improving transferability and, if the transfer medium is fabric, resulting in a good texture for the resulting transfer print.

[0164] The acid value of the adhesive resin is preferably 0 to 50 mg KOH / g, more preferably 2 to 40 mg KOH / g, and even more preferably 5 to 30 mg KOH / g.

[0165] The weight-average molecular weight (Mw) of the adhesive resin is, for example, 5,000 to 700,000, preferably 20,000 to 650,000, and more preferably 30,000 to 550,000. By adjusting the Mw of the adhesive resin to be above the lower limit, durability such as wash and tumble-dry fastness can be further improved, and by adjusting the Mw of the adhesive resin to be below the upper limit, transferability can be further improved.

[0166] The molecular weight distribution of the adhesive resin is not particularly limited and may be, for example, 3 to 20. In particular, from the viewpoint of achieving a better balance between transferability and durability such as wash and tumble dry fastness, it is preferably 4 to 12, more preferably 4 to 10, and even more preferably 5 to 8. The molecular weight distribution is expressed as the ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) (Mw / Mn).

[0167] Examples of the adhesive resins include vinyl resins, (meth)acrylic resins, polyester resins, olefin resins, urethane resins, fluororesins, silicone resins, epoxy resins, phenoxy resins, phenolic resins, and xylene resins. Among these, at least one selected from the group consisting of (meth)acrylic resins, polyester resins, and urethane resins is preferred, and (meth)acrylic resins are more preferred from the viewpoint of suppressing yellowing of the bonded portion.

[0168] The (meth)acrylic resin comprises structural units derived from low-Tg alkyl (meth)acrylate and C methacrylate. 1-5 It is preferable to include structural units derived from alkyl esters and / or styrene monomers (Aspect A), and more preferable to include structural units derived from low-Tg alkyl (meth)acrylate and structural units derived from styrene monomers (Aspect B) from the viewpoint of improving the water resistance of the resulting transfer print. Furthermore, it is preferable to include structural units derived from acid group-containing monomers in Aspects A and B (Aspect C) in addition to improving the stability of the (meth)acrylic resin and the durability of the resulting transfer print, such as wash and tumble dry fastness, tends to be further improved. Furthermore, it is also preferable to include structural units derived from cyclic alkyl (meth)acrylate in Aspects A, B, and C (Aspect D), or to include structural units derived from hydroxyl group-containing monomers in Aspects A, B, and C (Aspect E), and more preferable to include structural units derived from cyclic alkyl (meth)acrylate and structural units derived from hydroxyl group-containing monomers in Aspects A, B, and C (Aspect F). The low-Tg alkyl (meth)acrylate, methacrylate C 1-5 Alkyl esters, styrene monomers, acid group-containing monomers, cyclic alkyl (meth)acrylates, and hydroxyl group-containing monomers include low-Tg alkyl (meth)acrylates and C methacrylates listed in the "1-1-2b. Resins" section. 1-5 The descriptions of alkyl esters, styrene monomers, acid group-containing monomers, cyclic alkyl (meth)acrylates, and hydroxyl group-containing monomers can be applied mutatis mutandis, including their preferred embodiments.

[0169] Low Tg alkyl methacrylate and C methacrylate in 100% by mass of (meth)acrylic resin. 1-5The total content of structural units derived from alkyl esters, styrene monomers, and acid group-containing monomers is preferably 60% by mass or more, more preferably 80% by mass or more, and may be 100% by mass. The content of structural units derived from low-Tg alkyl methacrylate in 100% by mass of (meth)acrylic resin may be adjusted as appropriate depending on the target Tg, but is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, and even more preferably 30 to 60% by mass. C methacrylate 1-5 The total content of structural units derived from alkyl esters and styrene monomers is preferably 20 to 350 parts by mass, more preferably 50 to 250 parts by mass, and even more preferably 70 to 150 parts by mass, per 100 parts by mass of structural units derived from low-Tg alkyl (meth)acrylate. The content of structural units derived from acid group-containing monomers is low-Tg alkyl (meth)acrylate and C methacrylate. 1-5 The content of structural units derived from alkyl esters and styrene monomers is, for example, 0 to 8 parts by mass, preferably 0.5 to 5 parts by mass, and more preferably 1.0 to 3 parts by mass, per 100 parts by mass of the total structural units derived from alkyl esters and styrene monomers. The content of structural units derived from cyclic alkyl (meth)acrylates is low Tg alkyl (meth)acrylate and C methacrylate. 1-5 The content of structural units derived from alkyl esters and styrene monomers is, for example, 0 to 25 parts by mass, preferably 2 to 20 parts by mass, and more preferably 5 to 15 parts by mass, per 100 parts by mass of the total structural units derived from alkyl esters and styrene monomers. The content of structural units derived from hydroxyl group-containing monomers is low-Tg alkyl (meth)acrylate and C methacrylate. 1-5 For every 100 parts by mass of the total structural units derived from alkyl esters and styrene monomers, the amount is, for example, 0 to 15 parts by mass, preferably 1 to 10 parts by mass, and more preferably 2 to 8 parts by mass.

[0170] The (meth)acrylic resin is a low-Tg alkyl (meth)acrylate or C methacrylate. 1-5The (meth)acrylic resin may have structural units derived from monomers other than alkyl esters, styrene monomers, acid group-containing monomers, cyclic alkyl (meth)acrylic acid esters, and hydroxyl group-containing monomers. Examples of other monomers include those listed in the "1-1-2b. Resins" section. The content of structural units derived from other monomers in 100% by mass of the (meth)acrylic resin is preferably 40% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, and even more preferably 5% by mass or less, and may be 0% by mass.

[0171] When adding the adhesive resin to the adhesive resin-containing liquid, it is preferable to add it as an emulsion; that is, it is preferable that the adhesive resin is contained in the adhesive resin-containing liquid as emulsion particles. The shape of the emulsion particles is not particularly limited, but is usually spherical. The emulsion particles may be resin particles having a single-phase structure, or resin particles having a multi-phase structure (preferably a core-shell structure). The average particle diameter of the emulsion particles is, for example, 30 to 500 nm, preferably 80 to 300 nm, more preferably 100 to 300 nm, and even more preferably 150 to 250 nm.

[0172] The content of adhesive resin in the solid content (non-volatile content) of the adhesive resin-containing liquid is, for example, 60 to 100% by mass, preferably 80% to 99.5% by mass, and more preferably 90% to 99% by mass.

[0173] The adhesive resin-containing liquid may further contain one or more surfactants. The surfactants contained in the adhesive resin-containing liquid are the same as those described in the section "1-1-2d. Surfactants," including their preferred embodiments. The surfactant content in the solid content (non-volatile content) of the adhesive resin-containing liquid is, for example, 0.1 to 8% by mass, preferably 0.5 to 5% by mass, and more preferably 1 to 3% by mass.

[0174] The adhesive resin-containing liquid preferably further contains one or more solvents. The solvents act as diluents to adjust the viscosity of the adhesive resin-containing liquid. The description of "1-2-1c. Solvents" can be applied mutatis mutandis to the solvents contained in the adhesive resin-containing liquid, including their preferred embodiments. The solvent content in the adhesive resin-containing liquid is not particularly limited and can be set according to the desired viscosity of the adhesive resin-containing liquid, but is, for example, 40 to 90% by mass, preferably 50 to 88% by mass, and more preferably 60 to 85% by mass.

[0175] The adhesive resin-containing liquid may contain one or more additives other than the components described above, to the extent that the purpose of this disclosure is not hindered. For example, it may contain appropriate amounts of additives such as crosslinking agents, leveling agents, dispersants, UV absorbers, UV stabilizers, thickeners, wetting agents, plasticizers, stabilizers, defoamers, antioxidants, crosslinking accelerators, pH adjusters, and preservatives.

[0176] The adhesive resin-containing liquid preferably has a viscosity of 2 to 10 mPa·s at 25°C, and more preferably 3 to 7 mPa·s. By adjusting the viscosity of the adhesive resin-containing liquid to be above the lower limit, uneven drying can be reduced, and by adjusting it to be below the upper limit, workability such as inkjet ejection stability can be provided.

[0177] In printing adhesive resin-containing liquids, a drying process (hereinafter referred to as "drying process 4") may be performed as needed to evaporate some or all of the components (i.e., the solvent) of the printed adhesive resin-containing liquid excluding the solids. The apparatus and conditions for performing drying process 4 can be described by analogy to the description of the apparatus and conditions for performing drying process 1, including preferred embodiments.

[0178] 1-4-2. Coating of Adhesive Resin Powder The coating of adhesive resin powder can be performed by applying the adhesive resin powder to the object to which the adhesive resin is to be attached (the second ink if the second ink printing process is performed, or the first ink if the second ink printing process is not performed) while the object is in a wet state.

[0179] Means for attaching adhesive resin powder to the first or second ink while it is wet include, for example, a method of sprinkling and attaching the adhesive resin powder to the first or second ink after printing but before it dries, a method of bringing the adhesive resin powder to the ink by airflow and attaching it, a method of bringing the adhesive resin powder to the ink by electrostatic force and attaching it, and a method of attaching it by dipping, passing through the adhesive resin powder.

[0180] As described above, it is preferable not to adhere adhesive resin powder to substrates where ink receiving areas are not formed. However, depending on the method of applying the adhesive resin powder, it may adhere to substrates where ink receiving areas are not formed. In such cases, the adhesive resin attached to the unwanted parts can be removed using a known adhesive resin powder removal device (for example, a device that vibrates the substrate to remove the adhesive resin powder, a suction device that removes the adhesive resin powder by suction, an airbrush device that removes the adhesive resin powder from the substrate using a gas flow, etc.).

[0181] The resin constituting the adhesive resin powder is preferably a hot-melt resin. The melting point of the resin constituting the adhesive resin powder is preferably 100 to 140°C.

[0182] Examples of resins constituting the adhesive resin powder include vinyl resins, (meth)acrylic resins, polyester resins, olefin resins, urethane resins, fluororesins, silicone resins, epoxy resins, phenoxy resins, phenolic resins, and xylene resins. Among these, at least one selected from the group consisting of (meth)acrylic resins, polyester resins, and urethane resins is preferred.

[0183] The volume-average particle size of the adhesive resin powder is preferably 30 to 300 μm.

[0184] When coating with adhesive resin powder, it is preferable to perform the heat treatment 5 described below after coating. The heat treatment 5 causes the adhesive resin powder to melt and form a film, thereby forming an adhesive portion. In this case, it is preferable that the temperature of the heat treatment 5 is higher than the melting point of the resin constituting the adhesive resin powder.

[0185] 1-5. Heat Treatment 5 In the manufacture of the transfer medium, it is preferable to perform a heat treatment (hereinafter referred to as heat treatment 5) after at least one of the following steps: the ink receiving part formation step, the first ink printing step, the second ink printing step, and the adhesive part formation step. It is preferable to perform heat treatment 5 in the final stage of the manufacture of the transfer medium. By performing heat treatment 5, the printed components can be thoroughly dried.

[0186] In the heat treatment 5, of the total 100% by mass of the components (ink-receiving portion forming composition, first ink, second ink, adhesive resin-containing liquid) printed before the heat treatment 5, excluding the solid content, preferably 80 to 100% by mass, more preferably 90 to 100% by mass is evaporated.

[0187] The heat treatment 5 is preferably carried out by heating or contact with hot air. The heating temperature or hot air temperature is preferably 40 to 180°C, more preferably 80 to 160°C, and even more preferably 100 to 160°C. The heating time or hot air contact time is preferably 0.5 to 30 minutes, and more preferably 1 to 20 minutes.

[0188] 2. Transfer Medium By the above manufacturing method, a transfer medium can be manufactured having a substrate, an ink-receiving printed portion formed on the surface of the substrate so as to be detachable from the substrate, and a first ink portion formed from the first ink received in the printed portion. Such a transfer medium is also included in the scope of this disclosure.

[0189] Figures 1 to 3 are schematic cross-sectional views showing an example of a transfer medium.

[0190] In Figure 1, the transfer medium 100 includes a substrate 1, an ink-receiving printed portion 2 formed on the substrate 1, and a first ink portion 3 formed from the first ink received in the printed portion 2. In Figures 1 to 3, the structure is shown as if the first ink portion 3 is laminated on the ink-receiving printed portion 2 in order to clearly illustrate the configuration of each component. However, since the first ink portion 3 is a component formed from the first ink received in the printed portion 2, it is preferable that at least a part of the first ink portion 3 is formed in the ink-receiving printed portion 2, and the entire first ink portion 3 may be formed in the ink-receiving printed portion 2. Furthermore, the ink-receiving printed portion 2 may be formed only on the surface of the substrate 1 that corresponds to the surface on which the first ink portion 3 is formed, or, as shown in Figures 1 to 3, it may be formed on a wider surface that includes the surface on which the first ink portion 3 is formed. By forming the ink-receiving printed portion 2 on a wider surface that includes the surface on which the first ink portion 3 is formed, quality defects such as deterioration of image quality and transfer failure due to slight misalignment of the printing position of the first ink portion 3 can be suppressed. The ink-receiving printed portion 2 is preferably formed to protrude 0 to 3.0 mm from the outer edge of the first ink portion 3, more preferably 0.05 to 2.0 mm, and even more preferably 0.10 to 1.5 mm. If the transfer medium 100 has an adhesive portion 5 described later, it is preferable to adjust the width by which the ink-receiving printed portion 2 protrudes from the outer edge of the adhesive portion 5 to within the above range.

[0191] The transfer medium of this disclosure may further have an adhesive portion containing an adhesive resin laminated directly or via another member on the first ink portion. Figure 2 shows an example of a configuration in which the transfer medium 100 further has an adhesive portion 5 containing an adhesive resin. The adhesive portion 5 may be laminated directly on the first ink portion 3 as shown in Figure 2, or it may be laminated on the first ink portion 3 via another member as shown in Figure 3, which will be described later. Also, as shown in Figures 2 and 3, the adhesive portion 5 may be formed only on the portion where the first ink portion 3 is formed, or it may be formed not only on the portion where the first ink portion 3 is formed but also around it. However, it is preferable that the adhesive portion 5 is not formed on the substrate 1 where the ink-receiving printing portion 2 is not formed. Furthermore, in the transfer medium 100 having the adhesive portion 5, it is preferable that no other members are laminated on the adhesive portion 5, i.e., the adhesive portion 5 is the outermost layer.

[0192] The transfer medium of this disclosure may have a second ink portion directly laminated on the first ink portion. Figure 3 shows an example of a configuration in which the transfer medium 100 further has a second ink portion 4. It is preferable that the second ink portion 4 is directly laminated on the first ink portion 3. When the transfer medium 100 has a second ink portion 4, an adhesive portion 5 may or may not be formed on the second ink portion 4, but it is preferable that an adhesive portion 5 is formed on the second ink portion 4. Also, as shown in Figure 3, the second ink portion 4 may be formed only in the portion where the first ink portion 3 is formed, or it may be formed in addition to the portion where the first ink portion 3 is formed and also around it, but it is preferable that it is formed only in the portion where the first ink portion 3 is formed. However, it is preferable that the second ink portion 4 is not formed on the substrate 1 in which the ink-receiving printing portion 2 is not formed.

[0193] The following describes in detail each component constituting the transfer medium of this disclosure.

[0194] 2-1. Substrate The description in "1-1-1. Substrate" can be applied mutatis mutandis to the substrate of the transfer medium of this disclosure.

[0195] 2-2. Ink-receiving printed portion The ink-receiving printed portion is a member (i.e., an ink-receiving portion) that is formed by printing and capable of receiving ink. Preferably, the ink-receiving printed portion is formed by printing only at the transfer location, that is, the ink-receiving printed portion is formed only on the substrate surface, rather than on the entire substrate surface.

[0196] The ink-receiving printing portion preferably contains particles and resin.

[0197] The description in "1-1-2a. Particles" can be applied mutatis mutandis to the particles contained in the ink-receiving printing portion. The ink-receiving printing portion may contain one or more types of the aforementioned particles. The content of the particles is, for example, 20 to 80% by mass, preferably 30 to 65% by mass, and more preferably 35 to 55% by mass, of 100% by mass of the ink-receiving printing portion. By adjusting the particle content to be above the lower limit, ink absorption and transferability can be further improved, and by adjusting it to be below the upper limit, a decrease in transferability can be suppressed. Furthermore, the content of the particles is, for example, 20 to 300 parts by mass, preferably 50 to 230 parts by mass, and more preferably 70 to 180 parts by mass, per 100 parts by mass of the resin described later.

[0198] The description in "1-1-2b. Resin" can be applied mutatis mutandis to the resin contained in the ink-receiving printed portion. However, in the ink-receiving printed portion, the shape of the resin may be granular or continuous, but a continuous structure is preferred. The ink-receiving printed portion may contain one or more types of the resin. The resin content is, for example, 10 to 80% by mass, preferably 20 to 65% by mass, and more preferably 25 to 55% by mass, of 100% by mass of the ink-receiving printed portion. By adjusting the resin content to be above the lower limit, the wash and tumble-dry fastness can be further improved, and by adjusting it to be below the upper limit, the amount of particles can be increased, and the ink absorption can be further improved.

[0199] The ink-receiving printing portion may further contain a flocculant. The description in "1-1-2c. Flocculant" can be applied mutatis mutandis to the flocculant contained in the ink-receiving printing portion. The ink-receiving printing portion may contain one or more types of the flocculant. The content of the flocculant is, for example, 0.1 to 20% by mass, preferably 0.5 to 10% by mass, and more preferably 1.0 to 5% by mass, based on 100% by mass of the ink-receiving printing portion. By adjusting the content of the flocculant to be above the lower limit, the image quality can be further improved, and by adjusting it to be below the upper limit, the decrease in the water resistance of the resulting transfer print can be suppressed. The content of the flocculant is, for example, 0.1 to 50 parts by mass, preferably 1 to 30 parts by mass, and more preferably 3 to 15 parts by mass, based on 100 parts by mass of the resin.

[0200] The total content of the particles, resin, and flocculant is, for example, 50% by mass or more, preferably 70% by mass or more, and more preferably 80% by mass or more, based on 100% by mass of the ink-receiving printing area.

[0201] The ink-receiving printed portion may further contain a surfactant. The description in "1-1-2d. Surfactants" can be applied mutatis mutandis to the surfactant contained in the ink-receiving printed portion. The ink-receiving printed portion may contain one or more of the surfactants. The surfactant content is, for example, 0 to 8% by mass per 100% by mass of the ink-receiving printed portion, but from the viewpoint of improving wettability to the substrate, it is preferably 0.1 to 8% by mass, more preferably 0.5 to 5% by mass, and even more preferably 1.0 to 3% by mass.

[0202] The ink-receiving printing portion may further contain waxes. The description in "1-1-2e. Waxes" can be applied mutatis mutandis to the waxes contained in the ink-receiving printing portion. The content of the waxes is, for example, 0 to 30% by mass, preferably 5 to 20% by mass, of 100% by mass of the ink-receiving printing portion. The content of the waxes is, for example, 0 to 100 parts by mass, preferably 30 to 80 parts by mass, per 100 parts by mass of the resin.

[0203] The ink-receiving printing portion may contain one or more additives other than those described above, to the extent that the purpose of this disclosure is not hindered. The description of "1-1-2f. Additives" can be applied mutatis mutandis to such additives.

[0204] The ink-receiving printed portion is formed on the substrate surface so as to be detachable from the substrate. For example, the ink-receiving printed portion can be formed so as to be detachable from the substrate by using a substrate having a release layer on the surface on which the ink-receiving printed portion is formed, by including a release agent in the ink-receiving printed portion, or by using a resin with low adhesion to the substrate (for example, a resin with a low acid value) as the resin included in the composition for forming the ink-receiving portion.

[0205] The thickness of the ink-receiving printed area is preferably 30 nm to 30 μm, and more preferably 100 nm to 20 μm. Adjusting the thickness of the ink-receiving printed area to be above the lower limit tends to improve image quality and ink absorption, while adjusting it to be below the upper limit can reduce manufacturing costs.

[0206] 2-3. First Ink Portion The first ink portion of the transfer medium of this disclosure is formed from a first ink received in the ink-receiving printing portion. The first ink may be received in any part thereof (i.e., at least a part of the first ink portion may be formed in the ink-receiving printing portion), or all of the first ink may be received (i.e., all of the first ink portion may be formed in the ink-receiving printing portion).

[0207] Preferably, the first ink portion constitutes an image such as characters or patterns, which is the object to be transferred.

[0208] The description in "1-2-1. First Ink" can be applied mutatis mutandis to the first ink received in the ink-receiving printing section. Therefore, it is preferable that the first ink section contains a colorant. The description in "1-2-1a. Colorant" can be applied mutatis mutandis to the colorant contained in the first ink section. The first ink section may contain one or more of the above-mentioned colorants. The content of the above-mentioned colorants in the first ink section may be 0% by mass, but is preferably 1 to 80% by mass, and more preferably 10 to 60% by mass.

[0209] The first ink portion preferably further contains a resin. The description in "1-2-1b. Resin" can be applied mutatis mutandis to the resin contained in the first ink portion. However, in the first ink portion, the resin may be in the form of particles or in a continuous structure, but a continuous structure is preferred. The first ink portion may contain one or more types of resin.

[0210] The resin content in the first ink portion is, for example, 20 to 99% by mass, preferably 30 to 90% by mass, and more preferably 40 to 85% by mass.

[0211] Furthermore, if the first ink portion contains a resin, the resin may have a structure crosslinked with one or more crosslinking agents. The description in "1-2-1d. Crosslinking Agents" can be applied mutatis mutandis to the crosslinking agent. The amount of the crosslinking agent is not particularly limited, but is, for example, 0 to 10 parts by mass, preferably 0.05 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, and even more preferably 0.2 to 5 parts by mass, per 100 parts by mass of the resin.

[0212] The first ink portion may further contain a surfactant. Examples of surfactants included in the first ink portion are those described in the section "1-1-2d. Surfactants," and preferred embodiments thereof are also described therein. The first ink portion may contain one or more of the surfactants. The surfactant content in the first ink portion is, for example, 0.1 to 4% by mass, preferably 0.5 to 3% by mass, and more preferably 1 to 2.5% by mass.

[0213] The first ink portion may further contain additives other than those described above, to the extent that the purpose of this disclosure is not hindered. The description of additives in "1-2-1f. Additives" can be applied mutatis mutandis to the additives contained in the first ink portion. The first ink portion may contain one or more of the above-mentioned additives.

[0214] 2-4. Second Ink Section As described above, the transfer medium of this disclosure may have a second ink section directly laminated on the first ink section. The second ink section preferably functions as an opaque base to enhance the color development of the image formed by the first ink section, and therefore, the second ink section preferably contains a white pigment. The description in "1-3-1a. White Pigment" can be applied mutatis mutandis to the white pigment contained in the second ink section. The second ink section may contain one or more of the white pigments. The content of the white pigment in the second ink section is preferably 20 to 80% by mass, and more preferably 40 to 60% by mass.

[0215] The second ink portion preferably further contains a resin. Examples of resins included in the second ink portion are those listed in the "1-2-1b. Resin" section, and the preferred embodiments thereof are also the same. However, in the second ink portion, the resin may be in particulate form or in a continuous structure, but a continuous structure is preferred. The second ink portion may contain one or more types of the resin. The resin content in the second ink portion is, for example, 20 to 80% by mass, preferably 40 to 60% by mass.

[0216] Furthermore, if the second ink portion contains a resin, the resin may have a structure crosslinked with one or more crosslinking agents. Examples of such crosslinking agents include those listed in the "1-2-1d. Crosslinking Agents" section, and the preferred embodiments thereof are also the same. The amount of the crosslinking agent is not particularly limited, but is, for example, 0 to 10 parts by mass, preferably 0.1 to 8 parts by mass, and more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the resin.

[0217] The second ink portion may further contain a surfactant. Examples of surfactants included in the second ink portion are those listed in the "1-1-2d. Surfactants" section, and the preferred embodiments are the same. The surfactant content in the second ink portion is, for example, 0.1 to 4% by mass, preferably 0.5 to 3% by mass, and more preferably 1 to 2.5% by mass.

[0218] The second ink portion may contain additives other than those described above, to the extent that the purpose of this disclosure is not hindered. The description of additives in "1-3-1f. Additives" can be applied mutatis mutandis to the additives contained in the second ink portion. The second ink portion may contain one or more of the above-mentioned additives.

[0219] The thickness of the second ink portion is preferably 1 to 50 μm, more preferably 3 to 40 μm, and even more preferably 5 to 35 μm.

[0220] 2-5. Adhesive portion As described above, the transfer medium of this disclosure may further have an adhesive portion containing an adhesive resin laminated directly or via other components on the first ink portion. Having an adhesive portion can improve the adhesion between the transfer target object, such as the first ink portion, and the transfer medium, and therefore can improve the wet friction fastness and wash / tumble dry fastness of the resulting transfer print.

[0221] Examples of adhesive resins included in the adhesive portion include the resin described as an adhesive resin included in the adhesive resin-containing liquid in section "1-4-1. Printing of Adhesive Resin-Containing Liquid," and the resin described as a resin constituting the adhesive resin powder in section "1-4-2. Coating of Adhesive Resin Powder," and the preferred embodiments thereof are the same. However, in the adhesive portion, the shape of the adhesive resin may be particulate or continuous, but a continuous structure is preferred. The adhesive portion may contain one or more types of adhesive resins. The content of the adhesive resin in the adhesive portion is, for example, 60 to 100% by mass, preferably 80% to 99.5% by mass, and more preferably 90% to 99% by mass.

[0222] The adhesive portion may further contain one or more surfactants. The surfactants included in the adhesive portion are the same as those described in the section "1-1-2d. Surfactants," including their preferred embodiments. The surfactant content in the adhesive portion is, for example, 0.1 to 8% by mass, preferably 0.5 to 5% by mass, and more preferably 1 to 3% by mass.

[0223] The adhesive portion may contain one or more additives other than the components described above, to the extent that the purpose of this disclosure is not hindered. For example, it may contain appropriate amounts of additives such as crosslinking agents, leveling agents, dispersants, UV absorbers, UV stabilizers, thickeners, wetting agents, plasticizers, stabilizers, defoamers, antioxidants, crosslinking accelerators, pH adjusters, and preservatives.

[0224] The thickness of the adhesive portion is preferably 1 to 200 μm, more preferably 3 to 180 μm, and even more preferably 5 to 150 μm. However, when the adhesive portion is formed by printing an adhesive resin-containing liquid, the thickness of the adhesive portion can be made thinner, for example, 1 to 70 μm or 5 to 50 μm.

[0225] 2-6. Uses of the Transfer Medium The transfer medium of this disclosure can be suitably used for transferring images onto a transfer medium, that is, suitably used for manufacturing transfer printed materials. In this disclosure, "transfer printing" refers to transferring the first ink portion to the transfer medium by bringing the transfer medium into contact with the printed surface of the transfer medium (specifically, the surface on which the ink-receiving printed portion and the first ink portion are formed), and then peeling off the substrate. By using the transfer medium of this disclosure, no ink-receiving portion remains on the substrate after peeling, so the substrate can be easily reused.

[0226] In particular, the transfer medium of this disclosure is suitably used for thermal transfer to a transfer medium. Furthermore, the transfer medium of this disclosure is suitably used for transfers where the transfer medium is a fabric.

[0227] The following describes in detail a transfer printing method using the transfer medium of this disclosure, that is, a method for manufacturing a transfer print using the transfer medium of this disclosure.

[0228] 3. Manufacturing of Transfer Printed Materials A transfer printed material can be manufactured by a manufacturing method comprising a contact step of bringing a transfer medium into contact with an ink-receiving portion (i.e., an ink-receiving printing portion) forming surface of the transfer medium, and a peeling step of peeling the substrate from the transfer medium.

[0229] Figure 4 schematically shows a method for manufacturing a transfer print. In the transfer medium 100, the transfer medium 6 is brought into contact with the surface on which the ink-receiving printing portion 2 exists, and then the substrate 1 is peeled off to transfer the first ink portion 3 to the transfer medium 6, that is, to obtain a transfer print 200. The same transfer printing can also be performed in a transfer medium having a second ink portion and / or an adhesive portion.

[0230] 3-1. Contact Process The transfer medium used in the contact process is not particularly limited and can be metal, wood, plastic, paper, fabric, etc. The metals, wood, plastics, and paper that can be used as transfer mediums are the same as the examples of metals, wood, plastics, and paper that can be used as base materials as described above.

[0231] In particular, it is preferable to use a fabric as the transfer medium. The fabric is not particularly limited and includes all textile products such as cloths and woven fabrics made from natural fibers and / or synthetic fibers as raw materials. Examples of fabrics include woven fabrics, nonwoven fabrics, knitted fabrics, etc. The fibers constituting the fabric are also not particularly limited and include natural fibers, chemical fibers, or mixtures thereof.

[0232] Preferred natural fibers include, for example, silk, cotton, and wool. Chemical fibers include synthetic fibers, regenerated fibers, and semi-synthetic fibers. Preferred synthetic fibers include, for example, polyester fibers, nylon fibers, acrylic fibers, polyurethane fibers, polyethylene fibers, polypropylene fibers, and vinylon fibers. A preferred regenerated fiber is, for example, rayon. Preferred semi-synthetic fibers include acetate and triacetate. Among these, fabrics formed from cotton, polyester fibers, polypropylene fibers, nylon fibers, or mixtures thereof are preferred, and fabrics formed from cotton, polyester fibers, nylon fibers, or mixtures thereof are more preferred.

[0233] In this disclosure, transfer printing is preferably performed by thermal transfer, that is, the contact step is preferably performed under heating and pressure. Examples of such a contact step include a method in which a transfer medium is brought into contact with a transfer medium using a press or a heated drum, and then heated and pressurized.

[0234] The heating temperature in the contact step is not particularly limited, but is preferably 80 to 220°C, more preferably 120 to 200°C, and even more preferably 140 to 190°C. The pressure in the contact step is also not particularly limited, but is 100 to 600 g / cm². 2 Preferably, it is 200 to 500 g / cm³. 2 That is the case.

[0235] The heating and pressurizing time in the contact step is preferably 1 second or longer from the viewpoint of further improving transferability. There is no particular upper limit to the heating and pressurizing time, but from the viewpoint of productivity, it is preferably 1 minute or less, more preferably 30 seconds or less, and even more preferably 10 seconds or less.

[0236] 3-2. Peeling Process After the contact process, the substrate is peeled off the transfer medium to obtain the desired transfer print. Peeling occurs at the interface between the ink-receiving portion (i.e., the ink-receiving printed portion) and the substrate when peeling the transfer substrate from the transfer medium. In this disclosure, since the ink-receiving portion is printed only at the transfer position, the entire ink-receiving printed portion and the first ink portion can be transferred to the surface of the transfer medium, and therefore no ink-receiving portion remains on the peeled substrate, allowing the substrate to be reused.

[0237] Furthermore, from the viewpoint of further reducing the amount of printed material remaining on the substrate after peeling, it is preferable to peel off the substrate after the temperature of the transfer medium has dropped to 60°C or below (especially 40°C or below).

[0238] Furthermore, the obtained transfer print may be heated and pressurized using a press or heating drum. By performing additional heating and pressurizing treatment on the obtained transfer print, the printed portion, such as the first ink portion, is more firmly bonded to the transfer medium, further improving wash and tumble dry fastness. In addition, at this time, by placing release paper with an uneven surface on the surface of the printed portion of the transfer print and performing heating and pressurizing treatment, the unevenness derived from the release paper can be transferred to the surface of the printed portion of the transfer print, and a matte finish (non-glossy effect) can be imparted to the image on the transfer print. The heating temperature in this step is not particularly limited, but is preferably 80 to 200°C, and more preferably 100 to 180°C. The pressure in this step is also not particularly limited, but is preferably 100 to 600 g / cm². 2 Preferably, it is 200 to 500 g / cm³. 2 The heating and pressurizing time in this process is not particularly limited, but is preferably 1 second to 1 minute, and more preferably 3 seconds to 30 seconds.

[0239] As described above, since no printed areas such as ink receiving areas remain on the substrate after peeling, the substrate can be used repeatedly to manufacture transfer media and transfer prints.

[0240] This application claims the benefit of priority based on Japanese Patent Application No. 2024-218723, filed on 13 December 2024. The entire specification of Japanese Patent Application No. 2024-218723, filed on 13 December 2024, is incorporated herein by reference.

[0241] The contents of this disclosure will be explained in more detail below with reference to examples, but the contents of this disclosure are not limited by the examples below, and it is certainly possible to implement the disclosure with appropriate modifications to the extent that it is in line with the spirit of the preceding and following, and all such modifications are included in the technical scope of this disclosure. In the following, unless otherwise specified, "parts" means "parts by mass" and "%" means "percent mass".

[0242] (Emulsion Production Example 1) 1125 parts of deionized water were charged into a polymerization reactor equipped with a stirrer, reflux condenser, thermometer, nitrogen inlet tube, and dropping funnel A. The internal temperature was then raised to 75°C while stirring under a nitrogen gas flow. Monomer emulsion A, having the composition shown in Table 1, was charged into dropping funnel A. Next, while maintaining the internal temperature of the polymerization reactor at 75°C, 16.0 parts of monomer emulsion A and 50 parts of a 5% aqueous solution of an azo-based initiator [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name: V-50] (hereinafter, 5% V-50 aqueous solution) were added to start the initial polymerization. After 40 minutes, while maintaining the reaction system temperature at 75°C, the remaining monomer emulsion A was uniformly added dropwise over 240 minutes. Simultaneously with monomer emulsion A, 30 parts of the 5% V-50 aqueous solution were uniformly added dropwise over 240 minutes. After the dropwise addition was complete, the contents of the polymerizer were maintained at 75°C for 180 minutes, and the pH was adjusted to 8.5 and the solid content to 35% by adding 25% aqueous ammonia and deionized water, thereby terminating the polymerization. After the resulting reaction solution was cooled to room temperature, an acrylic resin emulsion containing resin emulsion particles (hereinafter referred to as emulsion 1) was obtained by filtering through a 300-mesh wire mesh. The average particle size of the emulsion particles contained in emulsion 1 was 220 nm, the Tg of the resin constituting the particles was 10°C, and the acid value was 24 mg KOH / g.

[0243] (Emulsion Production Example 2) The same procedure as in Emulsion Production Example 1 was carried out, except that the composition of monomer emulsion A was changed to the composition shown in Table 1, and the polymerization initiator used was changed from a 5% V-50 aqueous solution to a 5% ammonium persulfate aqueous solution, to obtain an acrylic resin emulsion containing resin emulsion particles (hereinafter referred to as Emulsion 2). The average particle size of the emulsion particles contained in Emulsion 2 was 190 nm, the Tg of the resin constituting the particles was -24°C, and the acid value was 24 mg KOH / g.

[0244] (Emulsion Production Example 3) 350 parts of deionized water were charged into a polymerization reactor equipped with a stirrer, reflux condenser, thermometer, nitrogen inlet tube, dropping funnel A, and dropping funnel B. The internal temperature was then raised to 75°C while stirring under a nitrogen gas flow. Monomer emulsion A, having the composition shown in Table 1, was charged into dropping funnel A. Monomer emulsion B, having the composition shown in Table 1, was charged into dropping funnel B. Next, while maintaining the internal temperature of the polymerization reactor at 75°C, 27.0 parts of monomer emulsion A, 5 parts of 5% potassium persulfate aqueous solution (oxidizing agent) and 10 parts of 2% sodium bisulfite aqueous solution (reducing agent), which are polymerization initiators, were added to start the initial polymerization. After 40 minutes, while maintaining the reaction system temperature at 80°C, the remaining monomer emulsion A was uniformly added dropwise over 105 minutes. Simultaneously with monomer emulsion A, 45 parts of 5% potassium persulfate aqueous solution and 40 parts of 2% sodium bisulfite aqueous solution were uniformly added dropwise over 105 minutes. Immediately after the addition of monomer emulsion A was completed, monomer emulsion B was uniformly added dropwise over 105 minutes. Simultaneously with monomer emulsion B, 50 parts of 5% potassium persulfate aqueous solution and 50 parts of 2% sodium bisulfite aqueous solution were uniformly added dropwise over 105 minutes. After the addition of monomer emulsion B was completed, the same temperature was maintained for 60 minutes. Thereafter, the pH was adjusted to 8.5 and the solid content to 45% by adding 25% aqueous ammonia and deionized water, and polymerization was completed. After the obtained reaction solution was cooled to room temperature, it was filtered through a 300-mesh wire mesh to obtain an acrylic resin emulsion containing resin emulsion particles (hereinafter referred to as emulsion 3). The average particle size of the emulsion particles in emulsion 3 was 230 nm, the Tg of the resin constituting these particles was 5°C, and the acid value was 24 mg KOH / g.

[0245] The average particle size of the emulsion particles contained in the emulsion, as well as the Tg and acid value of the resin constituting the emulsion particles, are as follows.

[0246] (Measurement of average particle size of emulsion particles) The average particle size of emulsion particles (cumulant average particle size) was measured at 25°C using a dynamic light scattering particle size distribution analyzer (manufactured by Otsuka Electronics Co., Ltd., model number: FPAR-1000) with the emulsion obtained in each production example as the measurement sample, and determined using cumulant analysis.

[0247] (Measurement of Tg of resin) The glass transition temperature (Tg) of the resin constituting the emulsion particles was measured by differential scanning calorimetry (DSC) under the following measurement conditions. Measuring instrument: DSC 3500 (product name, manufactured by NETZSCH) Sample container: Sealed aluminum container Sample weight: 10 mg ± 2 mg Measurement method: Thermal analysis was performed in an N2 atmosphere according to the following temperature programs (1) to (5). (1) Increase temperature from 20°C to 200°C at 10°C / min (2) Hold at 200°C for 5 minutes (3) Decrease temperature from 200°C to -50°C at 10°C / min (4) Hold at -50°C for 5 minutes (5) Increase temperature from -50°C to 300°C at 10°C / min After measurement, the glass transition temperature was analyzed from the DSC curve chart during the temperature increase in (5) using the analysis software proteus Analysis, and the value of the midpoint glass transition temperature was adopted.

[0248] (Measurement of the acid value of the resin) The acid value of the resin constituting the emulsion particles was determined by calculating the amount of potassium hydroxide in mg required to neutralize the acid groups present in 1 g of monomer components used in the production of the emulsion particles.

[0249]

[0250] The unit of each component amount in Table 1 is "parts". The abbreviations used in Table 1 mean the following: MMA: Methyl methacrylate CHMA: Cyclohexyl methacrylate St: Styrene 2EHA: 2-Ethylhexyl acrylate BA: n-Butyl acrylate HEMA: 2-Hydroxyethyl methacrylate AA: Acrylic acid t-DM: t-Dodecyl mercaptan Newcol 723: Aqueous solution of Newcol 723 (nonionic emulsifier) ​​manufactured by Nippon Emulsifier Co., Ltd., diluted with water to a concentration of 20% SR-10: Aqueous solution of Adekaria Soap SR-10 (reactive anionic emulsifier) ​​manufactured by ADEKA Corporation, diluted with water to a concentration of 20%

[0251] (Pigment Dispersion Production Example 1) Five parts of the dispersant Discoat N-14 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), six parts of propylene glycol, seventy parts of deionized water, and 100 parts of titanium dioxide CR-95 (manufactured by Ishihara Sangyo Co., Ltd.) were packed into a mixture containing 50% zirconia beads with a particle size of 0.5 mm. The mixture was dispersed using a bead mill and filtered through a 1 μm pore size filter (manufactured by Advantec, MCP-1-C10S) to obtain a white pigment dispersion containing 55% pigment (hereinafter referred to as Pigment Dispersion 1). The average particle size of the pigment was 330 nm.

[0252] (Pigment Dispersion Production Example 2) Three parts of the dispersant Joncryl 678 (manufactured by BASF), 1.3 parts of dimethylaminoethanol, and 81 parts of deionized water were stirred and mixed at 70°C. Next, 15 parts of the blue pigment C. I. Pigment Blue 15:3 LIONOL BLUE FG-7330 (manufactured by Toyo Ink Co., Ltd.), 0.1 parts of the surfactant Olfin D-10PG (manufactured by Nisshin Chemical Industry Co., Ltd.), and 0.5 mm particle size zirconia beads were packed to 50% by volume, dispersed using a bead mill, and filtered through a 1 μm pore size filter (Advantec, MCP-1-C10S) to obtain a blue pigment dispersion containing 15% pigment (hereinafter referred to as pigment dispersion 2). The average particle size of the pigment was 90 nm.

[0253] (Measurement of average particle size of pigments) The average particle size of the pigments (cumulant average particle size) was measured at 25°C using a dynamic light scattering particle size distribution analyzer (manufactured by Otsuka Electronics Co., Ltd., model number: FPAR-1000) with the pigment dispersions obtained in each production example as measurement samples, and determined using cumulant analysis.

[0254] (Preparation of ink-receiving part forming liquid 1) 7.5 parts of emulsion 1 as emulsion particles, 7.5 parts of Epostor MX200W (manufactured by Nippon Shokubai Co., Ltd., cross-linked particles without Tg, average particle size 0.35 μm), 0.25 parts of calcium chloride, 0.25 parts of calcium nitrate, 3 parts of diethylene glycol monobutyl ether, 20 parts of propylene glycol, 0.3 parts of the surfactant KF-6011 (manufactured by Shin-Etsu Chemical Co., Ltd.), 0.3 parts of Surfinol 440 (manufactured by Evonik), and a total of 100 parts of deionized water were mixed and filtered through a 1 μm pore size filter (manufactured by Advantec, MCP-1-C10S) to produce ink-receiving part forming liquid 1.

[0255] (Preparation of White Ink 1) White ink 1 was produced by mixing 15 parts of emulsion 2 as emulsion particles, 23 parts of pigment dispersion 1, 1.2 parts of Epocross WS-700 (manufactured by Nippon Shokubai Co., Ltd., 25% solids content) (0.3 parts as solids), 2 parts of diethylene glycol monobutyl ether, 15 parts of triethylene glycol, 0.3 parts of the surfactant KF-6011 (manufactured by Shin-Etsu Chemical Co., Ltd., polyether-modified silicone-based surfactant), and a total of 100 parts of deionized water, and filtering the mixture through a 1 μm pore size filter (manufactured by Advantec, Inc., MCP-1-C10S).

[0256] (Preparation of Cyan Ink 1) Cyan ink 1 was produced by preparing it in the same manner as the preparation of white ink 1, except that pigment dispersion 1 was changed to pigment dispersion 2.

[0257] (Preparation of Adhesive Resin-Containing Liquid 1) Adhesive resin-containing liquid 1 was prepared by mixing 25 parts of emulsion 3 as emulsion particles, 2 parts of diethylene glycol monobutyl ether, 15 parts of triethylene glycol, 0.6 parts of the surfactant KF-6011 (manufactured by Shin-Etsu Chemical Co., Ltd.), and a total of 100 parts of deionized water, and filtering the mixture through a 1 μm pore size filter (manufactured by Advantec, MCP-1-C10S).

[0258] [Examples and Comparative Examples] (Preparation of Inkjet Ejector) Three Mastermind printers (MMP-TX13) were prepared and designated as printer A, printer B, and printer C. A rubber heater was placed on the platen of each printer and heated to 50°C. Ink receiving area forming liquid 1 was filled into printer A. Cyan ink 1 and white ink 1 were filled into printer B. Adhesive resin containing liquid 1 was filled into printer C.

[0259] [Example 1-1] (Manufacturing of transfer medium - 1st time) Substrate (polyester resin film, 100 μm thick, 20 x 30 cm) placed on a rubber heater 2 A ) was placed, and an image was formed by the inkjet method. Specifically, a solid print (8.2 x 16.2 cm) was made using printer A with ink-receiving liquid 1. 2 The following procedure was performed. At this time, the discharge rate of the ink receiving part forming liquid 1 per unit area was 30 g / m². 2 Next, the printed substrate was transferred to the rubber heater of printer B, and solid printing (8 x 16 cm) was performed on the printed surface of the ink receiving liquid using cyan ink 1. 2 After doing that, a solid white ink print (8 x 16 cm) is applied on top of it. 2 The following was performed. At this time, the discharge rate of cyan ink 1 per unit area was 10 g / m². 2 The discharge rate of white ink 1 per unit area is 70 g / m². 2 The substrate printed with cyan ink 1 and white ink 1 was transferred to the rubber heater of printer C, and then solid printing (8 x 16 cm) was performed on the printed surface of white ink 1 with adhesive resin-containing liquid 1. 2The following procedure was performed. At this time, the discharge rate of adhesive resin-containing liquid 1 per unit area was 135 g / m². 2 The image-formed substrate was dried in a hot air dryer at 150°C for 15 minutes to prepare transfer medium 1.

[0260] (Manufacturing of transfer prints - 1st time) A Horizon International TP-630M transfer press was used. The heating temperature was 150°C, and the press load was 3kN (transfer pressure: 400g / cm²). 2 The settings were adjusted as follows: The fabric to be transferred (100% cotton white T-shirt made by Hanes) was placed on the lower platen, and the transfer medium 1 was placed on top of it with the printed side facing down, and stamped for 10 seconds. After stamping, once the temperature of the fabric had dropped to below 40°C, the base material was peeled off the fabric to obtain the transferred print. The obtained transferred print was then placed on the lower platen again, silicone release paper was placed on top of the transferred print, and stamped for 5 seconds to press the image onto the fabric to obtain the transferred print 1. Note that no printed areas formed by printing the ink-receiving liquid remained on the peeled base material, and all components printed on the base material were transferred to the transfer medium. This peeled base material was reused to carry out the following Examples 1-2.

[0261] [Example 1-2] (Manufacturing of transfer medium - 2nd time) Transfer medium 2 was prepared in the same manner as the first manufacturing of the transfer medium in Example 1-1, except that the substrate peeled off in the first manufacturing of the transfer print in Example 1-1 was used as the base material.

[0262] (Manufacturing of Transfer Printed Material - Second Time) Transfer printed material 2 was manufactured in the same manner as in the first manufacturing of transfer printed material in Example 1-1, except that transfer medium 1 was changed to transfer medium 2. In the second manufacturing of transfer printed material, no printed areas formed by printing the ink-receiving area forming liquid remained on the peeled substrate, and all components printed on the substrate were transferred to the transfer medium. In other words, it can be seen that by using the transfer medium manufactured by the method of this disclosure, the substrate peeled off in transfer printing can be reused as is. Furthermore, from the results of the characteristic evaluation described later, it can be seen that even when the substrate is reused, the characteristics of the resulting transfer printed material do not deteriorate.

[0263] [Comparative Example 1-1] (Preparation of Substrate) Polyester resin film (thickness 100 μm, 20 x 30 cm) 2 The ink-receiving area forming liquid 1 was applied to the entire surface of one side of the substrate using a bar coater. Then, it was dried in a hot air dryer at 110°C for 5 minutes to produce a substrate 1 coated with an ink-receiving layer.

[0264] (Transfer medium manufacturing - 1st time) Substrate 1 was placed on a rubber heater and an image was formed by the inkjet method. Specifically, a solid print (8 x 16 cm) was made on the ink-receiving layer surface using cyan ink 1 with printer B. 2 After doing that, solid print (8 x 16 cm) was done on top of it with white ink 1. 2 The following was performed. At this time, the discharge rate of cyan ink 1 per unit area was 10 g / m². 2 The discharge rate of white ink 1 per unit area is 70 g / m². 2 The printed substrate was then transferred to the rubber heater of printer C, and solid printing (8 x 16 cm) was performed on the printed surface of white ink 1 using adhesive resin-containing liquid 1. 2 The following procedure was performed. At this time, the discharge rate of adhesive resin-containing liquid 1 per unit area was 135 g / m². 2 The image-formed substrate was dried in a hot air dryer at 150°C for 15 minutes to prepare transfer medium 3.

[0265] (Manufacturing of transfer prints - 1st time) A Horizon International TP-630M transfer press was used. The heating temperature was 150°C, and the press load was 3kN (transfer pressure: 400g / cm²). 2The settings were adjusted as follows: The fabric to be transferred (100% cotton white T-shirt made by Hanes) was placed on the lower pressing iron, and the transfer medium 3 was placed on top of it with the print side facing down, and stamped for 10 seconds. After stamping, once the temperature of the fabric had dropped to below 40°C, the base material was peeled off the fabric to obtain the transferred print. The obtained transferred print was then placed on the lower pressing iron again, silicone release paper was placed on top of the transferred print, and stamped for 5 seconds to press the image onto the fabric to obtain the transferred print 3. In Comparative Example 1-1, as shown in Figure 5, the peeling of the substrate resulted in the transfer of the ink-receiving layer (2a) to the transfer medium (6a) in the portion where at least one of the first ink portion (3a) formed from cyan ink 1, the second ink portion (4a) formed from white ink 1, and the adhesive portion (5a) formed from adhesive resin-containing liquid 1 was laminated. However, the portion of the ink-receiving layer (2a) in which none of the first ink portion (3a), second ink portion (4a), or adhesive portion (5a) was laminated remained on the substrate (1a). Comparative Example 1-2 was then carried out using this peeled substrate (1b).

[0266] [Comparative Example 1-2] (Transfer medium manufacturing - 2nd time) The substrate peeled off in the first manufacturing of the transfer print of Comparative Example 1-1 was placed on a rubber heater, and an image was formed by the inkjet method. Specifically, using printer B, a solid print (8 x 16 cm) was made with cyan ink 1 on the surface on the peeled substrate where the transfer was performed (specifically, at position 7b in Figure 5). 2 After doing that, solid print (8 x 16 cm) was done on top of it with white ink 1. 2 The following was performed. At this time, the discharge rate of cyan ink 1 per unit area was 10 g / m². 2 The discharge rate of white ink 1 per unit area is 70 g / m². 2 The printed substrate was then transferred to the rubber heater of printer C, and solid printing (8 x 16 cm) was performed on the printed surface of white ink 1 using adhesive resin-containing liquid 1. 2 The following procedure was performed. At this time, the discharge rate of adhesive resin-containing liquid 1 per unit area was 135 g / m². 2 The image-formed substrate was dried in a hot air dryer at 150°C for 15 minutes to prepare the transfer medium 4.

[0267] (Manufacturing of Transfer Printed Material - Second Attempt) Except for changing transfer medium 3 to transfer medium 4, an attempt was made to manufacture a transfer printed material in the same manner as in the first attempt of manufacturing a transfer printed material in Comparative Example 1-1, but the image could not be transferred. In other words, the substrate that was peeled off in the transfer printing in the comparative example was unsuitable for reuse.

[0268] [Characterization] The following characteristics were evaluated for each transfer medium and transfer print prepared in the examples and comparative examples. The results are shown in Table 2.

[0269] (1) Image Quality In each transfer medium obtained in the examples and comparative examples, the first ink portion formed by cyan ink 1 was visually inspected and the image quality was evaluated according to the following evaluation criteria. ○: Satisfies both (a) and (b) below. △: Satisfies at least one of (c) and (d) below, and does not fall under (e) and (f). ×: Satisfies at least one of (e) and (f). (a) When viewed from the substrate side, there is no bleeding or unevenness in the first ink area. (b) When viewed from the printing surface side of the adhesive resin-containing liquid, there is no bleeding of the first ink area into the second ink area formed from white ink 1. (c) When viewed from the substrate side, there is bleeding and / or unevenness in the first ink area. (d) When viewed from the printing surface side of the adhesive resin-containing liquid, there is bleeding of the first ink area into the second ink area formed from white ink 1. (e) When viewed from the substrate side, the bleeding and / or unevenness of the first ink area is noticeable. (f) When viewed from the printing surface side of the adhesive resin-containing liquid, the bleeding of the first ink area into the second ink area formed from white ink 1 is noticeable.

[0270] (2) Ink Absorption The ink absorption of the second ink portion formed with white ink 1 in each transfer medium obtained in the examples and comparative examples was evaluated according to the following evaluation criteria. ○: Maximum overhang width from the printing area is 0.2 mm or less △: Maximum overhang width from the printing area is greater than 0.2 mm and less than or equal to 0.5 mm ×: Maximum overhang width from the printing area is greater than 0.5 mm

[0271] (3) Transferability The transferability of the substrate during the manufacturing of each transfer print in the examples and comparative examples was evaluated according to the following evaluation criteria. ○: Peels off easily, and no printed image remains on the substrate after peeling. △: Peels off easily, but no printed image remains on the substrate after peeling. ×: Printed image remains on the substrate after peeling.

[0272] (4) Wet friction fastness For each transfer print obtained in the examples and comparative examples, a wet friction test was performed on a Type II tester using attached white cloth made of cotton No. 3-1, in accordance with the method specified in JIS L0849, with a load of 200g and 100 back-and-forth movements, and evaluated using a grayscale of discoloration. In Comparative Examples 1-2, it was not possible to evaluate the wet friction fastness because not all of the printed images could be transferred. ○: Wet friction test staining grade 4 or higher △: Wet friction test staining grade 3-4 or grade 3 ×: Wet friction test staining grade 2-3 or lower

[0273] (5) Washing and Tumble Drying Fastness The transfer prints obtained in the examples and comparative examples were washed and tumble dried under the following conditions, and the samples obtained after tumble drying were used. (Washing conditions) ・Washing machine: Model number NA-F5B1 (Panasonic Corporation) ・Water volume: 32L ・Course: Rinse once (Wash → Rinse (1 time) → Spin dry) ・Detergent: Ariel Laundry Detergent Liquid Disinfectant Plus (P&G Corporation), amount used 35g (Tumble drying conditions) ・Tumble dryer: Model number NH-D503 (Panasonic Corporation) ・Course: Standard (Evaluation) The washing and tumble drying fastness of the samples obtained by the above method was evaluated based on the number of cracks in the print. In Comparative Examples 1-2, it was not possible to transfer all of the print images, so the washing and tumble drying fastness could not be evaluated. ○: 5 cracks or less △: 6 to 15 cracks ×: 16 or more cracks

[0274]

[0275] 1 Substrate 2 Ink-receiving printing area 3 First ink area 4 Second ink area 5 Adhesive area 100 Transfer medium 6 Transfer medium 200 Transfer print

Claims

1. A method for manufacturing a transfer medium, comprising: an ink receiving portion forming step of forming a releaseable ink receiving portion on the surface of a substrate by printing; and a first ink printing step of printing a first ink onto the releaseable ink receiving portion.

2. The method for manufacturing a transfer medium according to claim 1, wherein the printing is inkjet printing or printing by a jet dispenser.

3. The method for manufacturing a transfer medium according to claim 1, wherein the first ink is a color ink containing a colorant.

4. The method for manufacturing a transfer medium according to claim 3, further comprising a second ink printing step of printing a second ink onto the printing surface of the first ink, wherein the second ink is a white ink containing a white pigment.

5. The method for manufacturing a transfer medium according to claim 1, further comprising an adhesive portion forming step of forming an adhesive portion on the printed surface of the first ink, either directly or via another component.

6. The method for manufacturing a transfer medium according to claim 5, wherein the adhesive portion is formed by printing an adhesive resin-containing liquid or by coating with adhesive resin powder.

7. A method for manufacturing a transfer medium according to claim 5, wherein a heat treatment is performed after the adhesive portion formation step.

8. The method for manufacturing a transfer medium according to claim 1, wherein the transfer medium is used for thermal transfer to a transfer medium.

9. The method for manufacturing a transfer medium according to claim 1, wherein the transfer medium is used for transfer to a fabric.

10. A method for manufacturing a transfer print, comprising: a contact step of bringing a transfer medium into contact with an ink receiving portion forming surface of a transfer medium obtained by the manufacturing method according to any one of claims 1 to 9; and a peeling step of peeling the substrate from the transfer medium.

11. The method for manufacturing a transfer print according to claim 10, wherein in the peeling step, the peeling is performed so that no ink receiving portion remains on the substrate.

12. A transfer medium comprising a substrate, an ink-receiving printed portion formed on the surface of the substrate so as to be detachable from the substrate, and a first ink portion formed from a first ink received in the printed portion.

13. The transfer medium according to claim 12, wherein the ink-receiving printing portion is partially formed on the surface of the substrate.

14. The transfer medium according to claim 12, wherein the entirety of the ink-receiving printed portion and the first ink portion can be transferred to the surface of the transfer medium.

15. The transfer medium according to claim 12, used for thermal transfer to a transfer medium.

16. The transfer medium according to claim 12, used for transferring onto fabric.

17. The transfer medium according to claim 12, characterized in that the first ink portion is substantially absent on the substrate on which the ink-receiving printed portion is not formed.

18. The transfer medium according to claim 12, wherein the first ink portion includes a colorant.

19. The transfer medium according to claim 18, further comprising a second ink portion directly laminated on the first ink portion, wherein the second ink portion contains a white pigment.

20. The transfer medium according to claim 12, further comprising an adhesive portion containing an adhesive resin laminated directly or via another member on the first ink portion.

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