Method of manufacturing printed materials

Abstract

To provide a method for producing a print which hardly generates cracking in a white image after being washed.SOLUTION: A method for producing a print, including applying a pretreatment liquid to a cloth and applying a white ink to the cloth applied with the pretreatment liquid by an inkjet method is such that: the pretreatment liquid contains polyvalent metal salt, a surface active agent and water: the white ink contains white inorganic pigment, resin particles, a surface active agent and water; an amount of the white inorganic pigment is 5.0-15.0 mass% based on the total amount of the white ink; the total amount of the white inorganic pigment and the resin particles is 20-35 mass% based on the total amount of the white ink; and an application amount A(g / m2) of the resin particles of the white ink to the cloth, and an application amount B(g / m2) of the polyvalent metal salt of the pretreatment liquid to the cloth satisfy a relationship of A2 / B≥50.SELECTED DRAWING: None

Description

Technical Field

[0001] An embodiment of the present invention relates to a method for producing a printed textile.

Background Art

[0002] As a method for printing images such as characters, pictures, and patterns on fabrics such as woven fabrics, knitted fabrics, and nonwoven fabrics, printing methods using an inkjet process have attracted attention.

[0003] Images formed on dark-colored fabrics such as black tend to be less visible compared to light-colored fabrics such as white. Patent Document 1 describes a method in which a pretreatment agent containing a polyvalent metal salt is applied to a dark-colored fabric such as black, then an ink containing a white pigment is printed to form a white image, and a desired image is formed thereon. Further, Patent Document 1 describes performing a heat treatment after applying the pretreatment agent.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problem to be Solved by the Invention

[0005] It has been found that when a white image is formed by applying a pretreatment liquid containing a flocculant to a fabric and then applying white ink by a so-called wet-on-wet process without providing a drying step, cracks may occur in the white image after the obtained printed textile is washed. An embodiment of the present invention aims to provide a method for producing a printed textile in which cracks are less likely to occur in a white image after washing.

Means for Solving the Problem

[0006] One embodiment of the present invention includes applying a pretreatment liquid to a fabric, and applying white ink to the fabric to which the pretreatment liquid has been applied by an inkjet method, wherein the pretreatment liquid contains a polyvalent metal salt, a surfactant, and water, the white ink contains a white inorganic pigment, resin particles, a surfactant, and water, the content of the white inorganic pigment is 5.0 to 15.0 mass% relative to the total amount of the white ink, the total content of the white inorganic pigment and the resin particles is 20 to 35 mass% relative to the total amount of the white ink, and the application amount A (g / m of the resin particles in the white ink to the fabric 2 ), and the application amount B (g / m of the polyvalent metal salt in the pretreatment liquid to the fabric 2 ) satisfy the relationship of A 2 / B≧50. The present invention relates to a method for producing a printed textile.

Effects of the Invention

[0007] According to the embodiment of the present invention, it is possible to produce a printed textile in which cracks are less likely to occur in a white image after washing.

Modes for Carrying Out the Invention

[0008] Hereinafter, one embodiment of the present invention will be described in detail, but it goes without saying that the present invention is not limited to these embodiments, and various modifications and changes may be made.

[0009] The method for producing a printed textile according to one embodiment includes applying a pretreatment liquid to a fabric, and applying white ink to the fabric to which the pretreatment liquid has been applied by an inkjet method, wherein the pretreatment liquid contains a polyvalent metal salt, a surfactant, and water, the white ink contains a white inorganic pigment, resin particles, a surfactant, and water, the content of the white inorganic pigment is 5.0 to 15.0 mass% relative to the total amount of the white ink, the total content of the white inorganic pigment and the resin particles is 20 to 35 mass% relative to the total amount of the white ink, and the application amount A (g / m of the resin particles in the white ink to the fabric 2 ), and the application amount B (g / m of the polyvalent metal salt in the pretreatment liquid to the fabric 2 ) satisfy the relationship of A 2 / B≧50. When this method for producing a printed textile is used, it is possible to produce a printed textile in which cracks are less likely to occur in white images after washing.

[0010] When forming a white image on a dark-colored fabric by the wet-on-wet method, cracks tend to occur more easily after washing compared to the wet-on-dry method. While not being bound by theory, the mechanism by which cracks occur in the wet-on-wet method is presumed as follows. In the wet-on-wet method, liquid white ink is overlaid on the fabric that remains wet with the pretreatment liquid, so the white ink and the pretreatment liquid are prone to mixing. For this reason, an ink film is likely to be formed in a state where polyvalent metal salts and the like, which are components of the pretreatment liquid, are mixed inside the white ink layer. In addition, the polyvalent metal salts mixed into the ink layer dissolve in water during washing and are easily removed from the ink film. It is considered that when the polyvalent metal salts are removed from the white ink film, gaps are formed in the white ink film, making it brittle and prone to cracking.

[0011] In contrast, while not being bound by theory, it is presumed that in the method for producing a printed textile according to one embodiment, a printed textile in which cracks after washing are less likely to occur can be produced by the following effects. The total amount of the white inorganic pigment and resin particles in the white ink is 20 to 35 mass% relative to the total amount of the white ink, and since the white ink has a high solid content, the fluidity of the ink tends to decrease after the ink lands, and it is presumed that the white ink and the pretreatment liquid are relatively less likely to mix. Furthermore, the application amount A (g / m of the resin particles of the white ink to the fabric per unit area 2 ), and the application amount B (g / m of the polyvalent metal salt of the pretreatment liquid to the fabric per unit area 2 ) is A 2It is presumed that the strength of the ink film can be reinforced to suppress crack formation even after polyvalent metal salts are removed from the ink film by washing, by satisfying the relationship / B≧50 and by having the white inorganic pigment at 5.0-15.0% by mass relative to the total amount of white ink. In this way, it is presumed that even in the wet-on-wet method, it is possible to produce printed materials that are less prone to cracking after washing.

[0012] A method for producing a printed fabric according to one embodiment includes applying a pretreatment solution to a cloth and applying white ink to the cloth treated with the pretreatment solution using an inkjet method. The following describes the fabric, pretreatment solution, and white ink.

[0013] <Cloth> The method for producing a printed material according to one embodiment can be preferably used for printing on fabric. Examples of fibers included in the fabric include natural fibers such as cotton, silk, wool, and linen; and chemical fibers such as polyester, acrylic, polyurethane, nylon, rayon, cupro, and acetate. The fabric may contain one or more types of fibers. The fabric may also be woven, knitted, or nonwoven.

[0014] <Pretreatment solution> The pretreatment solution may contain polyvalent metal salts as a coagulant.

[0015] Polyvalent metal salts are composed of polyvalent metal ions with two or more valencies and anions. Examples of polyvalent metal ions with two or more valencies include Ca 2+ Mg 2+ Cu 2+ Ni 2+ Zn 2+ Ba 2+ Examples include Cl. - NO3 - CH3COO - , I - , Br - SO4 2- ClO3 -Examples include the following. Specifically, examples of polyvalent metal salts include calcium chloride, calcium nitrate, magnesium nitrate, magnesium sulfate, copper nitrate, calcium acetate, and magnesium acetate. The polyvalent metal salt may be in hydrated or anhydrous form.

[0016] These polyvalent metal salts may be used individually or in combination of two or more. The polyvalent metal salt content, in terms of active ingredient amount, is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more, relative to the total amount of pretreatment solution. On the other hand, the polyvalent metal salt content, in terms of active ingredient amount, is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, relative to the total amount of pretreatment solution. For example, the polyvalent metal salt content, in terms of active ingredient amount, is preferably 10 to 40% by mass, more preferably 15 to 35% by mass, and even more preferably 20 to 30% by mass, relative to the total amount of pretreatment solution. When using metal salt hydrates as polyvalent metal salts, the amount of active ingredient in the polyvalent metal salt is calculated on an anhydrous basis.

[0017] The pretreatment solution may contain a surfactant. Preferably, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, or combinations thereof can be used as the surfactant, with nonionic surfactants being more preferred. Furthermore, either low-molecular-weight surfactants or high-molecular-weight surfactants may be used.

[0018] The HLB value of the surfactant is preferably 5 to 20, more preferably 10 to 18, and even more preferably 14 to 18.

[0019] Here, the HLB value is one measure of the properties of a surfactant, and it quantifies the balance between hydrophilic and lipophilic groups in the molecule. Several calculation methods have been proposed for the HLB value, but in this specification, the value is calculated by the Griffin method and is calculated by the following formula (1). The same applies to the HLB values ​​of surfactants below. HLB value = 20 × (formula weight of hydrophilic part) / (molecular weight of surfactant) ... Equation (1)

[0020] Here, the "hydrophilic portion" refers to the hydrophilic part contained in the molecular structure of the surfactant, and is preferably a polyoxyalkylene group, an alcohol group with 3 or fewer carbon atoms in the main chain relative to a hydroxyl group, or a combination thereof. If the surfactant contains multiple hydrophilic portions, the amount of the hydrophilic portion in formula (1) above is the sum of these amounts. Examples of polyoxyalkylene groups include the polyoxyethylene group (polyethylene oxide; EO:-(CH2CH2O)). n -) Polyoxypropylene group (polypropylene oxide; PO:-(CH2CH2CH2O) n - ) are some examples. Furthermore, examples of alcohol groups include groups derived from methanol, ethanol, propanol, isopropanol, glycerin, polyglycerin, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, sucrose, mannitol, glycols, etc. (for example, -CH2CH2OH for ethanol).

[0021] The "hydrophobic portion" refers to the hydrophobic part contained in the molecular structure of the surfactant, and is preferably an aliphatic hydrocarbon group or aromatic hydrocarbon group derived from aliphatic alcohols, alkylphenols, fatty acids, etc., with a main chain having 4 or more carbon atoms relative to the hydroxyl group; a group derived from organosiloxanes, alkyl halides, etc.; or a combination thereof.

[0022] Examples of nonionic surfactants include ester-type surfactants such as glycerin fatty acid esters and fatty acid sorbitan esters; ether-type surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, and polyoxypropylene alkyl ethers; ether ester-type surfactants such as polyoxyethylene sorbitan fatty acid esters; acetylene-based surfactants; silicone-based surfactants; and fluorine-based surfactants. Among these, acetylene-based surfactants such as acetylene glycol-based surfactants can be preferably used.

[0023] Examples of acetylene-based surfactants include acetylene glycol-based surfactants, acetylene alcohol-based surfactants, and surfactants having an acetylene group.

[0024] The acetylene glycol-based surfactant is a glycol having an acetylene group, preferably a glycol having a symmetrical structure with the acetylene group located in the center, and may also have a structure in which ethylene oxide is added to the acetylene glycol. Examples of commercially available acetylene-based surfactants include the Surfinol series from Evonik Industries, such as "Surfinol 104E," "Surfinol 104H," "Surfinol 420," "Surfinol 440," "Surfinol 465," and "Surfinol 485," and the Orfin series from Nisshin Chemical Industry Co., Ltd., such as "Orfin E1004," "Orfin E1010," and "Orfin E1020" (all are product names).

[0025] Examples of silicone-based surfactants include polyether-modified silicone-based surfactants, alkyl-aralkyl copolymerized silicone-based surfactants, and acrylic silicone-based surfactants. Examples of commercially available silicone-based surfactants include "Sylface SAG002" and "Sylface 503A" manufactured by Nisshin Chemical Industry Co., Ltd. (both are product names).

[0026] Other nonionic surfactants include, for example, polyoxyethylene alkyl ether-based surfactants such as the Emulgen series manufactured by Kao Corporation, including "Emulgen 102KG," "Emulgen 103," "Emulgen 104P," "Emulgen 105," "Emulgen 106," "Emulgen 108," "Emulgen 120," "Emulgen 147," "Emulgen 150," "Emulgen 220," "Emulgen 350," "Emulgen 404," "Emulgen 420," "Emulgen 705," "Emulgen 707," "Emulgen 709," "Emulgen 1108," "Emulgen 4085," and "Emulgen 2025G" (all are product names).

[0027] Examples of anionic surfactants include the Emal series manufactured by Kao Corporation, such as "Emal 0," "Emal 10," "Emal 2F," "Emal 40," and "Emal 20C"; the Neoperex series, such as "Neoperex GS," "Neoperex G-15," "Neoperex G-25," and "Neoperex G-65"; the Perex series, such as "Perex OT-P," "Perex TR," "Perex CS," "Perex TA," "Perex SS-L," and "Perex SS-H"; and the Demol series, such as "Demol N," "Demol NL," "Demol RN," and "Demol MS" (all are product names).

[0028] Examples of cationic surfactants include the Acetamine series "Acetamine 24" and "Acetamine 86" manufactured by Kao Corporation, the Cortamine series "Cortamine 24P", "Cortamine 86P", "Cortamine 60W", and "Cortamine 86W", and the Sanizol series "Sanizol C" and "Sanizol B-50" (all are product names).

[0029] Examples of amphoteric surfactants include the Anchitol series manufactured by Kao Corporation, such as "Anchitol 20BS," "Anchitol 24B," "Anchitol 86B," "Anchitol 20YB," and "Anchitol 20N" (all are product names).

[0030] Surfactants may be used individually or in combination of two or more types.

[0031] The surfactant content, in terms of active ingredient amount, is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.2 to 3% by mass, relative to the total amount of the pretreatment solution.

[0032] The pretreatment solution may contain water. While there are no particular restrictions on the type of water used, it is preferable to use water that contains as few ionic components as possible. Examples of suitable water include ion-exchanged water, distilled water, and ultrapure water.

[0033] The amount of water is preferably 20-90% by mass, more preferably 30-70% by mass, and even more preferably 40-60% by mass, based on the total amount of pretreatment solution.

[0034] The pretreatment solution may contain other components as needed. Examples of other components include water-soluble organic solvents, defoamers, pH adjusters, antioxidants, and preservatives.

[0035] The pretreatment solution preferably contains a water-soluble organic solvent. As the water-soluble organic solvent, an organic compound that is liquid at room temperature and soluble in water can be used, and it is preferable to use a water-soluble organic solvent that mixes uniformly with the same volume of water at 1 atmosphere and 20°C. Examples include lower alcohols such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, and 2-methyl-2-propanol; glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and polypropylene glycol; glycerins such as glycerin, diglycerin, triglycerin, and polyglycerin; acetins such as monoacetin and diacetin; and ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol. Glycol ethers such as monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol dimethyl ether, and tetraethylene glycol diethyl ether can be used; triethanolamine, 1-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, β-thiodiglycol, sulfolane, etc. The boiling point of the water-soluble organic solvent is preferably 100°C or higher, and more preferably 150°C or higher.

[0036] Water-soluble organic solvents may be used individually, or two or more may be used in combination as long as they form a single phase with water. The content of the water-soluble organic solvent in the pretreatment solution is preferably 5 to 50% by mass, and more preferably 10 to 35% by mass, based on the total amount of the pretreatment solution.

[0037] The method for producing the pretreatment solution is not particularly limited and can be produced by any known method. For example, it can be obtained by dispersing all components together or in separate portions in a stirrer such as a three-in-one motor, and optionally passing it through a filter such as a membrane filter.

[0038] The pH of the pretreatment solution is preferably 3 to 9, and more preferably 4 to 8. The viscosity of the pretreatment solution is preferably 1 to 30 mPa·s at 23°C.

[0039] The pretreatment solution can preferably be used for textile printing. The method of applying the pretreatment solution is not particularly limited, but it is preferably applied by an inkjet method.

[0040] <White ink> White ink contains a white inorganic pigment as a coloring agent. Examples of white inorganic pigments include titanium dioxide, zinc oxide, zinc sulfide, antimony oxide, and zirconium oxide. Among these, titanium dioxide is preferred from the viewpoint of opacity. The average particle size of titanium dioxide is preferably 100 nm or more from the viewpoint of opacity, and preferably 600 nm or less from the viewpoint of discharge stability. When using titanium dioxide, it is preferable to use titanium dioxide that has been surface-treated with alumina or silica to suppress photocatalytic activity. The amount of surface treatment is preferably 5 to 20% by mass in the pigment.

[0041] Self-dispersing pigments may be used as white inorganic pigments. Self-dispersing pigments are pigments in which hydrophilic functional groups are introduced to the surface of the pigment by chemical or physical treatment. Ionic hydrophilic functional groups are preferred for introduction into the self-dispersing pigment, and by charging the pigment surface anionically or cationically, the pigment particles can be stably dispersed in water by electrostatic repulsion. Preferred anionic functional groups include carboxyl groups, sulfo groups, sulfino groups, sulfate ester groups, phosphate groups, phosphate ester groups, phosphite groups, and phosphite ester groups. Preferred cationic functional groups include quaternary ammonium groups and quaternary phosphonium groups. These hydrophilic functional groups may be directly bonded to the pigment surface or bonded via other atomic groups. Examples of other atomic groups include alkylene groups, phenylene groups, and naphthylene groups, but are not limited to these. Examples of pigment surface treatment methods include diazotization, sulfonation, hypochlorous acid treatment, humic acid treatment, and vacuum plasma treatment. As a white inorganic pigment, a pigment dispersion in which the pigment is pre-dispersed with a pigment dispersant may be used. A pigment dispersion dispersed with a pigment dispersant, as described later, may also be used.

[0042] White inorganic pigments may be used individually or in combination of two or more types.

[0043] From the viewpoint of the strength of the ink film, the amount of white inorganic pigment is preferably 5.0% by mass or more, more preferably 5.5% by mass or more, and even more preferably 6.0% by mass or more, relative to the total amount of white ink. From the viewpoint of the strength of the ink film, the amount of white inorganic pigment is preferably 15.0% by mass or less, more preferably 13.0% by mass or less, more preferably 11.0% by mass or less, and even more preferably 9.0% by mass or less, relative to the total amount of white ink. The amount of white inorganic pigment is preferably 5.0 to 15.0% by mass, more preferably 5.0 to 13.0% by mass, even more preferably 5.5 to 11.0% by mass, and even more preferably 6.0 to 9.0% by mass, relative to the total amount of white ink.

[0044] To stably disperse white inorganic pigments in white ink, pigment dispersants such as polymer dispersants and surfactant-type dispersants can be used. Examples of polymer dispersants include commercially available products such as the TEGO Disperse series from EVONIK, including "TEGO Disperse 740W," "TEGO Disperse 750W," "TEGO Disperse 755W," "TEGO Disperse 757W," and "TEGO Disperse 760W," and the Solsperse series from Lubrizol Japan, including "Solsperse 20000," "Solsperse 27000," "Solsperse 41000," "Solsperse 41090," "Solsperse 43000," "Solsperse 44000," and "Solsperse 46000." Examples include the Joncryl series from BASF Japan Ltd., such as "Joncryl 57," "Joncryl 60," "Joncryl 62," "Joncryl 63," "Joncryl 71," and "Joncryl 501"; products from Big Chemie Japan Co., Ltd., such as "DISPERBYK-102," "DISPERBYK-185," "DISPERBYK-190," "DISPERBYK-193," and "DISPERBYK-199"; and products from Daiichi Kogyo Seiyaku Co., Ltd., such as "Polyvinylpyrrolidone K-30" and "Polyvinylpyrrolidone K-90" (all are brand names). Examples of surfactant-type dispersants include anionic surfactants such as the Demol series manufactured by Kao Corporation, including "Demol P," "Demol EP," "Demol N," "Demol RN," "Demol NL," "Demol RNL," and "Demol T-45," and nonionic surfactants such as the Emulgen series manufactured by Kao Corporation, including "Emulgen A-60," "Emulgen A-90," "Emulgen A-500," "Emulgen B-40," "Emulgen L-40," and "Emulgen 420" (all are product names).

[0045] The pigment dispersant may be used alone or in combination of two or more types. When using a pigment dispersant, the amount in the white ink varies depending on the type and is not particularly limited, but generally, a mass ratio of 0.005 to 0.5 per 1 part pigment is preferred.

[0046] White ink may contain resin particles.

[0047] The resin particles are preferably dispersible in an aqueous solvent. The resin particles are preferably capable of dispersing in water without dissolving in water to form an oil-in-water (O / W) emulsion. The resin particles can be incorporated as an oil-in-water resin emulsion in the manufacture of white ink.

[0048] The resin particles may be self-emulsifying resin particles in which hydrophilic groups and / or hydrophilic segments are introduced into the resin to ensure stable dispersion in water, or they may be forced-emulsifying resin particles in which the resin is forcibly dispersed using a dispersant. The resin particles may be, for example, anionic, cationic, nonionic, or amphoteric, but anionic or nonionic is preferred.

[0049] Anionic resin particles may have anionic functional groups present on their surface, such as in self-emulsifying resins, or they may have surface treatments such as the application of an anionic dispersant to their surface. Typical anionic functional groups include carboxyl groups, sulfo groups, sulfino groups, sulfate ester groups, phosphate groups, phosphate ester groups, phosphite groups, and phosphite ester groups. Examples of anionic dispersants include anionic surfactants.

[0050] Nonionic resin particles may have nonionic functional groups present on their surface, such as in self-emulsifying resins, or they may have surface treatments such as the application of a nonionic dispersant to their surface. Typical nonionic functional groups include polyoxyalkylene glycol groups and hydroxyl groups. Examples of nonionic dispersants include nonionic surfactants.

[0051] From the viewpoint of inkjet ejection performance, the average particle size of the resin particles is preferably 600 nm or less, more preferably 500 nm or less, and more preferably 400 nm or less. For example, the average particle size of the resin particles may be in the range of 10 nm to 600 nm, or in the range of 50 nm to 500 nm. From the viewpoint of inkjet ejection performance, it is preferable to include resin particles with an average particle size of 100 nm or more. The amount of resin particles with an average particle size of 100 nm or more is preferably 20% by mass or more, and more preferably 50% by mass or more, relative to the total amount of resin particles in the ink. The higher the proportion of resin particles with an average particle size of 100 nm or more in the resin particles, the less likely structural viscosity is to develop, and therefore, ejection defects are less likely to occur even after being left for a predetermined time.

[0052] In this specification, the average particle size of resin particles is the volume-based median diameter in the particle size distribution measured by dynamic light scattering. The particle size distribution of resin particles can be measured at 25°C using a sample prepared by diluting a resin emulsion with water to a resin particle concentration of 0.5% by mass. As a dynamic light scattering particle size distribution analyzer, for example, the "nano Partica SZ-100 nanoparticle analyzer" (manufactured by Horiba, Ltd.) can be used. Furthermore, it is preferable to measure the average particle size of the resin particles in the state of the resin emulsion raw material before preparing the ink, as this eliminates the influence of the colorant, and the measured value can be used as the average particle size of the resin particles.

[0053] Examples of resin particle types include, Conjugated diene resins such as styrene-butadiene copolymers, methyl methacrylate-butadiene copolymers, and vinyl chloride-vinyl acetate copolymers; Acrylic resins such as polymers of acrylic acid esters and methacrylic acid esters, or copolymers thereof with styrene, etc. Vinyl resins such as ethylene-vinyl acetate copolymer, Alternatively, functionally modified resins using monomers containing functional groups such as carboxyl groups from these various resins; Examples of resin particles include melamine resin, urea resin, polyurethane resin, polyester resin, polyolefin resin, silicone resin, polyvinyl butyral resin, and alkyd resin. These resin particles may be made from individual resins or hybrid resin particles may be used.

[0054] The resin particles preferably include acrylic resin particles, polyurethane resin particles, or a combination thereof.

[0055] The polyurethane resin may be either aliphatic polyurethane or aromatic polyurethane. The polyurethane resin has a urethane skeleton. Examples of polyurethane resins include, for example, polyether-type polyurethane resins containing ether bonds in the main chain, polyester-type polyurethane resins containing ester bonds in the main chain, polycarbonate-type polyurethane resins containing carbonate bonds in the main chain, and polyester-ether-type polyurethane resins containing both ester and ether bonds in the main chain.

[0056] The resin particles preferably contain polyurethane resin. From the viewpoint of excellent adhesion to a variety of fabrics, it is even more preferable that they contain polyester-type polyurethane resin. The polyester-type polyurethane resin is preferably present in an amount of 10% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more, relative to the total amount of resin particles. For example, the amount of polyester-type polyurethane resin may be 100% by mass or less, or 95% by mass or less, relative to the total amount of resin particles.

[0057] Commercially available resin particle emulsions include the Impranil series (DLP-R, DLU, DLF) manufactured by Sumika Covestro Urethane Co., Ltd. Superflex series (300, 420, 460, 470, 500M, 740, 150HS, E2000) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Daicel Ornex Co., Ltd.'s DAOTAN series (TW6490 / 35WA, TW6492 / 35WA, TW6493 / 35WA, TW6450 / 35WA, VTW6463 / 36WA), Takelac series (W-6061, W-6010) manufactured by Mitsui Chemicals, Inc. Examples include "UW-1701F" and "UW-1005D-C1" manufactured by UBE Corporation (all are product names).

[0058] The resin particles may be used individually or in combination of two or more types. The amount of resin particles is preferably 12% by mass or more, more preferably 15% by mass or more, even more preferably 18% by mass or more, and even more preferably 21% by mass or more, relative to the total amount of white ink. The amount of resin particles is preferably 32% by mass or less, more preferably 30% by mass or less, even more preferably 28% by mass or less, and even more preferably 26% by mass or less, relative to the total amount of white ink. The amount of resin particles relative to the total amount of white ink is, for example, preferably 12 to 32% by mass, more preferably 15 to 30% by mass, even more preferably 18 to 28% by mass, and even more preferably 21 to 26% by mass.

[0059] In white ink, the total amount of white inorganic pigment and resin particles is preferably 20% by mass or more, more preferably 25% by mass or more, even more preferably 28% by mass or more, and even more preferably 30% by mass or more, relative to the total amount of white ink, from the viewpoint of making it difficult for the white ink and pretreatment solution to mix and reducing the occurrence of cracks in the white image after washing. On the other hand, the total amount of white inorganic pigment and resin particles is preferably 35% by mass or less, and more preferably 32% by mass or less, relative to the total amount of white ink. For example, the total amount of white inorganic pigment and resin particles is preferably 20 to 35% by mass, more preferably 25 to 35% by mass, even more preferably 28 to 32% by mass, and even more preferably 30 to 32% by mass, relative to the total amount of white ink.

[0060] From the viewpoint of further improving the ink film strength, the mass ratio of resin particles to white inorganic pigment in white ink, "resin particles / white inorganic pigment," is preferably 1.2 or higher, more preferably 1.5 or higher, even more preferably 2.0 or higher, and even more preferably 2.5 or higher. The mass ratio of resin particles to white inorganic pigment, "resin particles / white inorganic pigment," may be, for example, 5.0 or less, 4.5 or less, or 4.0 or less. The mass ratio of resin particles to white inorganic pigment in white ink, "resin particles / white inorganic pigment," is preferably 1.2 to 5.0, more preferably 1.5 to 4.5, even more preferably 2.0 to 4.0, and may be, for example, 2.5 to 4.0.

[0061] White ink may contain surfactants. As the surfactant, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, or combinations thereof can be preferably used, with nonionic surfactants being more preferable. In addition, either low molecular weight surfactants or high molecular weight surfactants may be used.

[0062] The HLB value of the surfactant is preferably 5 to 20, more preferably 10 to 18, and even more preferably 10 to 15.

[0063] For example, from the viewpoint of making the pretreatment solution and the white ink less likely to mix, the surfactant in the white ink may have a lower HLB than the surfactant in the pretreatment solution. For example, the surfactant in the white ink may have an HLB of less than 15, and the surfactant in the pretreatment solution may have an HLB of 15 or more.

[0064] As the surfactant, for example, one can be selected from those described in the pretreatment solution above. Among these, acetylene-based surfactants such as acetylene glycol-based surfactants can be preferably used.

[0065] The surfactant content, in terms of active ingredient amount, is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.2 to 3% by mass, relative to the total amount of white ink.

[0066] White ink can contain water. While there are no particular restrictions on the type of water, it is preferable to use water that contains as few ionic components as possible. In particular, from the viewpoint of the ink's storage stability, it is preferable to use water with a low content of polyvalent metal ions such as calcium. Suitable water options include, for example, deionized water, distilled water, or ultrapure water. From the viewpoint of adjusting the viscosity of the ink, water is preferably included in the total amount of white ink at a concentration of 30 to 70% by mass, more preferably 35 to 65% by mass, and even more preferably 40 to 60% by mass.

[0067] White ink may contain other components as needed. These other components may include water-soluble organic solvents, defoamers, antioxidants, pH adjusters, and preservatives.

[0068] It is preferable to incorporate a water-soluble organic solvent into the white ink. As the water-soluble organic solvent, an organic compound that is liquid at room temperature and soluble in water can be used, and it is preferable to use a water-soluble organic solvent that mixes uniformly with the same volume of water at 1 atmosphere and 20°C. From the viewpoint of on-board stability, the boiling point of the water-soluble organic solvent is preferably 100°C or higher, more preferably 150°C or higher, even more preferably 200°C or higher, and even more preferably 250°C or higher. As a water-soluble organic solvent, for example, one can be selected and used from those described in the pretreatment solution section above.

[0069] Water-soluble organic solvents may be used individually, or two or more may be used in combination as long as they form a single phase with water. The amount of water-soluble organic solvent is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and even more preferably 10 to 30% by mass, based on the total amount of white ink.

[0070] From the viewpoint of on-board stability, the water-soluble organic solvent is preferably 0.2 or more in mass ratio per 1 resin particle, more preferably 0.5 or more, even more preferably 0.7 or more, and even more preferably 0.9 or more.

[0071] The method for manufacturing white ink is not particularly limited and can be manufactured by any known method. For example, all components can be added together or in separate portions to a stirrer such as a three-in-one motor and dispersed, and the ink can be obtained by passing it through a filter such as a membrane filter, if desired.

[0072] From the viewpoint of ink storage stability, the pH of the white ink is preferably 7.0 to 10.0, and more preferably 7.5 to 9.0. From the viewpoint of inkjet ejection performance, for example, the viscosity of the white ink is preferably 1 to 30 mPa·s at 23°C.

[0073] White ink can be preferably used for textile printing. White ink can be applied to fabric by an inkjet method to form a white image. Color ink can then be applied to the fabric coated with white ink to form a non-white image. It is preferable to apply the white ink to fabric that has been treated with a pre-treatment solution.

[0074] <Method of manufacturing printed materials> A method for manufacturing a printed fabric according to one embodiment may include applying the above-described pretreatment solution to a cloth (hereinafter also referred to as the "pretreatment solution application step") and applying the above-described white ink to the cloth to which the pretreatment solution has been applied using an inkjet method (hereinafter also referred to as the "white ink application step"). The above-described cloth can be used as the cloth.

[0075] The pretreatment solution application process will be described below. The method of applying the pretreatment solution to the fabric is not particularly limited, and any method such as a spray method using an airbrush, immersion method, pad method, or coating method can be used, and various printing methods such as inkjet printing (inkjet method) or screen printing may also be used. The inkjet method is not particularly limited and may be any method such as piezo, electrostatic, or thermal. When using an inkjet printing device, it is preferable to eject droplets of pretreatment liquid or ink from the inkjet head based on a digital signal and to adhere the ejected droplets to the fabric.

[0076] The area to which the pretreatment solution is applied may be an area with the same shape as the image created with white ink, a wider area including the shape of the image created with white ink, or the entire surface of the cloth. It is preferable that the areas for applying the pretreatment solution, the areas for applying the white ink, and the areas for applying the colored ink overlap at least partially.

[0077] The amount of pre-treatment solution to apply to the fabric should be 5-300g / m². 2Preferably, 10-250 g / m² 2 More preferably, 15-200 g / m 2 This is even more preferable. The amount of pretreatment solution applied may be changed depending on the type of fabric.

[0078] From the perspective of improving the strength of the ink film, the amount of white ink resin particles applied per unit area to the fabric A (g / m²) 2 ), and the amount of polyvalent metal salt applied to the fabric per unit area B (g / m²) 2 ) is A 2 It is preferable that the relationship / B ≥ 50 is satisfied. A 2 / B is more preferably 60 or higher, even more preferably 80 or higher, even more preferably 100 or higher, and even more preferably 150 or higher. 2 / B may be, for example, 3000 or less, 2000 or less, 1000 or less, or 450 or less. For example, A 2 / B is preferably 50 to 3000, more preferably 60 to 2000, even more preferably 80 to 1000, even more preferably 100 to 450, and even more preferably 150 to 450. 2 When / B is 3000 or less, the color of the colored ink is well-developed when colored ink is layered on top of white ink.

[0079] The amount of pretreatment solution applied to the fabric is such that the amount of polyvalent metal salt applied to the fabric is 1 g / m². 2 Preferably, the amount is 3 g / m² or more. 2 It is more preferable that the amount be greater than or equal to 6 g / m². 2 It is even more preferable that the amount is greater than or equal to the above. The amount of pretreatment solution applied to the fabric is such that the amount of polyvalent metal salt applied to the fabric is 50 g / m 2 Preferably, the amount is 45 g / m² or less. 2 It is more preferable that the amount be less than or equal to 40 g / m². 2 It is even more preferable that the amount of pretreatment solution applied to the fabric is such that the amount of polyvalent metal salt applied to the fabric is 1 to 50 g / m². 2The amount is preferably such that it is 3 to 45 g / m². 2 It is more preferable that the amount be such that 6-40 g / m 2 It is even more preferable that the amount be greater than or equal to the above. The amount of polyvalent metal salt applied to the fabric in the pretreatment solution may be changed depending on the type of fabric.

[0080] The process of applying white ink will be explained. It is preferable to apply the white ink to the fabric using an inkjet method. The inkjet method is not particularly limited and may be any method such as a piezo method, electrostatic method, or thermal method. When using an inkjet printing device, it is preferable to eject droplets of pretreatment liquid or ink from the inkjet head based on a digital signal and to adhere the ejected droplets to the fabric.

[0081] When applying the pretreatment solution using an inkjet method, the application of the pretreatment solution and the application of the white ink may be performed using separate printing devices, or they may be performed using a single printing device.

[0082] It is preferable that the white ink be applied so that it at least partially overlaps with the area where the pretreatment solution is applied. It is preferable that the area where the pretreatment solution is applied and the area where the white ink is applied overlap at least partially.

[0083] The white ink may be applied to the cloth treated with the pretreatment solution using a wet-on-wet method, or it may be applied after the cloth treated with the pretreatment solution has been dried. In the wet-on-wet method, it is preferable that the white ink is applied while the moisture has not been completely removed from the cloth treated with the pretreatment solution. Preferably, the white ink can be applied while the cloth treated with the pretreatment solution remains wet. For example, it is preferable to apply the white ink to the cloth without performing a drying process such as heat drying after applying the pretreatment solution. The temperature of the cloth surface after applying the pretreatment solution and before applying the white ink is preferably 40°C or lower, and more preferably 35°C or lower. It is preferable that the white ink is applied when the amount of volatile components of the pretreatment solution remaining on the cloth is 90% by mass or more after applying the pretreatment solution. The time from applying the pretreatment solution to applying the white ink is preferably 0.1 to 200 seconds.

[0084] The amount of white ink applied to the fabric is not particularly limited, but for example, 50-500 g / m² 2 Preferably, 100-400 g / m 2 This is preferable.

[0085] The amount of white ink applied to the fabric is 10 g / m², where the amount of resin particles of the white ink applied to the fabric is 10 g / m². 2 The amount is preferably greater than or equal to 20 g / m². 2 It is more preferable that the amount be greater than or equal to 35 g / m². 2 It is even more preferable that the amount is greater than or equal to the above. The amount of white ink applied to the fabric is such that the amount of resin particles of white ink applied to the fabric is 200 g / m². 2 The amount is preferably less than or equal to 150 g / m². 2 It is more preferable that the amount be less than or equal to 100 g / m². 2 It is even more preferable that the amount of white ink applied to the fabric is such that the amount of resin particles of the white ink applied to the fabric is 10 to 200 g / m². 2 The amount is preferably such that it is 20-150 g / m². 2 It is more preferable that the amount be such that 35-100 g / m²2 It is even more preferable that the amount be greater than or equal to the above.

[0086] In the method for manufacturing printed materials, it is preferable to include a step of heat-treating the fabric after the step of applying white ink. The heat treatment temperature can be appropriately selected depending on the material of the fabric, etc. For example, a heat treatment temperature of 100°C or higher is preferred, and 120°C or higher is more preferred. From the viewpoint of reducing damage to the fabric, a heat treatment temperature of 200°C or lower is preferred. The heating device is not particularly limited, but for example, a heat press, roll heater, hot air device, infrared lamp heater, etc., can be used. The heating time can be set appropriately depending on the heating method, etc. For example, 1 second to 10 minutes is preferred, 5 seconds to 5 minutes is more preferred, and 30 seconds to 3 minutes is also acceptable.

[0087] The method for manufacturing printed materials may further include a step of applying color ink after the white ink application step (hereinafter also referred to as the "color ink application step").

[0088] Examples of colored inks include magenta ink, cyan ink, yellow ink, and black ink, excluding white ink.

[0089] Color inks may include non-white colorants as colorants. Non-white colorants may include, for example, pigments, dyes, or combinations thereof. Color inks preferably contain water. Color inks may also contain, as needed, resin particles, surfactants, water-soluble organic solvents, etc.

[0090] It is preferable to apply the color ink to the fabric using an inkjet method. The color ink may also be applied to the fabric coated with white ink using a wet-on-wet method, or it may be applied after the fabric coated with white ink has dried.

[0091] A step of heat-treating the fabric may be included after the color ink application step. A step of applying a post-treatment solution may be included after the color ink application step. For example, a step of heat-treating the fabric may be included after the color ink application step, followed by the application of a post-treatment solution. Furthermore, a step of heat-treating the fabric may be included after the application of the post-treatment solution.

[0092] This disclosure includes the following embodiments. <1> Applying the pretreatment solution to the cloth, The process includes applying white ink to the cloth to which the pretreatment liquid has been applied using an inkjet method. The aforementioned pretreatment solution comprises a polyvalent metal salt, a surfactant, and water. The white ink comprises a white inorganic pigment, resin particles, a surfactant, and water, wherein the white inorganic pigment is present in an amount of 5.0 to 15.0% by mass of the total amount of the white ink, and the sum of the white inorganic pigment and the resin particles is present in an amount of 20 to 35% by mass of the total amount of the white ink. Amount A (g / m²) of the resin particles of the white ink applied to the fabric 2 ), and the amount of the polyvalent metal salt applied to the fabric in the pretreatment solution B (g / m 2 ) but, A 2 The relationship / B ≥ 50 is satisfied. A method for manufacturing printed materials. <2> In the aforementioned white ink, the mass ratio of the resin particles to the white inorganic pigment, "resin particles / white inorganic pigment", is 2.5 or greater. <1> A method for manufacturing the printed material described above. <3> The white ink contains 50% by mass or more of polyester-type polyurethane resin relative to the total amount of resin particles. <1> or <2> A method for manufacturing the printed material described above. [Examples]

[0093] The embodiments of the present invention will be described in detail below with reference to examples. The present invention is not limited to the following embodiments. In the following explanation, unless otherwise specified, "%" indicates "mass%".

[0094] 1. Preparation of pretreatment solution Table 1 shows the formulations of the pretreatment solutions. The raw materials were mixed according to the proportions listed in Table 1 and filtered through a cellulose acetate membrane filter with a pore size of 3 μm to obtain pretreatment solutions UC1 and UC2.

[0095] The details of the raw materials listed in Table 1 are as follows: Pretreatment solutions UC1 and UC2 each contain 25% by mass of polyvalent metal salts as active ingredients. (Polyvalent metal salts) Calcium chloride (anhydrous): Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 95% by mass Calcium nitrate tetrahydrate: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 98.5% by mass.

[0096] (Water-soluble organic solvent) Diethylene glycol: Manufactured by Fujifilm Wako Pure Chemical Corporation

[0097] (Surfactants) Olphine E1020: Acetylene glycol-based surfactant, manufactured by Nisshin Chemical Industry Co., Ltd., active ingredient 100% by mass, HLB16

[0098] [Table 1]

[0099] 2. Preparation of white ink (1) Preparation of white pigment dispersion 250g of titanium dioxide "R62N" (manufactured by Sakai Chemical Industry Co., Ltd.) was used as a white pigment, and 10g of "Demol EP" (manufactured by Kao Corporation) (2.5g of active ingredient) was used as a pigment dispersant. This mixture was combined with 740g of ion-exchanged water, and 0.5mmΦ zirconia beads were dispersed using a bead mill (Shinmaru Enterprises, Ltd., DYNO-MILL KDL A type) at a packing density of 80% and a residence time of 2 minutes to obtain a white pigment dispersion (pigment content 25% by mass).

[0100] (2) Preparation of white ink Tables 2 and 3 show the formulations for white inks W1 to W10. The raw materials were mixed according to the proportions shown in the tables and filtered through a cellulose acetate membrane filter with a pore size of 3 μm to obtain white inks W1 to W10.

[0101] The details of the raw materials for the white inks W1 to W10 listed in Tables 2 and 3 are as follows:

[0102] (Pigment dispersion) White pigment dispersion: White pigment dispersion obtained by the above method, pigment content 25% by mass

[0103] (Resin emulsion) Superflex 740: Polyester-type polyurethane resin emulsion, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., average particle size 170 nm, resin content 40% by mass. Superflex E2000: Polyester-type polyurethane resin emulsion, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., average particle size 588 nm, resin content 50% by mass Superflex 470: Polycarbonate-type polyurethane resin emulsion, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., average particle size 108 nm, resin content 38% by mass. Impranyl DLU: Polyether-type polyurethane resin emulsion, manufactured by Sumika Covestro Urethane Co., Ltd., average particle size 495 nm, resin content 60% by mass

[0104] The average particle size of the resin particles in each of the above resin emulsions was measured using a dynamic light scattering particle size distribution analyzer, "nano Prtica SZ-100" (manufactured by Horiba, Ltd.). Each resin emulsion was diluted with purified water to a resin particle concentration of 0.5% by mass, and the volume-based median diameter was measured at a temperature of 25°C with the dispersion medium refractive index: 1.333, sample refractive index: 1.600, and calculation conditions: polydisperse and narrow.

[0105] (Water-soluble organic solvent) Glycerin: Manufactured by Fujifilm Wako Pure Chemical Corporation Diethylene glycol: Manufactured by Fujifilm Wako Pure Chemical Corporation

[0106] (Surfactants) Olphine E1010: Acetylene glycol-based surfactant, manufactured by Nisshin Chemical Industry Co., Ltd., active ingredient 100% by mass, HLB13

[0107] [Table 2]

[0108] [Table 3]

[0109] 3. Preparation of printed materials Using the pretreatment solutions UC1-UC2 and white inks W1-W10 prepared as described above, printed materials for Examples 1-9 and Comparative Examples 1-7 were prepared according to the following procedure. Tables 4-7 show the pretreatment solutions and their application amounts used in the preparation of the printed materials for Examples 1-9 and Comparative Examples 1-7, as well as the white ink and its application amounts. A 10cm x 20cm area of ​​a black cotton T-shirt (Toms Co., Ltd. "Printstar" (product name)) was treated with a predetermined amount of pretreatment solution using an inkjet method. After applying the pretreatment solution, without a drying process, white ink was applied to the treated area using an inkjet method in a predetermined amount. The image was a solid color. For both the application of the pretreatment solution and the white ink, a mastermind "MMP-8130" (product name) was used as the printing device. After applying the white ink, the fabric was heated and dried for 2 minutes at 160°C using a FUSION heat press to obtain a printed material with a 10cm x 20cm solid color image.

[0110] 4. Evaluation of cracks after washing The resulting printed materials were washed according to the AATCC 61 2A standard, and then the cracks in the image areas were judged according to the following criteria. The evaluation results are shown in Tables 4-7. A: No cracks have appeared at all. B: There are slight cracks. C: Cracks have appeared, but they do not affect practical use. D: There are many cracks, making it problematic for practical use.

[0111] [Table 4]

[0112] [Table 5]

[0113] [Table 6]

[0114] [Table 7]

[0115] Examples 1-9 showed suppressed cracking of the white image after washing. On the other hand, the amount of resin particles A (g / m²) of white ink applied to the fabric was... 2 ), and the amount of polyvalent metal salt applied to the fabric in the pretreatment solution B (g / m²) 2 ) but, A 2 Comparative Examples 1-5, which did not satisfy the relationship / B≧50, and Comparative Example 6, which used White Ink 8 with a large amount of white inorganic pigment, and Comparative Example 7, which used White Ink 7 with a small total amount of resin particles and white inorganic pigment in the white ink, all exhibited a large number of cracks after washing, which was at a level that posed a practical problem. Note that in Comparative Examples 1-3 and 5, A 2 In addition to not satisfying the relationship / B≧50, all of the white inks used had a small total amount of resin particles and white inorganic pigment in them.

Claims

1. Applying the pretreatment solution to the cloth, The process includes applying white ink to the cloth to which the pretreatment liquid has been applied using an inkjet method. The aforementioned pretreatment solution comprises a polyvalent metal salt, a surfactant, and water. The white ink comprises a white inorganic pigment, resin particles, a surfactant, and water, wherein the white inorganic pigment is present in an amount of 5.0 to 15.0% by mass of the total amount of the white ink, and the sum of the white inorganic pigment and the resin particles is present in an amount of 20 to 35% by mass of the total amount of the white ink. A (g / m²) of the resin particles of the white ink applied to the fabric. ２ ), and the amount B (g / m) of the polyvalent metal salt applied to the fabric in the pretreatment solution. ２ ) but, A ２ The relationship / B ≥ 50 is satisfied, The resin particles of the white ink include polyurethane resin. The application of the aforementioned white ink is carried out using a wet-on-wet method. A method for manufacturing printed materials.

2. The method for producing a printed article according to claim 1, wherein in the white ink, the mass ratio of the resin particles to the white inorganic pigment, "resin particles / white inorganic pigment", is 2.5 or more.

3. The method for producing a printed article according to claim 1 or 2, wherein the white ink contains 50% by mass or more of polyester-type polyurethane resin relative to the total amount of resin particles.

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