Ink set for textile printing and method for manufacturing printed materials

Abstract

To provide an ink set for printing which enables formation of a non-white image excellent in color development property.SOLUTION: An ink set for printing contains a pretreatment liquid containing a polyvalent metal salt, a water-soluble organic solvent and a surface active agent, white inkjet ink containing a white pigment, resin particles and a water-soluble organic solvent, and non-white inkjet ink containing a non-white pigment, resin particles, a water-soluble organic solvent and a surface active agent, wherein when surface tension of the pretreatment liquid is represented by X, surface tension of the white inkjet ink is represented by Y, surface tension of the non-white inkjet ink is represented by Z1, and surface tension of a liquid having such a composition that the surface active agent is excluded from the non-white inkjet ink is represented by Z2, the following expression 1, expression 2 and expression 3 are satisfied. (Expression 1) 33 mN / m≤X≤50 mN / m. (Expression 2) -5 mN / m≤Y-Z1≤10 mN / m. (Expression 3) 0 mN / m≤Z2-Z1≤10 mN / m.SELECTED DRAWING: None

Description

[Technical Field] 【0001】 Embodiments of the present invention relate to a printing ink set and a method for manufacturing a printed product. [Background technology] 【0002】 In addition to screen printing and roller printing, inkjet printing is gaining attention as a method for printing images such as letters, pictures, and patterns onto fabrics such as woven, knitted, and nonwoven materials. 【0003】 Images formed on dark-colored fabrics, such as black, tend to be less visible compared to images formed on 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, and then an ink containing a white pigment is printed to form a white image, on which a desired image is formed. Patent Document 1 also describes heat treatment being performed after applying the pretreatment agent. [Prior art documents] [Patent Documents] 【0004】 [Patent Document 1] Japanese Patent Publication No. 2009-30014 [Overview of the Initiative] [Problems that the invention aims to solve] 【0005】 When a pretreatment solution containing a coagulant is applied to a dark-colored cloth, and then white ink is applied to the substrate using a so-called wet-on-wet method without a drying step to form a white image, and then a non-white ink is applied to form a non-white image, sufficient color development may not be obtained in the non-white image. Embodiments of the present invention aim to provide a printing ink set capable of producing printed materials having non-white images with excellent color development, and a method for producing printed materials. [Means for solving the problem] 【0006】 One embodiment of the present invention relates to a textile printing ink set comprising a pretreatment solution containing a polyvalent metal salt, a water-soluble organic solvent, and a surfactant; a white inkjet ink containing a white pigment, resin particles, and a water-soluble organic solvent; and a non-white inkjet ink containing a non-white pigment, resin particles, a water-soluble organic solvent, and a surfactant, wherein when the surface tension of the pretreatment solution is X, the surface tension of the white inkjet ink is Y, the surface tension of the non-white inkjet ink is Z1, and the surface tension of the liquid having the composition obtained by removing the surfactant from the non-white inkjet ink is Z2, the set satisfies the following formulas 1, 2, and 3. (Formula 1) 33mN / m≦X≦50mN / m (Formula 2)-5mN / m≦Y-Z1≦10mN / m (Formula 3) 0mN / m≦Z2-Z1≦10mN / m Another embodiment of the present invention relates to a method for producing a printed fabric, comprising applying a pretreatment solution to a cloth, applying a white inkjet ink to the cloth to which the pretreatment solution has been applied by an inkjet method, and applying a non-white inkjet ink to the cloth to which the white inkjet ink has been applied by an inkjet method, wherein the pretreatment solution comprises a polyvalent metal salt, a water-soluble organic solvent, and a surfactant; the white inkjet ink comprises a white pigment, resin particles, and a water-soluble organic solvent; the non-white inkjet ink comprises a non-white pigment, resin particles, a water-soluble organic solvent, and a surfactant; and when the surface tension of the pretreatment solution is X, the surface tension of the white inkjet ink is Y, the surface tension of the non-white inkjet ink is Z1, and the surface tension of a liquid having the composition obtained by removing the surfactant from the non-white inkjet ink is Z2, the method satisfies the following formulas 1, 2, and 3. (Formula 1) 33mN / m≦X≦50mN / m (Formula 2)-5mN / m≦Y-Z1≦10mN / m (Formula 3) 0mN / m≦Z2-Z1≦10mN / m [Effects of the Invention] 【0007】 According to an embodiment of the present invention, a resist-dyed product having a non-white image with excellent color development can be produced. 【Embodiments for Carrying Out the Invention】 【0008】 Hereinafter, an embodiment of the present invention will be described in detail. However, it is needless to say that the present invention is not limited to these embodiments, and various modifications and changes may be made. 【0009】 <Ink set for resist dyeing> An ink set for resist dyeing according to one embodiment includes a pretreatment liquid containing a polyvalent metal salt, a water-soluble organic solvent, and a surfactant, a white inkjet ink containing a white pigment, resin particles, and a water-soluble organic solvent, and a non-white inkjet ink containing a non-white pigment, resin particles, a water-soluble organic solvent, and a surfactant. When the surface tension of the pretreatment liquid is X, the surface tension of the white inkjet ink is Y, the surface tension of the non-white inkjet ink is Z1, and the surface tension of a liquid having a composition obtained by removing the surfactant from the non-white inkjet ink is Z2, it is an ink set for resist dyeing that satisfies the following formulas (1), (2), and (3). (Formula 1) 33 mN / m ≤ X ≤ 50 mN / m (Formula 2) -5 mN / m ≤ Y - Z1 ≤ 10 mN / m (Formula 3) 0 mN / m ≤ Z2 - Z1 ≤ 10 mN / m When this ink set for resist dyeing is used, a non-white image with excellent color development can be formed. In particular, even when printing is performed on a dark-colored cloth by the wet-on-wet method, a non-white image with excellent color development can be formed. 【0010】 In the following description, the ink set for resist dyeing may be simply referred to as an ink set. Also, the white inkjet ink may be simply referred to as white ink. Also, the non-white inkjet ink may be simply referred to as non-white ink. 【0011】 Although not bound by a specific theory, it is considered that the ink set of one embodiment may act as follows. 【0012】 When a white image with excellent color development can be formed, the color development of a non-white image formed thereon also tends to be good. When the pretreatment liquid penetrates into the fabric, the amount of the aggregating agent on the fabric surface decreases. However, when the surface tension (X) of the pretreatment liquid is 33 mN / m or more, the pretreatment liquid hardly penetrates into the fabric, and a decrease in the amount of the aggregating agent on the fabric surface and a consequent decrease in the reactivity between the white ink and the aggregating agent are suppressed, and the color development of the white image can be improved. When the surface tension (X) of the pretreatment liquid is 50 mN / m or less, the pretreatment liquid easily levels on the fabric surface after landing on the fabric. Therefore, the uniformity of the white image can be improved, and thereby, the color development of the white image can be improved. 【0013】 When the surface tension (Y) of the white ink and the surface tension (Z1) of the non-white ink satisfy Y - Z1 ≤ 10 mN / m, the wet spreading of the non-white ink on the white image is likely to be suppressed, and even when pressure heating and drying such as heat pressing are performed, the non-white ink and the white ink are unlikely to mix, and the color development of the non-white ink can be made good. 【0014】 When the dots of the non-white ink become small, the color development of the non-white ink image tends to decrease due to the exposure of the underlying white image. When -5 mN / m ≤ Y - Z1 is satisfied, the dots of the non-white ink are unlikely to become small, and the color development of the non-white ink image can be improved. 【0015】 In the wet-on-wet method, if non-white ink is applied before the pretreatment solution and white ink have completely dried, the dots of non-white ink will overlap on a fluid coating film with a large amount of residual liquid. If heat drying is performed in this state using a heat press or the like, the color development of the non-white image after drying may be reduced. This is thought to be because the surfactant activity of the surfactant in the non-white ink decreases due to heat, causing the non-white ink dots to shrink and the underlying white image to be exposed. This decrease in surfactant activity is particularly likely to occur with nonionic surfactants. When the surface tension of the non-white ink (Z1) and the surface tension of the liquid with the composition of the non-white ink excluding the surfactant (Z2) satisfy Z2-Z1≦10mN / m, that is, when the difference in surface tension with and without the surfactant is 10mN / m or less, the effect of the decrease in surfactant activity on the surface tension is small, and in the wet-on-wet method, the color development of the non-white image after heat drying using a heat press or the like can be improved. 【0016】 One embodiment of the textile printing ink set includes a pretreatment solution containing a polyvalent metal salt, a water-soluble organic solvent, and a surfactant; a white inkjet ink containing a white pigment, resin particles, and a water-soluble organic solvent; and a non-white inkjet ink containing a non-white pigment, resin particles, a water-soluble organic solvent, and a surfactant. The textile printing ink set may, for example, contain two or more types of non-white inkjet inks. The textile printing ink set may further contain a post-treatment solution, etc. 【0017】 The following describes the pretreatment solution, white inkjet ink, and non-white inkjet ink. 【0018】 <Pretreatment solution> The pretreatment solution may contain polyvalent metal salts as a coagulant. 【0019】 Polyvalent metal salts generally tend to have high reactivity and can agglomerate the colorants of white ink well on a substrate with a relatively small amount. Therefore, when using polyvalent metal salts, the amount of the pretreatment liquid applied can be reduced. When the amount of the pretreatment liquid applied is large, it tends to prevent the penetration and drying of white ink and non-white ink, increasing the amount of liquid on the printed surface and making it easier to maintain the fluidity of the ink layer. For this reason, the dot size and shape of these inks are likely to be disturbed, and the color development is likely to decrease. 【0020】 Polyvalent metal salts are composed of polyvalent metal ions with a valence of 2 or more and anions. Examples of polyvalent metal ions with a valence of 2 or more include Ca 2+ , Mg 2+ , Cu 2+ , Ni 2+ , Zn 2+ , Ba 2+ and the like. Examples of anions include Cl - , NO3 - , CH3COO - , I - , Br - , SO4 2- , ClO3 - and the like. Specific examples of polyvalent metal salts include calcium chloride, calcium nitrate, magnesium nitrate, magnesium sulfate, copper nitrate, calcium acetate, magnesium acetate and the like. The polyvalent metal salt may be a hydrate or an anhydride. 【0021】 These polyvalent metal salts may be used alone or in combination of two or more. The content of the polyvalent metal salt is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more, based on the total amount of the pretreatment liquid in terms of the active ingredient amount. On the other hand, the content of the polyvalent metal salt is preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less, based on the total amount of the pretreatment liquid in terms of the active ingredient amount. The content of the polyvalent metal salt is preferably 10 - 50% by mass, more preferably 15 - 45% by mass, and even more preferably 20 - 40% by mass, based on the total amount of the pretreatment liquid in terms of the active ingredient amount. 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. 【0022】 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, polyethylene glycol, propylene glycol, 1,3-propanediol, 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 monobutyl ether. Glycol ethers such as 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. 【0023】 Water-soluble organic solvents may be used alone, 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 is preferably 1 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 the pretreatment solution. 【0024】 The pretreatment solution preferably contains 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. 【0025】 The HLB value of the surfactant is preferably 5 to 20, and more preferably 10 to 18. 【0026】 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. 【0027】 Examples of acetylene-based surfactants include acetylene glycol-based surfactants, acetylene alcohol-based surfactants, and surfactants having an acetylene group. 【0028】 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). 【0029】 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). 【0030】 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). 【0031】 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). 【0032】 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). 【0033】 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). 【0034】 Surfactants may be used individually or in combination of two or more types. 【0035】 The surfactant content 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, based on the total amount of the pretreatment solution. 【0036】 The pretreatment solution may contain other components as needed. Examples of other components include water, defoamers, pH adjusters, antioxidants, and preservatives. 【0037】 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. 【0038】 The amount of water is preferably 20-80% by mass, more preferably 30-70% by mass, and even more preferably 40-60% by mass, based on the total amount of pretreatment solution. 【0039】 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. 【0040】 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. 【0041】 From the viewpoint of good color development of white images and consequently good color development of non-white images, it is preferable that the following formula 1 is satisfied when the surface tension of the pretreatment solution is X. (Formula 1) 33mN / m≦X≦50mN / m 【0042】 From the viewpoint of good color development of white images and the resulting good color development of non-white images, X is preferably 33 mN / m or more, more preferably 34 mN / m or more, and even more preferably 35 mN / m or more. From the viewpoint of good color development of white images and the resulting good color development of non-white images, X is preferably 50 mN / m or less, more preferably 45 mN / m or less, and even more preferably 40 mN / m or less. X is preferably 33 mN / m to 50 mN / m, more preferably 34 mN / m to 45 mN / m, and even more preferably 35 mN / m to 40 mN / m. 【0043】 The surface tension of the pretreatment solution can be controlled by, for example, the type and amount of surfactants, water-soluble organic solvents, etc. 【0044】 In this specification, surface tension is defined as the dynamic surface tension at a frequency of 0.05 Hz, and is the value at 23°C. It can be determined according to the bubble pressure method (maximum bubble pressure method) under measurement conditions of 23°C and 0.05 Hz. For measurement, for example, the "SITA Messtechnik GmbH science line t60" manufactured by SITA Process Solutions can be used. 【0045】 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. 【0046】 <White inkjet ink> White inkjet ink contains white pigment as a colorant. Examples of white pigments include inorganic pigments such as titanium dioxide, zinc oxide, zinc sulfide, antimony oxide, and zirconium oxide. White pigments such as hollow resin microparticles and polymer microparticles can also be used. 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. 【0047】 Self-dispersing pigments may be used as white pigments. Self-dispersing pigments are pigments in which hydrophilic functional groups are introduced to the surface of the pigment by chemical or physical treatment. The hydrophilic functional groups to be introduced into self-dispersing pigments will be described later. As a white 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. 【0048】 White pigments may be used individually or in combination of two or more types. 【0049】 From the viewpoint of opacity and other factors, the content of the white pigment is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and even more preferably 5 to 15% by mass, relative to the total amount of white inkjet ink. 【0050】 To stably disperse white pigment in white inkjet 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). 【0051】 The pigment dispersant may be used alone or in combination of two or more types. When using a pigment dispersant, the amount in white inkjet 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. 【0052】 White inkjet inks may contain resin particles. 【0053】 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 inkjet ink. 【0054】 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. 【0055】 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. 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. 【0056】 From the viewpoint of inkjet ejection performance, the average particle diameter of the resin particles is preferably 600 nm or less, more preferably 300 nm or less, and even more preferably 200 nm or less. For example, the average particle diameter of the resin particles may be in the range of 10 nm to 600 nm, in the range of 50 nm to 300 nm, or in the range of 50 nm to 200 nm. In this specification, the average particle diameter of the resin particles is the volume-based average particle diameter obtained by dynamic light scattering. 【0057】 As for the type of resin particles, it is preferable to use a resin that forms a transparent coating film. 【0058】 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 (sometimes referred to as "urethane 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. 【0059】 The resin particles preferably include acrylic resin particles, urethane resin particles, or a combination thereof. The polyurethane resin may be either aliphatic polyurethane or aromatic polyurethane. Examples of polyurethane resins include ether-based polyurethane resins, ester-based polyurethane resins, ester-ether-based polyurethane resins, and carbonate-based polyurethanes. 【0060】 Commercially available resin particle emulsions include "Superflex 460," "Superflex 470," "Superflex 740," and "Superflex 150" from Daiichi Kogyo Seiyaku Co., Ltd., and "Movinyl 6763" and "Movinyl 6718" from Japan Coating Resin Co., Ltd. (all are product names). 【0061】 The resin particles may be used individually or in combination of two or more types. The amount of resin particles is preferably 5% by mass or more, more preferably 8% by mass or more, even more preferably 10% by mass or more, and even more preferably 12% by mass or more, relative to the total amount of white inkjet ink. The amount of resin particles A is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less, relative to the total amount of white inkjet ink. For example, the amount of resin particles relative to the total amount of white inkjet ink is preferably 5 to 30% by mass, more preferably 8 to 25% by mass, even more preferably 10 to 20% by mass, and even more preferably 12 to 20% by mass. 【0062】 It is preferable to incorporate a water-soluble organic solvent into the white inkjet 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 an equal volume of water at 1 atmosphere and 20°C. The boiling point of the water-soluble organic solvent is preferably 100°C or higher, and more preferably 150°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. 【0063】 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, and more preferably 10 to 40% by mass, relative to the total amount of white inkjet ink. 【0064】 White inkjet ink may contain other components as needed. These other components may include water, surfactants, pH adjusters, and preservatives. 【0065】 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. In particular, from the viewpoint of the storage stability of the ink, it is preferable to use a water with a low content of polyvalent metal ions such as calcium. For the water used, for example, deionized water, distilled water, or ultrapure water may be used. From the viewpoint of adjusting the viscosity of the ink, water is preferably included in the total amount of white inkjet 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. 【0066】 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. 【0067】 The HLB value of the surfactant is preferably 5 to 20, and more preferably 10 to 18. 【0068】 As nonionic surfactants, for example, those described in the pretreatment solution above can be selected and used. Among these, acetylene-based surfactants such as acetylene glycol-based surfactants can be preferably used. 【0069】 The surfactant content 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, based on the total amount of white inkjet ink. 【0070】 The method for manufacturing white inkjet 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. 【0071】 From the viewpoint of ink storage stability, the pH of white inkjet ink is preferably 7.0 to 10.0, and more preferably 7.5 to 9.0. The viscosity of the white inkjet ink is preferably 1 to 30 mPa·s at 23°C, for example, from the viewpoint of inkjet ejection performance. 【0072】 When the surface tension of white inkjet ink is Y, Y is preferably 28 mN / m or more, more preferably 30 mN / m or more, and even more preferably 32 mN / m or more. On the other hand, Y is preferably 50 mN / m or less, more preferably 45 mN / m or less, and even more preferably 42 mN / m or less. For example, Y is preferably 28 mN / m to 50 mN / m, more preferably 30 mN / m to 45 mN / m, and even more preferably 32 mN / m to 42 mN / m. 【0073】 The surface tension of white inkjet ink can be controlled, for example, by the type and amount of water-soluble organic solvents used. 【0074】 When the surface tension of a non-white inkjet ink is Z1, it is preferable that Y and Z1 satisfy the following formula 2 from the viewpoint of improving the color development of non-white images. (Formula 2)-5mN / m≦Y-Z1≦10mN / m 【0075】 From the viewpoint of improving the color development of non-white images, Y-Z1 is preferably -5 mN / m or higher, more preferably -3 mN / m or higher, and even more preferably -2 mN / m or higher. On the other hand, from the viewpoint of improving the color development of non-white images, Y-Z1 is preferably 10 mN / m or less, more preferably 8 mN / m or less, and even more preferably 6 mN / m or less. Y-Z1 is preferably between -5 mN / m and 10 mN / m, more preferably between -3 mN / m and 8 mN / m, and even more preferably between -2 mN / m and 6 mN / m. 【0076】 White inkjet ink can be preferably used for textile printing. White inkjet ink can be applied to a substrate by the inkjet method to form a white image. A non-white image can be formed by applying a non-white inkjet ink to a substrate that has been treated with white inkjet ink. It is preferable to apply the white inkjet ink to a substrate that has been treated with a pretreatment solution. 【0077】 <Non-white inkjet ink> Non-white inkjet inks include inks other than white ink, such as magenta ink, cyan ink, yellow ink, and black ink. 【0078】 Non-white inkjet inks may contain non-white pigments as colorants. 【0079】 Non-white pigments that can be used include organic pigments such as azo pigments, phthalocyanine pigments, polycyclic pigments, and blue-green lake pigments, as well as inorganic pigments such as carbon black and metal oxides. Examples of azo pigments include soluble azo lake pigments, insoluble azo pigments, and condensed azo pigments. Examples of phthalocyanine pigments include metallic phthalocyanine pigments and metal-free phthalocyanine pigments. Examples of polycyclic pigments include quinacridone pigments, perylene pigments, perinone pigments, isoindoline pigments, isoindolinone pigments, dioxazine pigments, thioindigo pigments, anthraquinone pigments, quinophthalone pigments, metal complex pigments, and diketopyrrolopyrrole (DPP). Examples of carbon black include furnace carbon black, lamp black, acetylene black, and channel black. These pigments may be used individually or in combination of two or more types. 【0080】 From the viewpoint of ejection stability and storage stability, the average particle size of non-white pigment particles in non-white ink is preferably 300 nm or less, more preferably 200 nm or less, and even more preferably 150 nm or less, as the volume-based average value of the particle size distribution measured by dynamic light scattering. 【0081】 Self-dispersing pigments may be incorporated as non-white pigments. Self-dispersing pigments are pigments in which hydrophilic functional groups are introduced to the surface of the pigment by chemical or physical treatment. The hydrophilic functional groups introduced into the self-dispersing pigment are preferably ionic, and by charging the pigment surface anionic or cationic, 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. 【0082】 These hydrophilic functional groups may be directly bonded to the pigment surface or bonded via other atomic groups. Examples of other atomic groups include, but are not limited to, alkylene groups, phenylene groups, and naphthylene groups. Examples of pigment surface treatment methods include diazotization, sulfonation, hypochlorite treatment, humic acid treatment, and vacuum plasma treatment. 【0083】 As self-dispersing pigments, for example, the CAB-O-JET series from Cabot Corporation, such as "CAB-O-JET200," "CAB-O-JET300," "CAB-O-JET250C," "CAB-O-JET260M," "CAB-O-JET270," and "CAB-O-JET450C," and from Orient Chemical Industries, Ltd., such as "BONJET BLACK CW-1," "BONJET BLACK CW-2," "BONJET BLACK CW-3," and "BONJET BLACK CW-4," can be preferably used (all are product names). As a non-white pigment, microencapsulated pigments in which a non-white pigment is coated with resin may be used. 【0084】 Pigment dispersions in which non-white pigments are pre-dispersed with a pigment dispersant may be used. Examples of commercially available pigment dispersions dispersed with a pigment dispersant include the HOSTAJET series from Clariant, the FUJI SP series from Fuji Pigment Co., Ltd., and "AC-AK1" (product name) from Dainichi Seika Kogyo Co., Ltd. Pigment dispersions dispersed with the pigment dispersant described later may also be used. 【0085】 From the viewpoint of further improving the color development of non-white images, the charge density of the non-white pigment is preferably 200 μeq / g or less, more preferably 150 μeq / g or less, and even more preferably 120 μeq / g or less. When the charge density of the non-white pigment is 200 μeq / g or less, it is easier to further improve the color development of non-white images. The mechanism is not clear, but it is presumed to be as follows: Depending on the type of cloth used as the substrate, the amount of flocculant remaining on the surface of the cloth differs. For example, with cloths that have low water absorption, the flocculant tends to remain on the surface of the cloth and is more likely to be mixed in with the white image. When the non-white pigment reacts with the flocculant mixed in with the white image, the aggregation of non-white pigment particles progresses, the pigment particles become larger, the number of particles decreases, the distribution of non-white pigment particles becomes uneven, and the color development tends to decrease. When the charge density of the non-white pigment is 200 μeq / g or less, the reactivity between the non-white pigment and the flocculant mixed in with the white image becomes low, making it easier for the non-white pigment particles to be distributed uniformly, and thus easier to further improve the color development. 【0086】 From the viewpoint of suppressing bleeding and forming sharp images on highly water-repellent fabrics such as water-repellent T-shirts, the charge density of the non-white pigment is preferably 30 μeq / g or more, and more preferably 50 μeq / g or more. The charge density of the non-white pigment is preferably, for example, 30 to 200 μeq / g, more preferably 30 to 150 μeq / g, and even more preferably 50 to 120 μeq / g. 【0087】 In this specification, the charge density of a pigment is the charge density measured by the flow potential method. The charge density of a pigment is the amount of charge per unit of solid content of the pigment in a pigment dispersion (unit: μeq / g). Specifically, the pigment dispersion to be measured is diluted 100 times with water to obtain a diluted solution, which is used as the sample. Titration is performed with a 0.0025N polydiallyldimethylammonium chloride solution, and the reaction endpoint at which the sample's flow potential becomes 0V is measured. The total charge of the sample (diluted pigment dispersion) can be determined from the amount of 0.0025N polydiallyldimethylammonium chloride solution used up to the reaction endpoint. The charge density of the pigment (μeq / g) is obtained by dividing the total charge of the sample (diluted pigment dispersion) by the amount of solid pigment contained in the sample. For measuring charge density, for example, a colloidal particle charge meter (AFG ANALYTIC GmbH's "Model CAS") can be used. 【0088】 Non-white pigments may be used individually or in combination of two or more types. 【0089】 From the viewpoint of print density and ink viscosity, the content of non-white pigment is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, and even more preferably 2 to 6% by mass, relative to the total amount of non-white inkjet ink. 【0090】 To stably disperse non-white pigments in non-white inkjet inks, pigment dispersants such as polymer dispersants and surfactant-type dispersants can be used. 【0091】 As a pigment dispersant, for example, one can be selected and used from those described above for the white inkjet ink. When using a pigment dispersant, the amount to be incorporated into a non-white inkjet 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. 【0092】 Non-white inkjet inks may contain resin particles. The resin particles are preferably dispersible in an aqueous solvent. The resin particles are preferably able to disperse 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 non-white inkjet inks. 【0093】 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. From the viewpoint of further improving the color development of non-white images, it is preferable that the resin particles in the non-white inkjet ink include forced-emulsification type resin particles. It is preferable that the resin in the forced-emulsification type resin particles does not have hydrophilic functional groups. 【0094】 The resin particles may be, for example, anionic resin particles, cationic resin particles, nonionic resin particles, or amphoteric resin particles, but anionic resin particles, nonionic resin particles, or a combination thereof are preferred. 【0095】 The anionic resin particles may be those in which the anionic functional groups of the resin are present on the surface of the resin particles, such as self-emulsifying resins, or they may be those that have undergone surface treatment, such as by attaching an anionic dispersant to the surface of the resin particles. Nonionic resin particles may have nonionic functional groups present on the surface of the resin, such as in self-emulsifying resins, or they may have surface treatments such as the application of a nonionic dispersant to the surface. Examples of anionic functional groups, anionic dispersants, nonionic functional groups, and nonionic dispersants include those described above for the resin particles of the white ink. 【0096】 From the viewpoint of inkjet ejection performance, the average particle diameter of the resin particles is preferably 600 nm or less, more preferably 300 nm or less, and even more preferably 200 nm or less. For example, the average particle diameter of the resin particles may be in the range of 10 nm to 600 nm, in the range of 50 nm to 300 nm, or in the range of 50 nm to 200 nm. 【0097】 As for the type of resin particles, it is preferable to use a resin that forms a transparent coating film. 【0098】 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. 【0099】 The resin particles preferably include acrylic resin particles, urethane resin particles, or a combination thereof. Examples of commercially available resin particle emulsions include the white ink example mentioned above. 【0100】 The resin particles may be used individually or in combination of two or more types. From the viewpoint of color development of non-white images, the amount of resin particles is preferably 10% by mass or more, more preferably 12% by mass or more, and even more preferably 14% by mass or more, relative to the total amount of non-white inkjet ink. When the amount of resin particles is 10% by mass or more relative to the total amount of non-white inkjet ink, even when heat drying is performed using a pressure-type heating device such as a heat press, the fluidity of the dots is suppressed, the mixing of non-white ink and white ink is easily suppressed, and the color development of the non-white ink tends to be better. The amount of resin particles is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less, relative to the total amount of non-white inkjet ink. For example, the amount of resin particles is preferably 10 to 30% by mass, more preferably 12 to 25% by mass, and even more preferably 14 to 20% by mass, relative to the total amount of non-white inkjet ink. 【0101】 Non-white inkjet inks preferably contain forced-emulsification resin particles. From the viewpoint of further improving the color development of non-white images, the amount of forced-emulsification resin particles is preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on the total amount of non-white inkjet ink. The higher the amount of forced-emulsification resin particles, the more likely it is that the increase in Z2-Z1, described later, can be suppressed. Although the mechanism is not clear, it is presumed that in the case of forced-emulsification resin particles, the dispersant used to disperse the resin particles can lower the surface tension of the solvent, and because forced-emulsification resin particles are dispersed by a dispersant, steric hindrance and intermolecular forces contribute more to dispersion stabilization compared to self-emulsifying resin particles, and they are less likely to aggregate even when in contact with polyvalent metal salts mixed in the white ink layer, thus making it easier to suppress dot shrinkage. 【0102】 The amount of forced-emulsification resin particles is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less, relative to the total amount of non-white inkjet ink. For example, the amount of forced-emulsification resin particles is preferably 3 to 30% by mass, more preferably 5 to 25% by mass, and even more preferably 10 to 20% by mass or more, relative to the total amount of non-white inkjet ink. The forced emulsification type resin particles are 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 of the resin particles in the non-white inkjet ink. 【0103】 Non-white inkjet inks may contain 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 an equal volume of water at 1 atmosphere and 20°C. The boiling point of the water-soluble organic solvent is preferably 100°C or higher, and more preferably 150°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. These 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 water-soluble organic solvent in non-white inkjet ink is preferably 10 to 50% by mass, and more preferably 20 to 40% by mass, relative to the total amount of non-white inkjet ink. 【0104】 Non-white inkjet inks preferably contain a surfactant. 【0105】 As surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, or combinations thereof can be preferably used, but nonionic surfactants are more preferred from the viewpoint of stability. In addition, either low molecular weight surfactants or high molecular weight surfactants may be used. 【0106】 The HLB value of the surfactant is preferably 5 to 20, and more preferably 10 to 18. As the surfactant, for example, one can be selected and used from those described above for the white inkjet ink. Among these, acetylene-based surfactants such as acetylene glycol-based surfactants can be preferably used. 【0107】 Surfactants may be used individually or in combination of two or more types. The surfactant content 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 non-white inkjet ink. 【0108】 Non-white inkjet inks may contain other components as needed. These other components may include water, pH adjusters, and preservatives. 【0109】 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. In particular, from the viewpoint of the storage stability of the ink, 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 an amount of 30 to 70% by mass relative to the total amount of non-white inkjet ink, and more preferably in an amount of 35 to 65% by mass. 【0110】 The method for manufacturing non-white inkjet 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. 【0111】 The pH of non-white inkjet ink is preferably 7.0 to 10.0, and more preferably 7.5 to 9.0, from the viewpoint of ink storage stability. The viscosity of non-white inkjet ink is preferably 1 to 30 mPa·s at 23°C, for example, from the viewpoint of inkjet ejection performance. 【0112】 When the surface tension of a non-white inkjet ink is Z1, Z1 is preferably 28 mN / m or more, more preferably 30 mN / m or more, and even more preferably 32 mN / m or more. On the other hand, Z1 is preferably 50 mN / m or less, more preferably 45 mN / m or less, and even more preferably 42 mN / m or less. For example, Z1 is preferably 28 mN / m to 50 mN / m, more preferably 30 mN / m to 45 mN / m, and even more preferably 32 mN / m to 42 mN / m. 【0113】 The surface tension of non-white inkjet inks can be controlled by, for example, the type and amount of surfactants, water-soluble organic solvents, etc. 【0114】 When Z2 is the surface tension of a liquid having a composition obtained by removing the surfactant from a non-white inkjet ink, from the viewpoint of improving the color development of non-white images, Z2-Z1 is preferably 10 mN / m or less, more preferably 8 mN / m or less, and even more preferably 6.5 mN / m or less. 【0115】 It is preferable that Z2-Z1 is 0 mN / m or greater. Z2-Z1 may also be higher than, for example, 0 mN / m. 【0116】 From the viewpoint of improving the color reproduction of non-white images, it is preferable that Z2-Z1 be between 0mN / m and 10mN / m, that is, satisfy the following equation 3. (Formula 3) 0mN / m≦Z2-Z1≦10mN / m 【0117】 It is more preferable that Z2-Z1 is between 0 mN / m and 6.5 mN / m, that is, that it satisfies equation 4 below. (Formula 4)0mN / m≦Z2-Z1≦6.5mN / m 【0118】 Z2-Z1 can be controlled, for example, by selecting resin particles, pigment particles, and water-soluble solvents. Furthermore, if the resin particles in non-white inks include forced-emulsification type resin particles, it is easier to reduce Z2-Z1. 【0119】 Non-white inkjet inks can be preferably used for textile printing. 【0120】 Non-white inkjet inks can be applied to a substrate by an inkjet method to form non-white images. It is preferable to apply non-white inkjet ink to a substrate that has been coated with white inkjet ink to form a non-white image. 【0121】 The ink set for printing 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. 【0122】 <Method of manufacturing printed materials> A method for manufacturing a printed fabric according to one embodiment may include applying a pretreatment solution to a cloth (hereinafter also referred to as the "pretreatment solution application step"), applying white inkjet 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"), and applying non-white inkjet ink to the cloth to which the white inkjet ink has been applied using an inkjet method (hereinafter also referred to as the "non-white ink application step"). As the pretreatment solution, the pretreatment solution described as the pretreatment solution included in the ink set of the above embodiment can be used. As the white inkjet ink, the ink described as the white inkjet ink included in the ink set of the above embodiment can be used. As the non-white inkjet ink, the ink described as the non-white inkjet ink included in the ink set of the above embodiment can be used. As the cloth, the cloth described as the cloth to which the ink set of the above embodiment can be used can be used. 【0123】 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. 【0124】 The area to which the pretreatment solution is applied may be an area with the same shape as the image created with white inkjet ink, a wider area including the shape of the image created with white inkjet ink, or the entire surface of the fabric. It is preferable that the areas for applying the pretreatment solution, the areas for applying the white inkjet ink, and the areas for applying the non-white inkjet ink overlap at least partially. 【0125】 The amount of pre-treatment solution to apply to the fabric should be 10-100 g / m². 2 Preferably, 20-75 g / m 2 More preferably, 30-50 g / m 2 That is even more preferable. 【0126】 The process of applying white ink will be explained. It is preferable to apply white inkjet 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. It is preferable that the white inkjet 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 inkjet ink is applied overlap at least partially. 【0127】 It is preferable that the white inkjet ink be applied to the cloth that has been treated with a pretreatment solution using a wet-on-wet method. It is preferable that the white inkjet ink be applied while the moisture has not been completely removed from the cloth that has been treated with the pretreatment solution. Preferably, the white inkjet ink can be applied while the cloth that has been treated with the pretreatment solution remains wet. For example, it is preferable to apply the white inkjet ink to the cloth without performing a drying process such as heat drying after applying the pretreatment solution to the cloth. The temperature of the cloth surface after applying the pretreatment solution and before applying the white inkjet ink is preferably 40°C or lower, and more preferably 35°C or lower. It is preferable that the white inkjet ink be applied while the amount of volatile components of the pretreatment solution remaining on the cloth after applying the pretreatment solution is 90% by mass or more. The time from applying the pretreatment solution to applying the white inkjet ink to the cloth is preferably 0.1 to 200 seconds. 【0128】 The amount of white inkjet ink applied to the fabric is not particularly limited, but for example, 50-400 g / m² 2 Preferably, 100-200 g / m 2 This is preferable. 【0129】 The process of applying non-white ink will be explained. Non-white inkjet ink is preferably applied to the fabric by 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. It is preferable that the non-white inkjet ink be applied such that it at least partially overlaps with the area where the white inkjet ink is applied. It is preferable that the area where the pretreatment solution is applied, the area where the white inkjet ink is applied, and the area where the non-white inkjet ink is applied at least partially overlap. 【0130】 It is preferable that the non-white inkjet ink be applied to the fabric coated with white inkjet ink using a wet-on-wet method. It is preferable that the non-white inkjet ink be applied without completely removing moisture from the fabric coated with white inkjet ink. Preferably, the non-white inkjet ink can be applied while the fabric coated with white inkjet ink remains wet. For example, it is preferable to apply the non-white inkjet ink to the fabric without performing a drying process such as heat drying after applying the white inkjet ink. The temperature of the fabric surface after applying the white inkjet ink and before applying the non-white inkjet ink is preferably 40°C or lower, and more preferably 35°C or lower. It is preferable that the non-white inkjet ink be applied when the amount of volatile components remaining from the white inkjet ink on the fabric is 90% by mass or more. The time between applying the white inkjet ink to the fabric and applying the non-white inkjet ink is preferably 0.1 to 200 seconds. 【0131】 The amount of non-white inkjet ink applied to the fabric is not particularly limited, but for example, 5-60 g / m² 2 Preferably, 10-30 g / m 2 This is preferable. 【0132】 One type of non-white inkjet ink may be applied, or two or more types of non-white inkjet ink may be applied. 【0133】 When applying the pretreatment solution using an inkjet method, the application of the pretreatment solution and the application of the white inkjet ink may be performed using separate printing devices, or they may be performed using a single printing device. For example, the application of white inkjet ink and non-white inkjet ink may be performed using a single printing device, or they may be performed using separate printing devices. For example, the application of pretreatment solution, white inkjet ink, and non-white inkjet ink may be performed using a single printing device. Alternatively, for example, two printing devices may be used, with one device used for applying the pretreatment solution and the other for applying the white inkjet ink and non-white inkjet ink. 【0134】 It is preferable to include a step of heat-treating the fabric after the step of applying non-white inkjet 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 150°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, and 5 seconds to 5 minutes is also acceptable. 【0135】 A step of applying a post-treatment solution may be included after the non-white ink application step. For example, a step of heat-treating the fabric may be included after the non-white ink application step, and then the post-treatment solution may be applied. For example, the post-treatment solution may be applied using a wet-on-wet method after the non-white ink application step. Furthermore, a step of heat-treating the fabric may be included after the application of the post-treatment solution. [Examples] 【0136】 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%". 【0137】 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 PT1 to PT5. 【0138】 The details of the raw materials listed in Table 1 are as follows. The amount of magnesium nitrate hexahydrate listed in Table 1 is the amount as hexahydrate. (Polyvalent metal salts) Magnesium nitrate hexahydrate: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., active ingredient (amount as anhydrous) 57.8% by mass (Surfactants) Olphine E1020: Acetylene glycol-based surfactant, manufactured by Nisshin Chemical Industry Co., Ltd., active ingredient 100% by mass Olphine E1010: Acetylene glycol-based surfactant, manufactured by Nisshin Chemical Industry Co., Ltd., active ingredient 100% by mass (Water-soluble organic solvent) Diethylene glycol: Manufactured by Fujifilm Wako Pure Chemical Corporation Triethylene glycol: Manufactured by Fujifilm Wako Pure Chemical Corporation Glycerin: Manufactured by Fujifilm Wako Pure Chemical Corporation 【0139】 [Table 1] 【0140】 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). 【0141】 (2) Preparation of white ink Table 2 shows the formulations for white inks W1 to W5. The raw materials were mixed according to the proportions shown in the table and filtered through a cellulose acetate membrane filter with a pore size of 3 μm to obtain white inks W1 to W5. 【0142】 The details of the raw materials for the white inks W1 to W5 listed in Table 2 are as follows. In Table 2, the amounts of resin emulsion and pigment dispersion are shown as the total amount including the aqueous medium, etc. 【0143】 (Pigment dispersion) White pigment dispersion: obtained by the method described above, pigment content 25% by mass 【0144】 (Resin emulsion) Superflex 740: Polyurethane resin emulsion, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., resin content 40.0% by mass Superflex 150: Polyurethane resin emulsion, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., resin content 30.0% by mass 【0145】 (Surfactants) Olphine E1020: Acetylene glycol-based surfactant, manufactured by Nisshin Chemical Industry Co., Ltd., active ingredient 100% by mass Olphine E1010: Acetylene glycol-based surfactant, manufactured by Nisshin Chemical Industry Co., Ltd., active ingredient 100% by mass 【0146】 (Water-soluble organic solvent) Glycerin: Manufactured by Fujifilm Wako Pure Chemical Corporation Diethylene glycol: Manufactured by Fujifilm Wako Pure Chemical Corporation 【0147】 [Table 2] 【0148】 3. Preparation of non-white ink Tables 3-6 show the formulations of non-white inks C1-C11 and C1X-C11X. Each of the non-white inks C1X-C11X has the same composition as non-white inks C1-C11, but without the surfactant. The raw materials were mixed according to the proportions shown in the table, filtered through a cellulose acetate membrane filter with a pore size of 3 μm, and non-white inks C1 to C11 and C1X to C11X were obtained. 【0149】 The details of the raw materials for the non-white inks C1-C11 and C1X-C11X listed in Tables 3-6 are as follows. In Tables 3-6, the amounts of resin emulsion and pigment dispersion are shown as the total amount including the aqueous medium, etc. 【0150】 (Pigment dispersion) AC-AK1: Dispersant-dispersed pigment dispersion, manufactured by Dainichi Seika Kogyo Co., Ltd., pigment content 14.0% by mass BONJET BLACK CW-1: Self-dispersing pigment dispersion, manufactured by Orient Chemical Industries, Ltd., pigment content 20.0% by mass. FUJI SP Black 8140: Self-dispersing pigment dispersion, manufactured by Fuji Pigment Co., Ltd., pigment content 15.0% by mass. BONJET BLACK CW-2: Self-dispersing pigment dispersion, manufactured by Orient Chemical Industry Co., Ltd., pigment content 15.0% by mass. 【0151】 (Resin emulsion) Movinyl 6763: Acrylic resin emulsion (forced emulsification type), manufactured by Japan Coating Resin Co., Ltd., resin content 45.0% by mass Movinyl 6718: Acrylic resin emulsion (forced emulsification type), manufactured by Japan Coating Resin Co., Ltd., resin content 45.0% by mass. Superflex 470: Polyurethane resin emulsion (self-emulsifying type), manufactured by Daiichi Kogyo Seiyaku Co., Ltd., resin content 38.0% by mass Superflex 740: Polyurethane resin emulsion (self-emulsifying type), manufactured by Daiichi Kogyo Seiyaku Co., Ltd., resin content 40.0% by mass Superflex 460: Polyurethane resin emulsion (self-emulsifying type), manufactured by Daiichi Kogyo Seiyaku Co., Ltd., resin content 38.0% by mass 【0152】 (Surfactants) Olphine E1010: Acetylene glycol-based surfactant, manufactured by Nisshin Chemical Industry Co., Ltd., active ingredient content 100% by mass Surfinol 465: Acetylene glycol-based surfactant, manufactured by Evonik Industries, active ingredient content 100% by mass. 【0153】 (Water-soluble organic solvent) Glycerin: Manufactured by Fujifilm Wako Pure Chemical Corporation Diethylene glycol: Manufactured by Fujifilm Wako Pure Chemical Corporation Ethylene glycol: Manufactured by Fujifilm Wako Pure Chemical Corporation Diethylene glycol monobutyl ether: Manufactured by Fujifilm Wako Pure Chemical Corporation 【0154】 4. Measurement of the charge density of the pigment Tables 3-6 show the charge densities of the pigment dispersions used in non-white inks C1-C11. The charge densities of each pigment dispersion listed in the table were obtained by the flow potential method using the following procedure. A colloidal particle charge meter (AFG ANALYTIC GmbH, Model CAS) was used to measure the charge density. The pigment dispersion to be measured was diluted 100-fold with deionized water and used as a sample. Titration was performed with a 0.0025N polydiallyldimethylammonium chloride solution (Fujifilm Wako Pure Chemical Industries, Ltd.), and the reaction endpoint at which the flow potential of the sample became 0V was measured. The total charge of the sample (aqueous dispersion of diluted pigment particles) was determined from the amount of 0.0025N polydiallyldimethylammonium chloride solution used up to the reaction endpoint. The charge density of the pigment (μeq / g) is obtained by dividing the total charge of the sample by the amount of solid pigment contained in the sample. 【0155】 5. Measurement of surface tension Tables 1-6 show the surface tensions of pretreatment solutions PT1-PT5, white inks W1-W5, and non-white inks C1-C11 and C1X-C11X. The surface tensions listed in Tables 1-6 were determined using the "SITA Messtechnik GmbH science line t60" from SITA Process Solutions under measurement conditions of 23°C and 0.05Hz. 【0156】 [Table 3] 【0157】 [Table 4] 【0158】 [Table 5] 【0159】 [Table 6] 【0160】 6. Preparation of printed materials Using the pretreatment solutions PT1-PT5, white inks W1-W5, and non-white inks C1-C11 prepared as described above, printed materials for Examples 1-14 and Comparative Examples 1-6 were prepared according to the following procedure. Tables 7-9 show the pretreatment solutions, white inks, and non-white inks used to prepare the printed materials for Examples 1-14 and Comparative Examples 1-6. A black cotton T-shirt (product name Printstar) manufactured by Toms Co., Ltd. was used as the base material. A 10cm x 20cm area of ​​the surface of this black cotton T-shirt was treated with a pretreatment solution using an inkjet method. The image was a solid color, and the amount of pretreatment solution applied was approximately 50g / m². 2 The pretreatment solution was applied, and without a drying step, white ink was applied to the pretreatment area using an inkjet method. The image was a solid color, and the amount of white ink applied was approximately 180 g / m². 2The following procedure was followed: After applying the white ink, a non-white ink was applied to the white ink-coated area using an inkjet method without a drying process. The image was a solid color, and the amount of non-white ink applied was approximately 20 g / m². 2 The following steps were taken: For the application of the pretreatment solution, the white ink, and the non-white ink, a Mastermind "MMP-8130" (product name) was used as the printing device. After applying the non-white ink, the material was heated and dried at 160°C for 2 minutes using a Fusion heat press to obtain a printed material with a solid image measuring 10 cm x 20 cm. 【0161】 7. Evaluation of printed materials The non-white images of the printed materials were visually evaluated, and the color development of the non-white images was judged according to the following criteria. The evaluation results are shown in the table. A: Excellent color reproduction for non-white images. B: Excellent color reproduction for non-white images. C: The color reproduction of non-white images is insufficient. 【0162】 [Table 7] 【0163】 [Table 8] 【0164】 [Table 9] 【0165】 The printed materials in Examples 1-14 exhibited excellent color development for non-white images. In contrast, Comparative Examples 1, 2, and 6, which did not satisfy Equation 3, Comparative Example 3, which did not satisfy Equation 2, and Comparative Examples 4 and 5, which did not satisfy Equation 1, all did not produce sufficient color in the non-white images.

Claims

[Claim 1] A pretreatment solution containing a polyvalent metal salt, a water-soluble organic solvent, and a surfactant, A white inkjet ink containing a white pigment, resin particles, and a water-soluble organic solvent, A non-white inkjet ink comprising a non-white pigment, resin particles, a water-soluble organic solvent, and a nonionic surfactant, A printing ink set that satisfies the following formulas 1, 2, and 3, where X is the surface tension of the pretreatment liquid, Y is the surface tension of the white inkjet ink, Z1 is the surface tension of the non-white inkjet ink, and Z2 is the surface tension of a liquid having the composition obtained by removing the nonionic surfactant from the non-white inkjet ink. (Formula 1) 33mN / m≦X≦50mN / m (Formula 2) -5mN / m≦Y-Z1≦10mN / m (Formula 3) 0mN / m≦Z2-Z1≦10mN / m [Claim 2] Furthermore, the ink set for printing according to claim 1 satisfies formula 4. (Formula 4) 0mN / m≦Z2-Z1≦6.5mN / m [Claim 3] The ink set for textile printing according to claim 1 or 2, wherein the non-white inkjet ink contains 5% by mass or more of forced-emulsification type resin particles relative to the total amount of the non-white inkjet ink. [Claim 4] Applying the pretreatment solution to the cloth, The process involves applying white inkjet ink to the fabric to which the pretreatment solution has been applied using an inkjet method. This includes applying a non-white inkjet ink to the fabric to which the white inkjet ink has been applied by an inkjet method, The aforementioned pretreatment solution comprises a polyvalent metal salt, a water-soluble organic solvent, and a surfactant. The aforementioned white inkjet ink comprises a white pigment, resin particles, and a water-soluble organic solvent. The non-white inkjet ink comprises a non-white pigment, resin particles, a water-soluble organic solvent, and a nonionic surfactant. A method for producing a printed material, wherein the surface tension of the pretreatment solution is X, the surface tension of the white inkjet ink is Y, the surface tension of the non-white inkjet ink is Z1, and the surface tension of the liquid having the composition obtained by removing the nonionic surfactant from the non-white inkjet ink is Z2, and the following formulas 1, 2, and 3 are satisfied. (Formula 1) 33mN / m≦X≦50mN / m (Formula 2) -5mN / m≦Y-Z1≦10mN / m (Formula 3) 0mN / m≦Z2-Z1≦10mN / m

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