Ink set for textile printing

Abstract

To provide an ink set for textile printing that makes it possible to produce a printed textile item having an image excellent in color development.SOLUTION: Provided is an ink set for textile printing including a white inkjet ink that includes a white pigment, resin particles A which have a film elongation of 1,000% or more, and resin particles B which have a film elongation of less than 1,000% and are ionic resin particles having an average particle size of 150 nm or less; and a non-white inkjet ink that includes a non-white pigment and resin particles C which have a film elongation of 500% or more and a resin skeleton different from those of the resin particles A and the resin particles B.SELECTED DRAWING: None

Description

[Technical field]

[0001] An embodiment of the present invention relates to a textile printing ink set. [Background technology]

[0002] 2. Description of the Related Art As a method for printing images such as letters, pictures and designs onto fabrics such as woven fabrics, knitted fabrics and nonwoven fabrics, in addition to screen printing and roller printing, ink-jet printing has been attracting attention.

[0003] Compared with light-colored cloth such as white, images formed on dark-colored cloth such as black tend to be difficult to see. Patent Document 1 describes a method in which a pretreatment agent containing a polyvalent metal salt is applied to dark-colored cloth such as black, and then an ink containing a white pigment is printed to form a white image, and a desired image is then formed thereon. Patent Document 1 also describes that a heat treatment is performed after the application of the pretreatment agent. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2009-30014 A Summary of the Invention [Problem to be solved by the invention]

[0005] When a non-white image is formed on a white image, the white image is retained on the surface of the fabric, and the non-white image is retained in the vicinity of the surface of the white image, thereby enhancing the color development of the image on the surface of the fabric substrate. In this case, it is expected that the ink is designed so that the white pigment and the non-white pigment remain on the surface of the fabric substrate. In addition, in the case of overprinting of a plurality of types of ink, there is a phenomenon in which the ink coating film is easily broken into small pieces and cracked during the drying process for removing non-volatile matter, resulting in a decrease in color development. In Patent Document 1, a heat treatment is performed after applying a pretreatment agent, but this does not sufficiently prevent the white pigment and the non-white pigment from penetrating into the interior of the fabric substrate, and there is room for improvement in color development from another aspect as well.

[0006] An object of one embodiment of the present invention is to provide a textile printing ink set that is capable of producing printed textile products with excellent color development properties. [Means for solving the problem]

[0007] One embodiment of the present invention relates to a textile printing ink set comprising: a white inkjet ink containing a white pigment, resin particles A having a film elongation of 1000% or more, and resin particles B which are ionic resin particles having a film elongation of less than 1000% and an average particle size of 150 nm or less; and a non-white inkjet ink containing a non-white pigment, and resin particles C having a film elongation of 500% or more and a resin skeleton different from that of the resin particles A and the resin particles B. Effect of the Invention

[0008] According to one embodiment of the present invention, it is possible to provide a textile printing ink set that is capable of producing printed textiles with excellent color development properties. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] Hereinafter, an 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.

[0010] The ink set of one embodiment is a textile printing ink set including: a white inkjet ink containing a white pigment, resin particles A having a film elongation of 1000% or more, and resin particles B which are ionic resin particles having a film elongation of less than 1000% and an average particle diameter of 150 nm or less; and a non-white inkjet ink containing a non-white pigment, and resin particles C having a film elongation of 500% or more and a resin skeleton different from that of the resin particles A and the resin particles B.

[0011] By using this ink set, it is possible to produce printed items having images with excellent color development properties.

[0012] In the present disclosure, the textile printing ink set is also simply referred to as an ink set. Resin particles A having a film elongation of 1000% or more are also referred to as resin particles A, resin particles B having a film elongation of less than 1000% and being ionic resin particles with an average particle diameter of 150 nm or less are also referred to as resin particles B, and resin particles C having a film elongation of 500% or more and a resin skeleton different from that of the resin particles A and the resin particles B are also referred to as resin particles C. The white inkjet ink is also referred to as white ink (W), and the non-white inkjet ink is also referred to as non-white ink (C).

[0013] Factors that affect the color development of a printed material obtained using a white ink and a non-white ink include, but are not limited to, the difficulty in mixing the white ink and the non-white ink on the substrate surface after the inks have been applied, the spreadability of the non-white image, and the hiding power of the white image.

[0014] Regarding the difficulty in mixing white ink and non-white ink, when a non-white ink (C) is applied onto a white image formed with white ink (W), if the white ink (W) and non-white ink (C) are highly miscible with each other, the inks will mix together, resulting in a decrease in the color development of the non-white image. Without being bound by theory, it is speculated that the non-white ink (C) acts as follows.

[0015] The resin particles C contained in the non-white ink (C) have a resin skeleton different from the resin particles A and B contained in the white ink (W), and therefore mixing of the white ink (W) and the non-white ink (C) on the substrate surface is suppressed, so that the non-white pigment remains on the substrate surface, enabling the formation of a non-white image with high color development. In the present disclosure, when two resins have different resin skeletons, this means that the monomer units constituting the resins or the reaction raw materials of the resins do not completely match.

[0016] Regarding the extensibility of the non-white image, without being bound by theory, it is speculated that the non-white ink (C) acts as follows.

[0017] Since the non-white ink (C) contains resin particles C with a film elongation of 500% or more, it spreads easily in the XY axis direction when heated and pressurized, and the non-white image formed has high extensibility, which makes the non-white image less likely to break and provides excellent color development.

[0018] As described later, the white ink (W) contains resin particles A, so it spreads easily in the XY axis directions when heated and pressurized, and the white image formed has high extensibility. If the non-white image formed on the white image has low extensibility and cannot follow the expansion of the white image, the non-white image breaks, resulting in a decrease in the color development of the non-white image.

[0019] More specifically, the concealment of the white image is considered to be the uniformity and whiteness of the white image. The white image formed by the white ink (W) is excellent in uniformity and whiteness, and therefore contributes to improving the color development of the printed matter. Without being bound by theory, it is assumed that the white ink (W) acts as follows.

[0020] The resin particles A contained in the white ink (W) have a film elongation of 1000% or more, so they easily stretch and spread well in the XY axis directions when heated and pressurized, making it easy to homogenize the ink distribution even when a fuzzy substrate is used. This makes it easy to improve the uniformity of the white image.

[0021] In addition, the resin particles B contained in the white ink (W) are small particles with an average particle diameter of 150 nm or less, so they easily penetrate into the gaps between the fibers of the substrate. In addition, because they are ionic, they coagulate when they come into contact with a pretreatment liquid containing a coagulant such as a polyvalent metal salt, and can exert a sealing effect that suppresses the penetration of ink components into the substrate. As a result, the whiteness of the white image can be increased. <White inkjet ink> The white ink (W) contains a white pigment, resin particles A having a film elongation of 1000% or more, and resin particles B which are ionic resin particles having a film elongation of less than 1000% and an average particle diameter of 150 nm or less.

[0022] The white ink (W) contains a white pigment as a coloring material, and as a result of containing the white pigment, the white ink can be used to form an image that exhibits a white color.

[0023] Examples of the white pigment include white inorganic pigments such as titanium oxide, zinc oxide, zinc sulfide, antimony oxide, and zirconium oxide. Among them, it is preferable to use titanium oxide from the viewpoint of hiding power. The average particle size of titanium oxide is preferably 100 nm or more from the viewpoint of hiding power, and is preferably 600 nm or less from the viewpoint of ejection stability.

[0024] As the white pigment, a pigment dispersion in which a pigment is previously dispersed with a pigment dispersant may be used. A pigment dispersion in which a pigment is dispersed with a pigment dispersant described below may also be used.

[0025] The white pigment may be used alone or in combination of two or more kinds.

[0026] From the viewpoint of hiding power and the like, the content of the white pigment is preferably from 1 to 30% by mass, more preferably from 3 to 20% by mass, and even more preferably from 5 to 15% by mass, based on the total amount of the white ink (W).

[0027] In order to stably disperse the white pigment in the white ink (W), a pigment dispersant such as a polymer dispersant or a surfactant-type dispersant can be used.

[0028] Examples of commercially available polymer dispersants include the TEGO Disperse series manufactured by EVONIK, such as "TEGO Disperse 740W," "TEGO Disperse 750W," "TEGO Disperse 755W," "TEGO Disperse 757W," and "TEGO Disperse 760W," and the Solsperse series manufactured by Lubrizol Japan, such as "Solsperse 20000," "Solsperse 27000," "Solsperse 41000," "Solsperse 41090," "Solsperse 43000," "Solsperse 44000," and "Solsperse 46000." Examples of such products include the Joncryl series manufactured by BASF Japan Ltd., such as "Joncryl 57", "Joncryl 60", "Joncryl 62", "Joncryl 63", "Joncryl 71", and "Joncryl 501", and the like; products manufactured by BYK Japan Ltd., such as "DISPERBYK-102", "DISPERBYK-185", "DISPERBYK-190", "DISPERBYK-193", and "DISPERBYK-199", and products manufactured by Daiichi Kogyo Seiyaku Co., Ltd., such as "Polyvinylpyrrolidone K-30" and "Polyvinylpyrrolidone K-90" (all of which are trade names).

[0029] Examples of surfactant-type dispersants include anionic surfactants such as the Demol series manufactured by Kao Corporation, "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, "Emulgen A-60," "Emulgen A-90," "Emulgen A-500," "Emulgen B-40," "Emulgen L-40," and "Emulgen 420" (all trade names).

[0030] The above pigment dispersants may be used alone or in combination of two or more.

[0031] When a pigment dispersant is used, the amount of the pigment dispersant blended in the white ink (W) varies depending on the type and is not particularly limited, but in general, the mass ratio of the active ingredient (pigment concentration) to pigment is preferably 0.005 to 0.5.

[0032] The white ink (W) may contain resin particles A.

[0033] The resin particles A are preferably resin particles that can be dispersed in an aqueous solvent. The resin particles A are preferably resin particles that can be dispersed in water without dissolving in water to form an oil-in-water (O / W) emulsion.

[0034] The resin particles A are preferably contained in the white ink (W) in a dispersed state as resin particles. The resin particles A can be blended as a water dispersion of resin particles when producing the white ink (W).

[0035] The resin particles A may be ones in which the functional groups of the resin are present on the surface of the resin particles, such as a self-emulsifying resin, or ones in which the surface of the resin particles has been subjected to a surface treatment, such as by attaching a dispersant to the surface.

[0036] The resin particles A may be, for example, anionic, cationic, nonionic, or amphoteric, but are preferably anionic or nonionic, and more preferably anionic.

[0037] The anionic resin particles may be those in which an anionic functional group of the resin is present on the surface of the resin particles, such as a self-emulsifying resin, or those that have been subjected to a surface treatment such as attaching an anionic dispersant to the surface of the resin particles. Representative examples of the anionic functional group include a carboxy group, a sulfo group, a sulfino group, a sulfate ester group, a phosphoric acid group, a phosphoric acid ester group, a phosphorous acid group, and a phosphorous acid ester group. Examples of the anionic dispersant include an anionic surfactant.

[0038] The nonionic resin particles may be those in which the nonionic functional group of the resin is present on the surface of the resin particles, such as a self-emulsifying resin, or those that have been subjected to a surface treatment such as attaching a nonionic dispersant to the surface of the resin particles. Representative examples of the nonionic functional group include a polyoxyalkylene glycol group and a hydroxyl group. Examples of the nonionic dispersant include a nonionic surfactant.

[0039] The film elongation of the resin particles A is 1000% or more, and from the viewpoint of further improving the uniformity of the white image, it is preferably 1100% or more, and more preferably 1200% or more. The film elongation of the resin particles A may be 2000% or less, 1800% or less, or in the range of 1700%. The film elongation of the resin particles A may be in the range of 1000 to 2000%, 1100 to 1800%, or 1200 to 1700%.

[0040] In this specification, the film elongation of the resin particles can be measured according to the following procedure. First, an aqueous dispersion of the resin particles is applied onto a polytetrafluoroethylene sheet so that the film thickness after drying is 500 μm, and the sheet is dried at 23° C. for 15 hours, and then dried at 80° C. for 6 hours and at 120° C. for 20 minutes, and then peeled off from the sheet to prepare a resin film. This resin film is cut into a column shape with a width of 2 cm and a length of 4 cm to prepare a resin film test piece. Using a tensile tester, the resin film test piece is stretched at a measurement temperature of 20° C. and a measurement speed of 200 mm / min to measure the length of elongation until the resin film test piece breaks, and the value expressed as a percentage relative to the original length is taken as the film elongation. As the tensile tester, a Tensilon universal testing machine RTC-1225A (manufactured by Orientec Co., Ltd.) can be used.

[0041] The average particle diameter of the resin particles A is preferably 1.5 times or more the average particle diameter of the resin particles B. The average particle diameter of the resin particles A may be 8 times or less the average particle diameter of the resin particles B. The average particle diameter of the resin particles A may be in the range of 1.5 to 8 times the average particle diameter of the resin particles B. When the average particle diameter of the resin particles A is larger than the average particle diameter of the resin particles B, the resin particles A tend to remain on the aggregated resin particles B, and the resin particles B tend to exhibit a better sealing effect, which tends to further improve the whiteness of the white image.

[0042] The average particle diameter of the resin particles A is preferably larger than 150 nm, and more preferably 160 nm or more. The larger the average particle diameter of the resin particles A, the smaller the contact area between the resin particles A and the pretreatment liquid, and the less the bond between the resin particles is affected by the pretreatment liquid, so that a more uniform ink film can be formed. The average particle diameter of the resin particles A may be 160 nm or more. The average particle diameter of the resin particles A may be 600 nm or less, 500 nm or less, or 300 nm or less. The average particle diameter of the resin particles A may be, for example, larger than 150 nm and 600 nm or less, in the range of 160 to 500 nm, or in the range of 160 to 300 nm.

[0043] In this specification, the average particle size of the resin particles is the volume-based median size in the particle size distribution measured by dynamic light scattering. The particle size distribution of the resin particles can be measured at 25°C using a measurement sample prepared by diluting a dispersion of the resin particles with water to a resin particle concentration of 0.5% by mass. As a dynamic light scattering type particle size distribution measuring device, for example, a "Nano Particle Analyzer nano Partica SZ-100" (manufactured by Horiba, Ltd.) can be used.

[0044] The average particle diameter of the resin particles is preferably measured in the state of a raw material resin particle dispersion before preparing the ink, since this makes it possible to eliminate the influence of the colorant, and the measured value can be used as the average particle diameter of the resin particles.

[0045] As the type of resin particles A, it is preferable to use a resin that forms a transparent coating film.

[0046] The type of resin particles A is, for example, 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 of these with styrene, etc.; Vinyl resins such as ethylene-vinyl acetate copolymers, Or functional group-modified resins of these various resins using monomers containing functional groups such as carboxyl groups; Examples of the resin particles include melamine resin, urea resin, polyurethane resin, polyester resin, polyolefin resin, silicone resin, polyvinyl butyral resin, alkyd resin, etc. Resin particles of a single resin of these may be used, or hybrid type resin particles may be used.

[0047] The resin particles A may be used alone or in combination of two or more kinds.

[0048] Commercially available aqueous dispersions of resin particles A include "Implanir DLP", "Implanir DLP-R", "Implanir DLV", "Implanir DLI", "Implanir 1016", "Implanir 1116", "Implanir DLS", "Implanir DL1537", "Implanir DL1554", "Implanir DL1380", "Implanir LP CGL 105", "Implanir DLN-SD", "Implanir LP DSB 1069", and "Implanir DLN-W50" manufactured by Sumika Covestro Urethane Co., Ltd., and "Superflex E2000", "Superflex 740", "Superflex 500M", and "Superflex 300" manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (all trade names).

[0049] From the viewpoint of film elongation, the resin particles A preferably contain polyurethane resin particles.

[0050] The content (solid content) of the resin particles A in the white ink (W) is preferably 5% by mass or more, more preferably 8% by mass or more, and even more preferably 10% by mass or more. The content (solid content) of the resin particles A in the white ink (W) is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less. The content (solid content) of the resin particles A in the white ink (W) is, for example, preferably 5 to 25% by mass, and even more preferably 8 to 15% by mass.

[0051] The white ink (W) contains resin particles B.

[0052] Resin particles B are preferably resin particles that can be dispersed in an aqueous solvent. Resin particles B are preferably resin particles that can be dispersed in water without dissolving in water to form an oil-in-water (O / W) emulsion.

[0053] The resin particles B are preferably contained in the white ink (W) in a dispersed state as resin particles. The resin particles B can be blended as a water dispersion of resin particles when producing the white ink (W).

[0054] The resin particles B are preferably ionic. The resin particles B may be anionic, cationic, or amphoteric, but are more preferably anionic.

[0055] Anionic resin particles are dispersible resins with negative charge, that is, the surface of the resin particles is negatively charged. The anionic functional group of the resin may be present on the surface of the resin particles, as in the case of self-emulsifying resins, or the surface of the resin particles may be subjected to a surface treatment, such as attaching an anionic dispersant to the surface of the resin particles. Examples of the anionic functional group include a carboxy group, a sulfo group, a sulfino group, a sulfate ester group, a phosphoric acid group, a phosphoric acid ester group, a phosphorous acid ester group, a phosphorous acid ester group, and the like. Examples of the anionic dispersant include an anionic surfactant and the like.

[0056] The film elongation of resin particles B is less than 1000%. The film elongation of resin particles B may be 800% or less, or 600% or less. The film elongation of resin B may be 100% or more, or 200% or more. The film elongation of resin particles B may be, for example, in the range of 100 to 800%, or in the range of 200 to 600%.

[0057] The average particle size of the resin particles B is preferably 150 μm or less.

[0058] The average particle size of the resin particles B is more preferably 120 nm or less, further preferably 100 nm or less, and further preferably 80 nm or less. As the average particle size of the resin particles B becomes smaller, the contact area with the pretreatment liquid tends to become larger, and the reactivity with the pretreatment liquid may also become higher.

[0059] The average particle size of the resin particles B is preferably 10 nm or more, more preferably 30 nm or more, and even more preferably 50 nm or more. The average particle size of the resin particles B is, for example, preferably 10 to 150 nm, more preferably 30 to 120 nm, more preferably 50 to 100 nm, and even more preferably 50 to 80 nm.

[0060] The charge density of the resin particles B is preferably 10 μeq / g or more.

[0061] From the viewpoint of further improving the whiteness of the white image, the charge density of the resin particles B is more preferably 60 μeq / g or more, and even more preferably 90 μeq / g or more. In general, the higher the charge density of the resin particles, the more likely it is that the dispersion stabilization of the resin particles will depend on electrostatic repulsion rather than solvation. When the charge density of the resin particles B is 60 μeq / g or more, salting out tends to occur more easily when the resin particles come into contact with the pretreatment liquid, and the filling effect is easily exerted even on substrates with many gaps between fibers, making it easier to obtain a higher whiteness.

[0062] The charge density of the resin particles B is preferably 500 μeq / g or less, more preferably 300 μeq / g or less, and even more preferably 200 μeq / g or less. The charge density of the resin particles B is, for example, preferably 10 to 500 μeq / g, more preferably 60 to 300 μeq / g, and even more preferably 90 to 200 μeq / g.

[0063] In this specification, the charge density of the resin particles is a charge density measured by a streaming potential method, and is the amount of charge per solid content of the aqueous dispersion of the resin particles (unit: μeq / g).

[0064] Specifically, the diluted solution obtained by diluting the aqueous dispersion of resin particles to be measured 100 times with water is titrated with a 0.0025N polydiallyldimethylammonium chloride solution while measuring the reaction end point at which the streaming potential of the diluted solution becomes 0 V, and the total charge of the diluted solution can be calculated from the amount of 0.0025N polydiallyldimethylammonium chloride solution used up to this reaction end point. The charge density of the resin particles (μeq / g) is the value obtained by dividing the total charge of the diluted solution by the solid content of the resin particles contained in the diluted solution.

[0065] For example, a colloid particle charge meter ("Model CAS" manufactured by AFG ANAYTIC GmbH) can be used as the charge density measuring device.

[0066] As the type of resin particles B, it is preferable to use a resin that forms a transparent coating film.

[0067] The type of resin particles B is, for example, 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 of these with styrene, etc.; Vinyl resins such as ethylene-vinyl acetate copolymers, Or functional group-modified resins of these various resins using monomers containing functional groups such as carboxyl groups; Examples of the resin particles include melamine resin, urea resin, polyurethane resin, polyester resin, (oxidized) polyolefin resin, silicone resin, polyvinyl butyral resin, alkyd resin, etc. Resin particles of these resins alone may be used, or hybrid type resin particles may be used.

[0068] The resin particles B may be used alone or in combination of two or more kinds.

[0069] Commercially available aqueous dispersions of resin particles B include "Superflex 420", "Superflex 150HS", "Superflex 460", and "Superflex 470" manufactured by Daiichi Kogyo Seiyaku Co., Ltd., "DAOTAN TW6450", "DAOTAN TW6460", and "DAOTAN VTW1262" manufactured by Daicel Allnex Corporation, "ELITEL KT9204" and "ELITEL KT8803" manufactured by Unitika Ltd., "NeoRez R-966" and "NeoRez R-4000" manufactured by DSM, and "AQUACER507" manufactured by BYK (all trade names).

[0070] The resin particles B preferably contain at least one of an (oxidized) polyolefin resin and a polyurethane resin.

[0071] The (oxidized) polyolefin resin is more preferably anionic. When the resin particles B are an anionic (oxidized) polyethylene resin, the whiteness of the white image is further improved by using the resin particles B in combination with a pretreatment liquid containing a flocculant. The reason for this is presumed to be, but is not limited to, as follows.

[0072] Due to its ionic nature, anionic oxidized polyolefin resins undergo an aggregation reaction when they come into contact with an aggregating agent. In addition, since oxidized polyolefin resins are generally highly hydrophobic resins, they tend to orient themselves at the interface of aqueous inks. For this reason, when ink droplets of white ink (W) land on a surface coated with a pretreatment liquid containing an aggregating agent, the (oxidized) polyolefin resin, among the various components in the ink, comes into contact with the surface coated with the pretreatment liquid first and undergoes an aggregation reaction, forming an aggregating layer. This aggregating layer is thought to suppress the ink from penetrating into the fabric, increasing the amount of ink remaining on the fabric surface, thereby improving the whiteness of the white image.

[0073] The (oxidized) polyolefin resin preferably has a melting point of 125° C. or higher. The melting point may be 150° C. or lower. When the (oxidized) polyolefin resin has a melting point of 125° C. or higher, the whiteness of the white image is improved, particularly when a polyester fabric is used as the fabric to be printed. The reason for this is presumed to be, but is not limited to, as follows.

[0074] When using polyester fabric as the printing target, it is generally dried at 120°C or less to prevent loss of color due to re-sublimation of the dye used in the polyester. By using (oxidized) polyolefin resin with a melting point higher than this drying temperature, it becomes easier to maintain the particle shape even on the printed material, and it is thought that the effect of improving whiteness due to diffuse reflection can be obtained.

[0075] Examples of the (oxidized) polyolefin resin include polyethylene resin, oxidized polyethylene resin, polypropylene resin, and oxidized polypropylene resin. Among them, (oxidized) polyethylene resin is preferable because the melting point can be easily adjusted to a preferred value. The polyethylene resin may be a high-density polyethylene resin.

[0076] The polyurethane resin preferably has a charge density of 60 μeq / g or more.

[0077] The polyurethane resin is preferably a carbonate-based urethane resin.

[0078] In view of the above, it is preferable that the resin particles B contain at least one of an anionic (oxidized) polyolefin resin and a polyurethane resin having a charge density of 60 μeq / g or more.

[0079] The content (solid content) of resin particles B in the white ink (W) is preferably 1% by mass or more, and more preferably 2% by mass or more. The content (solid content) of resin particles B in the white textile inkjet ink is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 8% by mass or less. The content (solid content) of resin particles B in the white textile inkjet ink is, for example, preferably 1 to 15% by mass, more preferably 2 to 10% by mass, and even more preferably 2 to 8% by mass.

[0080] The total content (solid content) of resin particles A and resin particles B is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 90% by mass or more, and even more preferably 95% by mass or more, based on the total amount (solid content) of resin particles in the white textile printing inkjet ink, and may be 100% by mass.

[0081] In the white ink (W), the content of resin particles A is preferably greater than the content of resin particles B.

[0082] From the viewpoint of further improving the uniformity of the white image, the mass ratio of resin particles A to resin particles B, "resin particles A / resin particles B", is preferably 1.2 or more, more preferably 1.5 or more, and even more preferably 1.8 or more. When the mass ratio of resin particles A to resin particles B is 2.5 or more, unevenness is more easily alleviated even on a substrate with a lot of fuzz, and the uniformity of the white image is more easily improved. In addition, "resin particles A / resin particles B" may be 5 or less, or may be 3 or less.

[0083] The total content of the resin particles A and the resin particles B in the white ink (W) is preferably equal to or greater than the content of the white pigment. From the viewpoint of further improving the uniformity of the white image, the mass ratio of the total of the resin particles A and the resin particles B to the white pigment, "(resin particles A+resin particles B) / white pigment", is preferably equal to or greater than 1, and more preferably equal to or greater than 1.2. When the mass ratio of the total of the resin particles A and the resin particles B to the white pigment, "(resin particles A+resin particles B) / white pigment", is equal to or greater than 1, the white pigment tends to be less likely to enter the gaps between the resin particles A, the bonds between the resin particles A are less likely to be affected, and the uniformity is more likely to be further improved. "(resin particles A+resin particles B) / white pigment" may be equal to or less than 3, or may be equal to or less than 2.

[0084] The white ink (W) preferably contains water, and the main solvent may be water.

[0085] The water is not particularly limited, but it is preferable that the water contains as few ionic components as possible. In particular, from the viewpoint of storage stability of the ink, it is preferable that the content of polyvalent metal ions such as calcium is small. As the water, for example, ion-exchanged water, distilled water, ultrapure water, etc. may be used.

[0086] From the viewpoint of adjusting the ink viscosity, the water content is preferably 30 to 70 mass %, more preferably 35 to 65 mass %, and even more preferably 40 to 60 mass %, of the total amount of the white ink (W).

[0087] It is preferable that a water-soluble organic solvent is blended in the white ink (W). As the water-soluble organic solvent, an organic compound that is liquid at room temperature and dissolves in water can be used, and it is preferable to use a water-soluble organic solvent that is uniformly mixed with the same volume of water at 20° C. under 1 atmosphere. For example, 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, dipropylene glycol, tripropylene glycol, and polypropylene glycol; glycerins such as glycerin, diglycerin, triglycerin, and polyglycerin; acetins such as monoacetin and diacetin; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethyl ether, ethyl ... Glycol ethers such as ethylene 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; triethanolamine, 1-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, β-thiodiglycol, and sulfolane can be used. The boiling point of the water-soluble organic solvent is preferably 100° C. or higher, and more preferably 150° C. or higher.

[0088] These water-soluble organic solvents may be used alone or in combination of two or more kinds as long as they form a single phase with water. The content of the water-soluble organic solvent in the white ink (W) is preferably 5 to 50% by mass, and more preferably 10 to 40% by mass.

[0089] The white ink (W) preferably contains a surfactant.

[0090] As the surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, or a combination thereof can be preferably used, and a nonionic surfactant is more preferable. In addition, either a low molecular weight surfactant or a high molecular weight surfactant may be used.

[0091] The HLB value of the surfactant is preferably 5-20, and more preferably 10-18.

[0092] 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, fluorine-based surfactants, etc. Among these, acetylene-based surfactants such as acetylene glycol-based surfactants can be preferably used.

[0093] Examples of the acetylene-based surfactant include acetylene glycol-based surfactants, acetylene alcohol-based surfactants, and surfactants having an acetylene group.

[0094] The acetylene glycol 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 have a structure in which ethylene oxide is added to acetylene glycol.

[0095] Commercially available acetylene surfactants include, for example, the Surfynol series manufactured by Evonik Industries Ltd., such as "Surfynol 104E," "Surfynol 104H," "Surfynol 420," "Surfynol 440," "Surfynol 465," and "Surfynol 485," and the Olfin series manufactured by Nissin Chemical Industry Co., Ltd., such as "Olfin E1004," "Olfin E1010," and "Olfin E1020" (all trade names).

[0096] Examples of silicone surfactants include polyether-modified silicone surfactants, alkyl / aralkyl-co-modified silicone surfactants, and acrylic silicone surfactants.

[0097] Commercially available silicone surfactants include, for example, "Silface SAG002" and "Silface SAG503A" manufactured by Nissin Chemical Industry Co., Ltd. (both are trade names).

[0098] Other nonionic surfactants include polyoxyethylene alkyl ether 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 trade names).

[0099] Examples of anionic surfactants include Kao Corporation's EMAL series, such as "EMAL 0," "EMAL 10," "EMAL 2F," "EMAL 40," and "EMAL 20C," the Neopelex series, such as "Neopelex GS," "Neopelex G-15," "Neopelex G-25," and "Neopelex G-65," the Pelex series, such as "Pelex OT-P," "Pelex TR," "Pelex CS," "Pelex TA," "Pelex SS-L," and "Pelex SS-H," and the Demol series, such as "Demol N," "Demol NL," "Demol RN," and "Demol MS" (all product names).

[0100] Examples of cationic surfactants include the Acetamine series (manufactured by Kao Corporation) such as "Acetamine 24" and "Acetamine 86", the Cortamine series (manufactured by Kao Corporation) such as "Cortamine 24P", "Cortamine 86P", "Cortamine 60W", and "Cortamine 86W", and the Sanisol series (manufactured by Kao Corporation) such as "Sanisol C" and "Sanisol B-50" (all trade names).

[0101] Examples of amphoteric surfactants include the Amphitol series manufactured by Kao Corporation, such as "Amphitol 20BS," "Amphitol 24B," "Amphitol 86B," "Amphitol 20YB," and "Amphitol 20N" (all trade names).

[0102] The above-mentioned surfactants are preferably used alone, but two or more of them may be used in combination.

[0103] The content of the surfactant is preferably from 0.01 to 10% by mass, more preferably from 0.1 to 5% by mass, and even more preferably from 0.2 to 3% by mass, based on the total amount of the white ink (W).

[0104] The white ink (W) may contain other components as necessary, such as a pH adjuster and a preservative.

[0105] The method for producing the white ink (W) is not particularly limited, and the ink can be produced by a known method. For example, all the components are charged into a stirrer such as a three-one motor all at once or in portions, dispersed, and, if desired, passed through a filter such as a membrane filter to obtain an ink. More specifically, other components may be mixed with the white pigment, resin particles A, resin particles B, and water as necessary, and examples of the other components include those described above as components that can be contained in the white ink (W), such as surfactants, water-soluble organic solvents, and pigment dispersants. The resin particles A may be used in the form of an aqueous dispersion of the resin particles A. Similarly, the resin particles B may be used in the form of an aqueous dispersion of the resin particles B. The white pigment may be used in the form of a pigment dispersion in which the pigment is previously dispersed with a pigment dispersant. These components can be mixed all at once or in portions.

[0106] The pH of the white ink (W) is preferably from 7.0 to 10.0, and more preferably from 7.5 to 9.0, from the viewpoint of storage stability of the ink.

[0107] The viscosity of the white textile printing inkjet ink is preferably 1 to 30 mPa·s at 23° C., for example, from the viewpoint of inkjet dischargeability. <Non-white inkjet ink> The non-white ink (C) contains a non-white pigment, and resin particles C having a film elongation of 500% or more and a resin skeleton different from the resin particles A and the resin particles B.

[0108] The non-white ink (C) contains a non-white pigment as a coloring material.

[0109] As the non-white pigment, organic pigments such as azo pigments, phthalocyanine pigments, polycyclic pigments, and dye lake pigments, and inorganic pigments such as carbon black and metal oxides can be used. As the azo pigments, soluble azo lake pigments, insoluble azo pigments, and condensed azo pigments can be used. As the phthalocyanine pigments, metal phthalocyanine pigments and metal-free phthalocyanine pigments can be used. As the polycyclic pigments, quinacridone pigments, perylene pigments, perinone pigments, isoindoline pigments, isoindolinone pigments, dioxazine pigments, thioindigo pigments, anthraquinone pigments, quinophthalone pigments, metal complex pigments, and diketopyrrolopyrrole (DPP) can be used. As the carbon black, furnace carbon black, lamp black, acetylene black, channel black, and the like can be used. These pigments may be used alone or in combination of two or more.

[0110] From the viewpoints of ejection stability and storage stability, the average particle size of the pigment particles in the non-white ink (C) 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 in the particle size distribution measured by dynamic light scattering.

[0111] The non-white pigment may be a self-dispersing pigment. A self-dispersing pigment is a pigment in which a hydrophilic functional group is introduced to the surface of the pigment by chemical or physical treatment. The hydrophilic functional group introduced to the self-dispersing pigment is preferably ionic, and by charging the pigment surface anionically or cationic, the pigment particles can be stably dispersed in water by electrostatic repulsion. As the anionic functional group, a carboxy group, a sulfo group, a sulfino group, a sulfate ester group, a phosphoric acid group, a phosphoric acid ester group, a phosphorous acid group, a phosphorous acid ester group, and the like are preferred. As the cationic functional group, a quaternary ammonium group, a quaternary phosphonium group, and the like are preferred.

[0112] These hydrophilic functional groups may be bonded directly to the pigment surface or via other atomic groups. Examples of the other atomic groups include, but are not limited to, alkylene groups, phenylene groups, naphthylene groups, etc. Methods for treating the pigment surface include diazotization treatment, sulfonation treatment, hypochlorous acid treatment, humic acid treatment, vacuum plasma treatment, etc.

[0113] As the self-dispersing pigment, for example, the CAB-O-JET series manufactured by Cabot Corporation, such as "CAB-O-JET200", "CAB-O-JET300", "CAB-O-JET250C", "CAB-O-JET260M", "CAB-O-JET270", "CAB-O-JET450C", and "CAB-O-JET465M", and Orient Chemical Industries Co., Ltd.'s "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).

[0114] As the pigment, a microencapsulated pigment in which the pigment is coated with a resin may be used.

[0115] The non-white pigment may be a pigment dispersion in which the pigment is previously dispersed with a pigment dispersant. Commercially available pigment dispersions dispersed with a pigment dispersant include, for example, HOSTAJET series manufactured by Clariant and FUJI SP series manufactured by Fuji Pigment Co., Ltd. A pigment dispersion dispersed with a pigment dispersant described below may also be used.

[0116] The pigments may be used alone or in combination of two or more kinds.

[0117] From the viewpoints of print density and ink viscosity, the pigment content of the non-white ink (C) is preferably 1 to 10 mass %, more preferably 2 to 8 mass %, and even more preferably 2 to 6 mass %, relative to the total amount of the non-white ink (C).

[0118] The non-white ink (C) may contain a pigment dispersant, typically a polymer dispersant or a surfactant-type dispersant, in order to stably disperse the pigment in the ink.

[0119] The pigment dispersant can be selected from those described above for the white ink (W), for example.

[0120] When a pigment dispersant is used, the amount of the pigment dispersant blended in the non-white ink (C) varies depending on the type of pigment dispersant and is not particularly limited. In general, however, the mass ratio of the active ingredient (pigment concentration) to the pigment is preferably 0.005 to 0.5.

[0121] The non-white ink (C) has a film elongation of 500% or more and contains resin particles C having a resin skeleton different from those of the resin particles A and the resin particles B.

[0122] The film elongation of the resin particles C may be 600% or more, or 1000% or less, or 800% or less. The film elongation of the resin particles C may be, for example, in the range of 500 to 1000%.

[0123] The resin particles C are preferably resin particles that can be dispersed in an aqueous solvent. The resin particles C are preferably resin particles that can be dispersed in water without dissolving in water to form an oil-in-water (O / W) emulsion.

[0124] The resin particles C are preferably contained in the non-white ink (C) in a dispersed state as resin particles. The resin particles can be blended as a water dispersion of resin particles when producing the non-white ink (C).

[0125] The resin particles C may be, for example, anionic resin particles, cationic resin particles, nonionic resin particles, or amphoteric resin particles. However, anionic resin particles, nonionic resin particles, or a combination thereof are preferred, and anionic resin particles are more preferred.

[0126] The anionic resin particles may be those in which an anionic functional group of the resin is present on the surface of the resin particles, such as a self-emulsifying resin, or those that have been subjected to a surface treatment such as attaching an anionic dispersant to the surface of the resin particles. Representative examples of the anionic functional group include a carboxy group, a sulfo group, a sulfino group, a sulfate ester group, a phosphoric acid group, a phosphoric acid ester group, a phosphorous acid group, and a phosphorous acid ester group. Examples of the anionic dispersant include an anionic surfactant.

[0127] The nonionic resin particles may be those in which the nonionic functional group of the resin is present on the surface of the resin particles, such as a self-emulsifying resin, or those that have been subjected to a surface treatment such as attaching a nonionic dispersant to the surface of the resin particles. Representative examples of the nonionic functional group include a polyoxyalkylene glycol group, a carboxy group, and a hydroxy group. Examples of the nonionic dispersant include a nonionic surfactant.

[0128] As the type of resin particles C, it is preferable to use a resin that forms a transparent coating film.

[0129] The type of resin particles C is, for example, Conjugated diene resins such as styrene-butadiene copolymers, methyl methacrylate-butadiene copolymers, and vinyl chloride-vinyl acetate copolymers; (Meth)acrylic resins such as polymers of acrylic acid esters and methacrylic acid esters, or copolymers thereof with styrene or the like; Vinyl resins such as ethylene-vinyl acetate copolymers, Or functional group-modified resins of these various resins using monomers containing functional groups such as carboxyl groups; Examples of the resin particles include melamine resin, urea resin, polyurethane resin, polyester resin, polyolefin resin, silicone resin, polyvinyl butyral resin, alkyd resin, etc. Resin particles of a single resin such as these may be used, or hybrid type resin particles may be used.

[0130] The resin particles C may be used alone or in combination of two or more kinds.

[0131] Commercially available aqueous dispersions of resin particles C include "Mowinyl 6750", "Mowinyl 6751D", "Mowinyl 6770", and "Mowinyl 6775" manufactured by Japan Coating Resins Co., Ltd. (all trade names).

[0132] The resin particles (C) preferably contain a (meth)acrylic resin.

[0133] As described above, the resin particles C have a resin skeleton different from that of the resin particles A and resin particles B contained in the white ink (W). As an example, when the resin particles A are a polyurethane resin and the resin particles B are an (oxidized) polyolefin resin or a polyurethane resin, it is preferable that the resin particles C are a (meth)acrylic resin.

[0134] Resin particles C have a resin skeleton different from resin particles A and resin particles B, so that mixing on the substrate surface can be suppressed. Furthermore, resin particles C have a resin skeleton that is relatively flexible but harder than resin particles A, so that the resin particles C can easily return to the original film thickness after stretching while obtaining the ability to follow the expansion and contraction of the white image, and the color development can be further improved. From this viewpoint, it is preferable that resin particles C are (meth)acrylic resin, and resin particles A and resin particles B are urethane resin, polyolefin resin, or polyester resin, respectively. In another example, it is preferable that resin particles C are (meth)acrylic resin, resin particles A are urethane resin, and resin particles B are urethane resin, polyolefin resin, or polyester resin. By using urethane resin for resin particles A with high film elongation, it is possible to further improve the ability to follow the cloth substrate, suppress cracks in the image, and further improve the color development of the non-white image.

[0135] The content (solid content) of the resin particles C in the non-white ink (C) is preferably 3% by mass or more, and more preferably 5% by mass or more. The content (solid content) of the resin particles C in the non-white ink (C) is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less. The content (solid content) of the resin particles C in the non-white ink (C) is, for example, preferably 3 to 25% by mass, and more preferably 5 to 20% by mass.

[0136] The non-white ink (C) may contain resin particles D other than the resin particles C. It is preferable that the resin particles D have the same resin skeleton as the resin particles A.

[0137] The resin particles D are preferably resin particles that can be dispersed in an aqueous solvent. The resin particles D are preferably resin particles that can be dispersed in water without being dissolved in water to form an oil-in-water (O / W) emulsion.

[0138] The resin particles D are preferably contained in the non-white ink (C) in a dispersed state as resin particles. The resin particles can be blended as an aqueous dispersion of resin particles when producing the non-white ink (C).

[0139] The resin particles D 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, and anionic resin particles are more preferred.

[0140] The anionic resin particles may be those in which an anionic functional group of the resin is present on the surface of the resin particles, such as a self-emulsifying resin, or those that have been subjected to a surface treatment such as attaching an anionic dispersant to the surface of the resin particles. Representative examples of the anionic functional group include a carboxy group, a sulfo group, a sulfino group, a sulfate ester group, a phosphoric acid group, a phosphoric acid ester group, a phosphorous acid group, and a phosphorous acid ester group. Examples of the anionic dispersant include an anionic surfactant.

[0141] The nonionic resin particles may be those in which the nonionic functional group of the resin is present on the surface of the resin particles, such as a self-emulsifying resin, or those that have been subjected to a surface treatment such as attaching a nonionic dispersant to the surface of the resin particles. Representative examples of the nonionic functional group include a polyoxyalkylene glycol group, a carboxy group, and a hydroxy group. Examples of the nonionic dispersant include a nonionic surfactant.

[0142] The film elongation of the resin particles D is preferably 1000% or more, and more preferably 1200% or more. The film elongation of the resin particles D may be 2000% or less, or may be 1700% or less.

[0143] As the type of resin particles D, it is preferable to use a resin that forms a transparent coating film.

[0144] The type of resin particles D is, for example, 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 of these with styrene, etc.; Vinyl resins such as ethylene-vinyl acetate copolymers, Or functional group-modified resins of these various resins using monomers containing functional groups such as carboxyl groups; Examples of the resin particles include melamine resin, urea resin, polyurethane resin, polyester resin, polyolefin resin, silicone resin, polyvinyl butyral resin, alkyd resin, etc. Resin particles of a single resin such as these may be used, or hybrid type resin particles may be used.

[0145] The resin particles D may be used alone or in combination of two or more kinds.

[0146] Commercially available aqueous dispersions of resin particles D include "Implanir DLP", "Implanir DLP-R", "Implanir DLV", "Implanir DLI", "Implanir 1016", "Implanir 1116", "Implanir DLS", "Implanir DL1537", "Implanir DL1554", "Implanir DL1380", "Implanir LP CGL 105", "Implanir DLN-SD", "Implanir LP DSB 1069", and "Implanir DLN-W50" manufactured by Sumika Covestro Urethane Co., Ltd., and "Superflex E2000", "Superflex 740", "Superflex 500M", and "Superflex 300" manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (all trade names).

[0147] When the non-white ink (C) contains resin particles D, the content (solid content) of the resin particles D in the non-white ink (C) is preferably 3% by mass or more, and more preferably 5% by mass or more. The content (solid content) of the resin particles D in the non-white ink (C) is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less. The content (solid content) of the resin particles D in the non-white ink (C) is, for example, preferably 3 to 25% by mass, and more preferably 5 to 20% by mass.

[0148] When the non-white ink (C) contains resin particles D, the mass ratio of resin particles C to resin particles D, "resin particles C / resin particles D", is preferably 0.5 or more, more preferably 0.8 or more, and is preferably 2 or less, more preferably 1.5 or less.

[0149] The content (solid content) of the resin particles in the non-white ink (C) is preferably 3% by mass or more, more preferably 5% by mass or more, and particularly preferably 10% by mass or more. The content (solid content) of the resin particles in the non-white ink (C) is preferably 25% by mass or less, more preferably 20% by mass or less. The content (solid content) of the resin particles in the non-white ink (C) is, for example, preferably 3 to 25% by mass, and more preferably 5 to 20% by mass.

[0150] When the resin particles contained in the non-white ink (C) are resin particles C and resin particles D, the total content (solid content) of resin particles C and resin particles D is preferably 3% by mass or more, and more preferably 5% by mass or more. The total content (solid content) of resin particles C and resin particles D in the non-white ink (C) is preferably 25% by mass or less, and more preferably 20% by mass or less. The total content (solid content) of resin particles C and resin particles D in the non-white ink (C) is, for example, preferably 3 to 25% by mass, and more preferably 5 to 20% by mass.

[0151] The non-white ink (C) preferably contains water, and the main solvent may be water.

[0152] The water is not particularly limited, but is preferably one that contains as few ionic components as possible. In particular, from the viewpoint of the storage stability of the ink, it is preferable that the content of polyvalent metal ions such as calcium is small. As the water, for example, ion-exchanged water, distilled water, ultrapure water, etc. may be used.

[0153] From the viewpoint of adjusting the ink viscosity, the water content is preferably 30 to 70 mass % and more preferably 35 to 65 mass % based on the total amount of the non-white ink (C).

[0154] The non-white ink (C) may contain a water-soluble organic solvent. As the water-soluble organic solvent, an organic compound that is liquid at room temperature and dissolves in water may be used, and it is preferable to use a water-soluble organic solvent that is uniformly mixed with the same volume of water at 20°C under 1 atmosphere. The boiling point of the water-soluble organic solvent is preferably 100°C or higher, and more preferably 150°C or higher.

[0155] The water-soluble organic solvent can be selected from those described above for the white ink (W), for example.

[0156] These water-soluble organic solvents may be used alone or in combination of two or more kinds as long as they form a single phase with water.

[0157] The content of the water-soluble organic solvent in the non-white ink (C) is preferably 10 to 50% by mass, and more preferably 20 to 40% by mass, based on the total amount of the non-white ink (C).

[0158] The non-white ink (C) preferably contains a surfactant.

[0159] As the surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, or a combination thereof can be preferably used, with a nonionic surfactant being more preferred. In addition, either a low molecular weight surfactant or a high molecular weight surfactant may be used.

[0160] The HLB value of the surfactant is preferably 5-20, and more preferably 10-18.

[0161] The surfactant may be selected from those described above for the white ink (W), and among them, acetylene-based surfactants such as acetylene glycol-based surfactants are preferably used.

[0162] The surfactants may be used alone or in combination of two or more.

[0163] The content of the surfactant is preferably from 0.01 to 10% by mass, more preferably from 0.1 to 5% by mass, and even more preferably from 0.2 to 3% by mass, based on the total amount of the non-white ink (C).

[0164] The non-white ink (C) may contain other components as necessary, such as a pH adjuster and a preservative.

[0165] The method for producing the non-white ink (C) is not particularly limited, and the ink can be produced appropriately by a known method. For example, all the components are charged into a stirrer such as a three-one motor all at once or in portions, dispersed, and, if desired, passed through a filter such as a membrane filter to obtain an ink. More specifically, other components may be mixed with the non-white pigment, resin particles C, and water as necessary, and examples of the other components include those described above as components that can be contained in the non-white ink (C), such as resin particles D, surfactants, water-soluble organic solvents, and pigment dispersants. The resin particles C may be used in the form of an aqueous dispersion of the resin particles C. Similarly, the resin particles D may be used in the form of an aqueous dispersion of the resin particles D. The non-white pigment may be used in the form of a pigment dispersion in which the pigment is dispersed in advance with a pigment dispersant. These components can be mixed all at once or in portions.

[0166] The pH of the non-white ink (C) is preferably from 7.0 to 10.0, and more preferably from 7.5 to 9.0, from the viewpoint of storage stability of the ink.

[0167] The viscosity of the non-white ink (C) at 23° C. is preferably 1 to 30 mPa·s, for example, from the viewpoint of inkjet dischargeability. <Textile printing ink set> The textile printing ink set of one embodiment includes a white ink (W) and a non-white ink (C). The textile printing ink set may include one or more types of non-white ink (C). The textile printing ink set may further include a pre-treatment liquid including a polyvalent metal salt, water, and a water-soluble organic solvent. The textile printing ink set may also include a post-treatment liquid, etc.

[0168] The white ink (W) may be the white ink (W) described above, and the non-white ink (C) may be the non-white ink (C) described above.

[0169] By applying a white ink (W) to a fabric using this printing ink set and then applying a non-white ink (C) thereon, a printed textile having a non-white image with excellent color development can be produced. In particular, even when the non-white ink (C) is applied by a wet-on-wet method after the application of the white ink (W), a printed textile having a non-white image with excellent color development can be produced.

[0170] When the textile printing ink set contains a pretreatment liquid, the pretreatment liquid is applied to the fabric, and then the white ink (W) is applied, and further the non-white ink (C) is applied. When the textile printing ink set of one embodiment is used, even when each process is a wet-on-wet process, it is possible to produce a printed textile having a non-white image with excellent color development.

[0171] The pretreatment liquid may contain a polyvalent metal salt.

[0172] Polyvalent metal salts are composed of divalent or higher polyvalent metal ions and anions. Examples of divalent or higher polyvalent metal ions include Ca 2+ , Mg 2+ , Cu 2+ , Ni 2+ , Zn 2+ , B.A. 2+ Examples of the anion include Cl. - , NO3 - , CH3COO - , I - , Br - , ClO3 - Specific examples of polyvalent metal salts include calcium chloride, calcium nitrate, magnesium nitrate, copper nitrate, calcium acetate, and magnesium acetate.

[0173] These polyvalent metal salts may be used alone or in combination of two or more.

[0174] The content of the polyvalent metal salt (amount of active ingredient) is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, based on the total amount of the pretreatment liquid. On the other hand, the content of the polyvalent metal salt (amount of active ingredient) is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, based on the total amount of the pretreatment liquid. The content of the polyvalent metal salt (amount of active ingredient) is, for example, preferably 5 to 40% by mass, more preferably 10 to 35% by mass, and even more preferably 15 to 30% by mass, based on the total amount of the pretreatment liquid.

[0175] When a metal salt hydrate is used as the polyvalent metal salt, the amount of the polyvalent metal salt (amount of active ingredient) is the amount converted into the anhydrate.

[0176] The pretreatment liquid preferably contains water, and the main solvent may be water.

[0177] The water is not particularly limited, but is preferably one that contains as few ionic components as possible. Examples of water include ion-exchanged water, distilled water, and ultrapure water.

[0178] The content of water is preferably 20 to 80 mass %, more preferably 30 to 70 mass %, and further preferably 40 to 60 mass %, based on the total amount of the pretreatment liquid.

[0179] The pretreatment liquid preferably contains a water-soluble organic solvent. As the water-soluble organic solvent, an organic compound that is liquid at room temperature and dissolves in water can be used, and it is preferable to use a water-soluble organic solvent that is uniformly mixed with the same volume of water at 20°C under 1 atmosphere. The boiling point of the water-soluble organic solvent is preferably 100°C or higher, and more preferably 150°C or higher. As the water-soluble organic solvent, for example, those described above for the white ink (W) can be used.

[0180] The water-soluble organic solvent may be used alone or in combination of two or more kinds as long as it forms a single phase with water. The content of the water-soluble organic solvent is preferably 1 to 50 mass %, more preferably 5 to 40 mass %, and further preferably 10 to 30 mass %, based on the total amount of the pretreatment liquid.

[0181] The pretreatment liquid preferably contains a surfactant. As the surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, or a combination thereof can be preferably used, and a nonionic surfactant is more preferable. In addition, either a low molecular weight surfactant or a high molecular weight surfactant may be used.

[0182] The HLB value of the surfactant is preferably 5-20, and more preferably 10-18.

[0183] As the surfactant, for example, those described above in relation to the white ink (W) can be used.

[0184] The surfactants may be used alone or in combination of two or more.

[0185] The content of the surfactant is preferably from 0.01 to 10% by mass, more preferably from 0.1 to 5% by mass, and even more preferably from 0.2 to 3% by mass, based on the total amount of the pretreatment liquid.

[0186] The pretreatment liquid may contain other components as necessary, such as a defoamer, a pH adjuster, an antioxidant, and a preservative.

[0187] The method for producing the pretreatment liquid is not particularly limited, and the pretreatment liquid can be produced by any known method. For example, the pretreatment liquid can be obtained by dispersing all the components in a stirrer such as a three-one motor or in portions, and passing the mixture through a filter such as a membrane filter, if desired.

[0188] The pH of the pretreatment liquid is preferably 3-9, and more preferably 4-8.

[0189] The viscosity of the pretreatment liquid at 23°C is preferably 1 to 30 mPa·s.

[0190] <Manufacturing method for printed items> A method for producing a printed textile product using a textile printing ink set can include, as necessary, a step of applying a pretreatment liquid to a cloth (hereinafter also referred to as a "pretreatment liquid application step"), a step of applying a white ink (W) to the cloth to which the pretreatment liquid has been applied in a wet-on-wet manner by an inkjet method (hereinafter also referred to as a "white ink (W) application step"), and a step of applying a non-white ink (C) to the cloth to which the white ink (W) has been applied in a wet-on-wet manner by an inkjet method (hereinafter also referred to as a "non-white ink (C) application step").

[0191] Examples of the fabric include natural fibers such as cotton, silk, wool, and hemp; chemical fibers such as polyester, acrylic, polyurethane, nylon, rayon, cupra, and acetate; and blends of these fibers. The fabric may be woven, knitted, or nonwoven.

[0192] The pretreatment liquid application step will be described.

[0193] The method for applying the pretreatment liquid to the fabric is not particularly limited, and any method can be used, such as a spraying method using an airbrush or the like, a dipping method, a pad method, or a coating method. Furthermore, various printing methods such as inkjet printing (inkjet method) and screen printing may also be used.

[0194] The inkjet method is not particularly limited, and may be any of a piezoelectric method, an electrostatic method, a thermal method, etc. When an inkjet printing device is used, it is preferable to eject droplets of the pretreatment liquid or ink from an inkjet head based on a digital signal and to cause the ejected droplets to adhere to the cloth.

[0195] The area to which the pretreatment liquid is applied may be an area having the same shape as the image made of white ink (W), a wider area including the shape of the image made of white ink (W), or the entire surface of the fabric.

[0196] It is preferable that the application area of ​​the pretreatment liquid, the application area of ​​the white ink (W) and the application area of ​​the non-white ink (C) at least partially overlap.

[0197] The amount of pretreatment liquid applied to the fabric is 10 to 100 g / m 2 is preferable, and 20 to 75 g / m 2 More preferably, 30 to 50 g / m 2 is more preferred.

[0198] The white ink (W) application step will be described.

[0199] The white ink (W) 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 piezoelectric method, an electrostatic method, or a thermal method. When an inkjet printing device is used, it is preferable to eject droplets of the pretreatment liquid or ink from an inkjet head based on a digital signal and to allow the ejected droplets to adhere to the fabric.

[0200] It is preferable that the white ink (W) is applied so that the application area overlaps at least partially with the application area of ​​the pretreatment liquid. It is preferable that the application area of ​​the pretreatment liquid and the application area of ​​the white ink (W) at least partially overlap.

[0201] The white ink (W) is preferably applied to the cloth to which the pretreatment liquid has been applied by a wet-on-wet method. The white ink (W) is preferably applied in a state in which moisture is not completely removed from the cloth to which the pretreatment liquid has been applied. Preferably, the white ink (W) can be applied in a state in which the cloth to which the pretreatment liquid has been applied is kept wet. For example, it is preferable to apply the white ink (W) to the cloth without performing a drying process such as heat drying after applying the pretreatment liquid to the cloth. The temperature of the cloth surface after applying the pretreatment liquid and before applying the white ink (W) is preferably 40° C. or lower, more preferably 35° C. or lower. After applying the pretreatment liquid, it is preferable to apply the white ink (W) in a state in which the remaining amount of the volatile matter of the pretreatment liquid on the cloth is 90% by mass or more. The time from applying the pretreatment liquid to the cloth to applying the white ink (W) is preferably 0.1 to 200 seconds.

[0202] The amount of white ink (W) applied to the fabric is not particularly limited, but is, for example, 50 to 400 g / m 2 is preferable, and 100 to 200 g / m 2 is more preferred.

[0203] The non-white ink (C) application step will be described.

[0204] The non-white ink (C) 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 piezoelectric method, an electrostatic method, or a thermal method. When an inkjet printing device is used, it is preferable to eject droplets of the pretreatment liquid or ink from an inkjet head based on a digital signal and to allow the ejected droplets to adhere to the fabric.

[0205] It is preferable that the non-white ink (C) is applied so that the application area at least partially overlaps with the application area of ​​the white ink (W). It is preferable that the application area of ​​the pretreatment liquid, the application area of ​​the white ink (W), and the application area of ​​the non-white ink (C) at least partially overlap.

[0206] The non-white ink (C) is preferably applied by a wet-on-wet method to the cloth to which the white ink (W) has been applied. The non-white ink (C) is preferably applied in a state in which moisture is not completely removed from the cloth to which the white ink (W) has been applied. Preferably, the non-white ink (C) can be applied in a state in which the cloth to which the white ink (W) has been applied is kept wet. For example, it is preferable to apply the non-white ink (C) to the cloth without performing a drying process such as heat drying after applying the white ink (W) to the cloth. The temperature of the cloth surface after applying the white ink (W) and before applying the non-white ink (C) is preferably 40° C. or lower, more preferably 35° C. or lower. After applying the white ink (W), it is preferable to apply the non-white ink (C) in a state in which the remaining amount of the volatile matter of the white ink (W) on the cloth is 90% by mass or more. The time from applying the white ink (W) to applying the non-white ink (C) to the cloth is preferably 0.1 to 200 seconds.

[0207] The amount of the non-white textile printing ink (C) applied to the fabric is not particularly limited, but may be, for example, 5 to 60 g / m 2 is preferable, and 10 to 30 g / m 2 is more preferred.

[0208] One type of non-white ink (C) may be applied, or two or more types of non-white inks (C) may be applied.

[0209] When the pretreatment liquid, the white ink (W) and the non-white ink (C) are applied by an inkjet method, each ink may be applied by a separate printing device, or may be applied by using a single printing device.

[0210] For example, the application of the pretreatment liquid, the application of the white ink (W), and the application of the non-white ink (C) may be performed using one printing device. Also, for example, two printing devices may be used, with one of them applying the pretreatment liquid and the other applying the white ink (W) and the non-white ink (C).

[0211] It is preferable to provide a step of heat treating the fabric after the step of applying the non-white ink (C).

[0212] The heat treatment temperature can be appropriately selected depending on the material of the fabric, etc. The heat treatment temperature is, for example, preferably 100° C. or higher, more preferably 150° C. or higher. From the viewpoint of reducing damage to the fabric, the heat treatment temperature is preferably 200° C. or lower.

[0213] The heating device is not particularly limited, but for example, a heat press, a roll heater, a hot air device, an infrared lamp heater, or the like can be used.

[0214] The heat treatment time may be appropriately set depending on the heating method and the like, and is, for example, preferably 1 second to 10 minutes, and may be 5 seconds to 5 minutes.

[0215] A step of applying a post-treatment liquid may be provided after the step of applying the non-white ink (C). For example, a step of heat treating the fabric may be provided after the step of applying the non-white ink (C), and then the post-treatment liquid may be applied. For example, the post-treatment liquid may be applied by a wet-on-wet method after the step of applying the non-white ink (C). Furthermore, a step of heat treating the fabric may be provided after applying the post-treatment liquid.

[0216] Several embodiments of the present disclosure are presented below.

[0217] <1> A textile printing ink set comprising: a white inkjet ink containing a white pigment, resin particles A having a film elongation of 1000% or more, and resin particles B which are ionic resin particles having a film elongation of less than 1000% and an average particle diameter of 150 nm or less; and a non-white inkjet ink containing a non-white pigment, and resin particles C having a film elongation of 500% or more and which have a resin skeleton different from that of the resin particles A and the resin particles B.

[0218] <2> The content of resin particles in the non-white inkjet ink is 10% by weight or more based on the total amount of the non-white inkjet ink. <1> 2. The textile printing ink set according to claim 1 .

[0219] <3> The resin particles A contain a polyurethane resin. <1> or <2> 2. The textile printing ink set according to claim 1 .

[0220] <4> The resin particles B contain at least one of an anionic oxidized polyethylene resin and a polyurethane resin having a charge density of 60 μeq / g or more. <1> ~ <3> 13. The textile printing ink set according to claim 12,

[0221] <5> The resin particles C contain a (meth)acrylic resin. <1> ~ <4> 13. The textile printing ink set according to claim 12,

[0222] <6> The non-white inkjet ink (C) contains resin particles D having the same resin skeleton as that of the resin particles A. <1> ~ <5> 13. The textile printing ink set according to claim 12,

[0223] <7> The resin particles D contain a polyurethane resin. <6> 2. The textile printing ink set according to claim 1 .

[0224] <8> The resin particles A contain a polyurethane resin, and the resin particles D contain a polyurethane resin. <6> A textile printing ink set according to claim 1 EXAMPLES

[0225] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples.

[0226] In the following description, unless otherwise specified, "%" means "mass %" except for film elongation. The content shown in each table is the total amount of raw materials blended as a solution or dispersion, etc., and the percentage of pigment content, resin content, active ingredient, etc. is also shown.

[0227] 1. Preparation of pretreatment solution The formulation of the pretreatment liquid is shown in Table 1. The raw materials were mixed in the compounding ratio shown in Table 1 and filtered through a cellulose acetate membrane filter having a pore size of 3 μm to obtain pretreatment liquids PT1 and PT2.

[0228] Details of the raw materials listed in Table 1 are as follows. (polyvalent metal salts) Magnesium nitrate hexahydrate: Fujifilm Wako Pure Chemical Industries, Ltd. Calcium chloride: Fujifilm Wako Pure Chemical Industries, Ltd. (Water-soluble organic solvent) Diethylene glycol: Fujifilm Wako Pure Chemical Industries, Ltd. Glycerin: Fujifilm Wako Pure Chemical Industries, Ltd. (Surfactant) Olfine E1020: Acetylene glycol surfactant, manufactured by Nissin Chemical Industry Co., Ltd.

[0229] [Table 1]

[0230] 2. Preparation of White Inkjet Ink (1) Preparation of white pigment dispersion 350 g of titanium dioxide "R62N" (manufactured by Sakai Chemical Industry Co., Ltd.) was used as a white pigment, and 14 g (3.5 g of active ingredient) of "Demol EP" (manufactured by Kao Corporation) was used as a pigment dispersant. These were mixed with 636 g of ion-exchanged water, and 0.5 mmΦ zirconia beads were dispersed using a bead mill (manufactured by Shinmaru Enterprises Co., Ltd., DYNO-MILL KDL A type) with a filling rate of 80% and a residence time of 2 minutes, to obtain a white pigment dispersion (pigment content 35% by mass). (2) Preparation of white inkjet ink The formulations of the white inkjet inks W1 to W6 are shown in Table 2. The raw materials were mixed in the blending ratios shown in the table and filtered through a cellulose acetate membrane filter with a pore size of 3 μm to obtain the white inks W1 to W6.

[0231] Details of the raw materials of the white inkjet inks W1 to W6 listed in Table 2 are as follows. (Pigment Dispersion) White pigment dispersion: Obtained by the above method, pigment content 35% by mass (Resin particles A) Dispersion A1: "Superflex 740" aqueous dispersion of polyurethane resin particles, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., resin content 40% by mass, anionic (Resin particle B) Dispersion B1: "Superflex 420", aqueous dispersion of polyurethane resin particles, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., resin content 32% by mass, anionic Dispersion B2: "Superflex 150HS", aqueous dispersion of polyurethane resin particles, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., resin content 30% by mass, anionic Dispersion B3: "Eliteru KT9204", water dispersion of polyester resin particles, manufactured by Unitika Ltd., resin content 30% by mass, anionic Dispersion B4: "AQUACER507", water dispersion of oxidized polyethylene resin, manufactured by BYK Japan Co., Ltd., resin content 35% by mass, melting point of resin component 130°C, anionic (Surfactant) Surfactant 1: "Olfine E1010", an acetylene glycol surfactant, manufactured by Nissin Chemical Industry Co., Ltd. (Water-soluble organic solvent) Glycerin: Fujifilm Wako Pure Chemical Industries, Ltd. Diethylene glycol: Fujifilm Wako Pure Chemical Industries, Ltd.

[0232] 3. Preparation of Non-white Inkjet Inks The formulations of the non-white inkjet inks C1 to C5 are shown in Table 3. The raw materials were mixed in the blending ratios shown in the table and filtered through a cellulose acetate membrane filter with a pore size of 3 μm to obtain the non-white inks C1 to C5.

[0233] Details of the raw materials of the non-white inkjet inks C1 to C5 listed in Table 3 are as follows. (Pigment Dispersion) Non-white pigment dispersion: "CAB-O-JET465M", manufactured by Cabot Japan Co., Ltd., pigment content 15% by mass (Resin particle C) Dispersion C1: "Mowinyl 6751D", water dispersion of acrylic resin particles, manufactured by Japan Coating Resin Co., Ltd., resin content 50% by mass, anionic Dispersion C2: "Movinyl 6750", water dispersion of acrylic resin particles, manufactured by Japan Coating Resin Co., Ltd., resin content 50% by mass, anionic (Resin particle D) Dispersion D1: "Superflex 740", aqueous dispersion of polyurethane resin particles, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., resin content 40% by mass, anionic Dispersion D2: "Superflex 420", aqueous dispersion of polyurethane resin particles, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., resin content 32% by mass, anionic (Surfactant) Surfactant 1: "Olfine E1010", an acetylene glycol surfactant, manufactured by Nissin Chemical Industry Co., Ltd. (Water-soluble organic solvent) Glycerin: Fujifilm Wako Pure Chemical Industries, Ltd. Diethylene glycol: Fujifilm Wako Pure Chemical Industries, Ltd.

[0234] 4. Measurement of resin particle film elongation Tables 2 and 3 show the film elongation of the resin particles in each of the resin particle dispersions used in the white inkjet inks W1 to W6 or the non-white inkjet inks C1 to C5, excluding dispersions B3 and B4. The film elongation of the resin particles shown in the tables is a value obtained by the following procedure.

[0235] First, the aqueous dispersion of each resin particle was applied onto a polytetrafluoroethylene sheet so that the film thickness after drying was 500 μm, and the sheet was dried at 23 ° C for 15 hours, and then further dried at 80 ° C for 6 hours and at 120 ° C for 20 minutes, and then peeled off from the sheet to prepare a resin film. This resin film was cut into a column shape with a width of 2 cm and a length of 4 cm to prepare a resin film test piece. Using a Tensilon universal testing machine RTC-1225A (manufactured by Orientec Co., Ltd.), the resin film test piece was stretched at a measurement temperature of 20 ° C and a measurement speed of 200 mm / min, and the length of the resin film test piece until it broke was measured, and the value expressed as a percentage relative to the original length was taken as the film elongation.

[0236] 5. Measurement of the average particle size of resin particles The average particle diameter of the resin particles in each of the resin particle dispersions used in the white inkjet inks W1 to W6 is shown in Table 2. The average particle diameter of the resin particles listed in the table is the volume-based median diameter measured at a temperature of 25°C using a dynamic light scattering particle size distribution measuring device "Nano Prtica SZ-100 Nanoparticle Analyzer" (manufactured by Horiba, Ltd.) by diluting each aqueous dispersion of resin particles with purified water to a particle concentration of 0.5% by mass, with the following settings: dispersion medium refractive index: 1.333, sample refractive index: 1.600, and calculation conditions: polydisperse / narrow.

[0237] 6. Measurement of charge density of resin particles Table 2 shows the charge density of the resin particles in each of the resin particle dispersions used in the white inkjet inks W1 to W6, except for Dispersion B4. The charge density of the resin particles listed in the table is a value obtained by the streaming potential method according to the following procedure. A colloid particle charge meter (Model CAS, manufactured by AFG ANALYTIC GmbH) was used to measure the charge density. The aqueous dispersion of the resin particles to be measured was diluted 100 times with ion-exchanged water, and titrated with a 0.0025N polydiallyldimethylammonium chloride solution (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). The reaction end point at which the streaming potential of the sample becomes 0 V was measured, and the total charge amount of the sample (diluted aqueous dispersion of resin particles) was calculated from the amount of the 0.0025N polydiallyldimethylammonium chloride solution used up to the reaction end point. The charge density (μeq / g) of the resin particles is calculated by dividing the total charge amount of the sample (diluted aqueous dispersion of resin particles) by the solid content amount of the resin particles contained in the sample.

[0238] [Table 2]

[0239] [Table 3]

[0240] 7. Preparation of printed items Using the pretreatment liquid, white inkjet ink, and non-white inkjet ink prepared above, printed items of Examples 1 to 7 and Comparative Examples 1 to 4 were prepared according to the following procedure.

[0241] Table 4 shows the types and coating amounts of the pretreatment liquids, white inkjet inks, and non-white inkjet inks used in producing the printed items of Examples 1 to 7 and Comparative Examples 1 to 4. (1) A black polyester T-shirt (product name: Glimmer) manufactured by Toms Corporation was used as a substrate, and the pretreatment liquid was applied to a 10 cm x 20 cm area of ​​the surface of the T-shirt by the inkjet method. (2) After the pretreatment liquid was applied, a white inkjet ink was applied by an inkjet method to the area where the pretreatment liquid had been applied, without carrying out a drying step. (3) After the white inkjet ink was applied, a non-white inkjet ink was applied by inkjet method to half (10 cm x 10 cm) of the area where the white inkjet ink was applied, without carrying out a drying step. (4) After applying the non-white inkjet ink, the material was dried by heating at 120° C. for 1 minute using a heat press machine manufactured by FUSION, to obtain a printed material.

[0242] A printing device "MMP-8130" manufactured by Mastermind was used to apply the pretreatment liquid, the white inkjet ink, and the non-white inkjet ink.

[0243] 8. Evaluation of printed items The whiteness of the white image and the color development of the non-white image of the obtained printed matter were evaluated according to the following criteria. The evaluation results are shown in Table 4. (1) Whiteness of white image A: The whiteness is very high and the uniformity of the white image is also good. B: The whiteness of the white image is somewhat low, but the uniformity of the white image is good, or the whiteness of the white image is high, but slight unevenness is observed in the white image. C: The whiteness of the white image is low and / or there is a lot of unevenness in the white image. (2) Color development of non-white images A: High color development and excellent ink color reproducibility, with no breaks in non-white images B: The ink has slightly low color reproducibility but high color development and no breakage of non-white images, or the ink has high color development and excellent color reproducibility, but slight breakage of non-white images is observed. C: Poor color development and poor color reproducibility, and / or many breaks in non-white images are observed D: Poor color development and poor color reproducibility, and many breaks in non-white images are observed

[0244] [Table 4]

[0245] The printed products of Examples 1 to 7 were excellent in color development of non-white images, and the printed products of Examples 1 to 7 were excellent in whiteness of white images.

[0246] In contrast, the color development of non-white images was poor in Comparative Examples 1 and 2, which used non-white inkjet inks C4 and C5 that did not contain resin particles C. In particular, the non-white inkjet ink C5 had low film elongation of the dispersion D2 used, and many breaks were observed in the non-white images.

[0247] In Comparative Example 3 using the white inkjet ink W5 not containing the resin particles B, the ink did not settle sufficiently, resulting in poor color reproducibility and poor color development of the non-white image. In addition, the whiteness of the white image was also low, and the black color of the T-shirt could not be sufficiently concealed.

[0248] In Comparative Example 4, which used the white inkjet ink W6 that did not contain resin particles A, the non-white image had many broken parts and was poor in color development. In addition, the uniformity of the white image was low, and the black color of the T-shirt could not be sufficiently concealed.

Claims

1. a white ink-jet ink containing a white pigment, resin particles A having a film elongation of 1000% or more, and resin particles B which are ionic resin particles having a film elongation of less than 1000% and an average particle diameter of 150 nm or less; A textile printing ink set comprising: a non-white pigment; and a non-white ink-jet ink comprising resin particles C having a film elongation of 500% or more and a resin skeleton different from those of the resin particles A and the resin particles B.

2. 2. The textile printing ink set according to claim 1, wherein the content of the resin particles is 10% by weight or more based on the total amount of the non-white inkjet inks.

3. The textile printing ink set according to claim 1 , wherein the resin particles A contain a polyurethane resin.

4. 2. The textile printing ink set according to claim 1, wherein the resin particles B contain at least one of an anionic oxidized polyethylene resin and a polyurethane resin having a charge density of 60 μeq / g or more.

5. The textile printing ink set according to claim 1 , wherein the resin particles C contain a (meth)acrylic resin.

6. The textile printing ink set according to claim 1 , wherein the non-white inkjet ink contains resin particles D having the same resin skeleton as the resin particles A.

7. The textile printing ink set according to claim 6, wherein the resin particles D contain a polyurethane resin.

8. The textile printing ink set according to claim 6, wherein the resin particles A contain a polyurethane resin, and the resin particles D contain a polyurethane resin.

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