Ink set for inkjet textile printing, image forming method, and image formed product

Abstract

To provide an ink set for inkjet textile printing which enables formation of an image having excellent texture as well as high wet rubbing fastness and washing fastness, and also to provide an image forming method and an image formed product.SOLUTION: An ink set for inkjet textile printing includes ink and at least one treatment liquid. The ink includes pigment, a pigment-dispersing agent, and a solvent. The pigment-dispersing agent is a block copolymer including a hydrophilic block A and a hydrophobic block B. At least one of the treatment liquid and the ink contains a crosslinking agent. The crosslinking agent includes at least one of a vinyl ether compound, an epoxy compound, a carbodiimide compound, an oxazoline compound, an isocyanate compound, and an aziridine compound.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an ink set for ink-jet textile printing, an image forming method, and an image formed product. [Background technology]

[0002] Methods for forming an image on a fabric such as cloth or nonwoven fabric include screen printing, roller printing, etc. In recent years, inkjet printing, which forms an image on a fabric by an inkjet method, has become widespread because it allows dyeing in a short time and has high production efficiency.

[0003] There are two types of coloring materials for textile printing inks: dyes and pigments. Inks using dyes have the advantage of being highly color-developing, and of having high color fastness because they react with the functional groups of the fibers. On the other hand, they require processing steps such as a steaming process to fix the dye and a process to remove any unfixed dye, and the workload involved in these processes is problematic.

[0004] On the other hand, inks using pigments are preferred over dyes because they are more convenient since they can form images with high lightfastness and do not require processing steps such as a step of removing unfixed dye. From the viewpoint of improving the fastness of images, the addition of a crosslinking agent to the ink has been considered.

[0005] Patent Document 1 discloses a pigment-containing aqueous ink composition for textile printing ink jet printing, for example, a composition containing a pigment, a random copolymer as a pigment dispersant, and a crosslinking agent.

[0006] Patent Document 2 discloses a method of producing a printed material by inkjet printing an ink composition for inkjet printing containing a pigment and a crosslinkable binder component onto a textile product, and then heat-treating the printed material with water vapor. Patent Document 2 describes that the crosslinkable binder component is melted or softened and crosslinked to form a film by heat-treating the printed material with water vapor.

[0007] On the other hand, Patent Document 3 describes an ink composition for inkjet textile printing that contains a pigment, an AB block polymer, which is a polymer of different monomers A and B as a polymer dispersant, and a urethane resin, and in the examples, describes a configuration that does not contain a crosslinking agent. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] JP 2022-148532 A [Patent Document 2] JP 2020-204115 A [Patent Document 3] JP 2016-210921 A Summary of the Invention [Problem to be solved by the invention]

[0009] According to the findings of the present inventors, the above-mentioned Patent Document 1 considers improving fastness by using an ink containing a random copolymer as a pigment dispersant and a crosslinking agent, but the fastness of the image is insufficient. In addition, the image quality is deteriorated due to the influence of the crosslinking agent, and the image quality is also unsatisfactory.

[0010] In addition, in the above-mentioned Patent Document 2, a crosslinkable binder component is crosslinked by a crosslinking agent to form a film in the image area formed on the fabric, so that the image quality is deteriorated due to the influence of the crosslinking agent, and further the texture is unsatisfactory.

[0011] On the other hand, in Patent Document 3, fastness is improved by adding a urethane resin as a binder component, but the fastness of the image is insufficient. When the present inventors used it in combination with a crosslinking agent, it was difficult to improve fastness, and when they tried to improve it, the texture was also insufficient, and it was not possible to achieve both fastness and texture.

[0012] The present invention has been made in view of the above circumstances, and has an object to provide an ink set for ink-jet textile printing, an image forming method, and an image formed product which have excellent texture, wet rub fastness, and washing fastness, and further have good image quality, even with a small amount of binder component. [Means for solving the problem]

[0013] In order to solve the above problems, the present inventors conducted extensive research and discovered that one of the causes of the decrease in fastness of an image is the influence of the hydrophilic site of a pigment dispersant. By selecting a crosslinker that reacts with the hydrophilic site of the pigment dispersant, the wet rub fastness and washing fastness of the image area could be improved.

[0014] The present inventors also found that by using a block copolymer containing a hydrophilic block A and a hydrophobic block B as a pigment dispersant, peeling of the pigment dispersant from the pigment in the ink can be suppressed and cross-linking can be performed between the pigment dispersants, thereby providing an ink set for ink-jet textile printing that is even more excellent in wet rub fastness and wash fastness as well as good texture and image quality, and thus completed the present invention.

[0015] That is, the above problem can be solved by the following configuration.

[0016] [1] An ink-jet printing ink set comprising an ink-jet ink and at least one treatment liquid, The ink-jet ink comprises a pigment, a pigment dispersant, and a solvent; The pigment dispersant is a block copolymer including a hydrophilic block A and a hydrophobic block B, At least one of the treatment liquid and the ink-jet ink contains a crosslinking agent, the crosslinking agent contains at least one compound selected from the group consisting of vinyl ether compounds, epoxy compounds, carbodiimide compounds, oxazoline compounds, isocyanate compounds, and aziridine compounds; Ink set for inkjet textile printing.

[0017] [2] The pigment dispersant is It is an ABA type block copolymer containing two hydrophilic blocks A and one hydrophobic block B. [1] An ink set for ink-jet textile printing.

[0018] [3] The crosslinking agent is contained at least in the treatment liquid, The content of the crosslinking agent in the treatment liquid is The content is 0.1% by mass or more based on the total mass of the treatment liquid. [1]-[2] An ink set for ink-jet textile printing.

[0019] [4] The content of the crosslinking agent in the inkjet ink is 3.0% by mass or less based on the total mass of the inkjet ink, [1] to [3] above, an ink set for ink-jet textile printing.

[0020] [5] On the surface of the fabric, The method includes a step of applying a treatment liquid and a step of applying an inkjet ink by an inkjet method, The ink-jet ink comprises a pigment, a pigment dispersant, and a solvent; The pigment dispersant is a block copolymer including a hydrophilic block A and a hydrophobic block B, At least one of the treatment liquid and the ink-jet ink contains a crosslinking agent, the crosslinking agent contains at least one compound selected from the group consisting of vinyl ether compounds, epoxy compounds, carbodiimide compounds, oxazoline compounds, isocyanate compounds, and aziridine compounds; Image forming method.

[0021] [6] The amount of the crosslinking agent applied to the fabric per unit area X1g / m 2 and, The amount of the pigment dispersant applied to the fabric per unit area Y1g / m 2The ratio X1 / Y1 is in the range of 0.05 to 10. The image forming method according to [5].

[0022] [7] A method for manufacturing a print medium comprising: the image portion includes a pigment and a pigment dispersant crosslinked by a crosslinking agent, The pigment dispersant is a block copolymer including a hydrophilic block A and a hydrophobic block B, the crosslinking agent contains at least one compound selected from the group consisting of vinyl ether compounds, epoxy compounds, carbodiimide compounds, oxazoline compounds, isocyanate compounds, and aziridine compounds; Image formation.

[0023] [8] The amount of the crosslinking agent per unit area contained in the image area is X2 g / m 2 and, The amount of the pigment dispersant per unit area contained in the image portion is Y2 g / m 2 The ratio X2 / Y2 is in the range of 0.05 to 10. [7] The image-formed product according to the above. Effect of the Invention

[0024] According to the present invention, there are provided an ink set for ink-jet textile printing, an image forming method, and an image formed product which are excellent in texture, wet rub fastness, and wash fastness, and further in image quality. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0025] Hereinafter, an embodiment of the present invention will be described, but the present invention is not limited to the following embodiment. In this specification, a numerical range expressed using "to" means a range including the numerical values ​​before and after "to" as the lower and upper limits.

[0026] 1. Inkjet textile printing ink set The ink set for ink-jet printing according to one embodiment of the present invention includes an ink-jet ink (hereinafter, referred to as "ink") and at least one treatment liquid. At least one of the ink and the treatment liquid includes a crosslinking agent.

[0027] In particular, the treatment liquid applied before the application of ink is also called a "pre-treatment liquid", and the treatment liquid applied after the application of ink is also called a "post-treatment liquid".

[0028] 1-1. Crosslinking agent The inkjet printing ink set according to one embodiment of the present invention includes a crosslinking agent, which includes at least one compound selected from the group consisting of a vinyl ether compound, an epoxy compound, a carbodiimide compound, an oxazoline compound, an isocyanate compound, and an aziridine compound.

[0029] The crosslinking agent reacts with hydrophilic functional groups (such as hydroxyl groups, carboxyl groups, amino groups, and sulfonic acid groups) in the pigment dispersant and fabric described below, which have hydrogen atoms bonded to nitrogen atoms or oxygen atoms, thereby suppressing swelling of the image area due to water and improving wet friction fastness and washing fastness.

[0030] The crosslinking agent may be synthesized using a known technique, or a commercially available product may be used. Examples of the crosslinking agent include those described in paragraphs 0130 and 0235 of JP-A-2020-2220 and paragraphs 0066 to 0073 of JP-A-2020-203965.

[0031] Examples of the vinyl ether compound include 1,4-butanediol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, and the like.

[0032] Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, etc. Examples of commercially available products include the Denacol series manufactured by Nagase ChemteX Corporation.

[0033] Examples of the carbodiimide compound include carbodiimide, N,N'-dimethylcarbodiimide, N-ethyl,N'-isopropylcarbodiimide, N,N'-diisopropylcarbodiimide, N,N'-dicyclohexylcarbodiimide, N,N'-diphenylcarbodiimide, N,N'-diacetylcarbodiimide, N,N'-bis(2-propene)-carbodiimide, N,N'-dipyrrolidylcarbodiimide, N,N'-diethoxycarbodiimide, bis(trimethylsilyl)carbodiimide, 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimide metho-p-toluenesulfonate, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, calcium cyanamide, and polymers having a carbodiimide structure in the main chain or side chain. Examples of commercially available products include Carbodilite manufactured by Nisshinbo Chemical Co., Ltd.

[0034] Examples of the oxazoline compound include 2-oxazoline, 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline, 2-(n-propyl)-2-oxazoline, 2-(isopropyl)-2-oxazoline, 2-cyclohexyl-2-oxazoline, 2-phenyl-2-oxazoline, 2-pyrrolidyl-2-oxazoline, 2-acetyl-2-oxazoline, 2-(2-propene)-2-oxazoline, 4,5-dimethyl-2-oxazoline, 2,4,4-trimethyl-2-oxazoline, 5-phenyl-2-(2-propynylamino)-2-oxazoline-4-one, 4-ethoxymethylene-2-phenyl-2-oxazoline-5-one, and polymers having an oxazoline structure in the main chain or side chain. Examples of commercially available products include the Epocross series manufactured by Nippon Shokubai Co., Ltd.

[0035] Examples of the isocyanate compound include phenylene diisocyanate, cyclohexane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, bis(isocyanatomethyl)cyclohexane, norbornene diisocyanate, lysine diisocyanate, polymers of the above diisocyanates, and reaction products of 1 mole of diol and 2 moles of diisocyanate. In addition, in order to increase stability in a solvent containing water, blocked isocyanates stabilized by masking the isocyanate group with a blocking agent are preferably used. Examples of commercially available blocked isocyanates include Meikanate series manufactured by Meisei Chemical Industry Co., Ltd.

[0036] Examples of the aziridine compound include trimethylolpropane-tri-β-aziridinylpropionate, tetramethylolmethane-tri-β-aziridinylpropionate, N,N'-diphenylmethane-4,4'-bis(1-aziridinecarbosamide), N,N'-hexamethylene-1,6'-bis(1-aziridinecarbosamide), N,N'-toluene-2,4'-bis(1-aziridinecarbosamide), etc. Examples of commercially available products include the Chemitite series manufactured by Nippon Shokubai Co., Ltd.

[0037] Among the above crosslinking agents, epoxy compounds, oxazoline compounds, and isocyanate compounds are preferred from the viewpoint of improving storage stability and wet friction fastness. From the viewpoint of achieving good image quality in addition to storage stability and wet friction fastness, epoxy compounds and isocyanate compounds are more preferred. From the viewpoint of achieving good texture in addition to storage stability, wet friction fastness, and image quality, isocyanate compounds are even more preferred. Epoxy compounds and isocyanate compounds not only form a crosslinked structure with the pigment dispersant, but also crosslink well with the hydrophilic functional groups contained in the fabric. Therefore, the wet heat fastness is further improved. Furthermore, epoxy compounds and isocyanate compounds have high affinity with additives such as aggregating agents contained in the ink, and are unlikely to hinder the wetting and spreading of the ink. Therefore, unevenness in the pigment concentration can be suppressed, and image quality is improved.

[0038] When the treatment liquid contains a crosslinking agent, the content of the crosslinking agent is preferably 0.1% by mass to 4.0% by mass, and more preferably 0.5% by mass to 2.0% by mass, based on the total mass of the treatment liquid. By making the content 0.1% by mass or more, a crosslinked structure is sufficiently formed, so that wet rubbing fastness can be improved. By making the content 4.0% by mass or less, both wet rubbing fastness and texture can be achieved.

[0039] The crosslinking agent may be contained in the ink, the treatment liquid, or both the ink and the treatment liquid. When the crosslinking agent is contained in the treatment liquid, the crosslinking agent may be contained in the pre-treatment liquid, the post-treatment liquid, or both.

[0040] From the viewpoint of efficiently promoting a crosslinking reaction with the pigment dispersant and improving wet rub fastness, the crosslinking agent is preferably contained in the pretreatment liquid and / or the ink, and more preferably contained in the ink.

[0041] From the viewpoint of improving the storage stability of the ink, the crosslinking agent is preferably contained in the treatment liquid, and more preferably in the pre-treatment liquid.

[0042] In addition, when the ink contains a crosslinking agent, it is preferable for crosslinking between hydrophobic sites of the dispersion. The content of the crosslinking agent in the ink is preferably 5% by mass to 1000% by mass, and more preferably 10% by mass to 100% by mass, based on the total mass of the pigment dispersant. The content of the crosslinking agent in the ink is more preferably 25% by mass to 100% by mass, and most preferably 25% by mass to 50% by mass, based on the total mass of the pigment dispersant. By making it 5% by mass or more, the crosslinking agent can be sufficiently crosslinked with the pigment dispersant. In addition, by making it 1000% by mass or less, both wear resistance and texture can be achieved.

[0043] From the viewpoint of improving the storage stability of the ink, the content of the crosslinking agent relative to the total mass of the ink is preferably 3.0 mass% or less, more preferably 2.0 mass% or less, even more preferably 1.0 mass% or less, and most preferably 0.1 mass% or less.

[0044] Regarding the relative relationship between the content of the crosslinking agent in each of the treatment liquid and the ink, it is preferable that the content of the crosslinking agent in the total mass of the treatment liquid is higher than the content of the crosslinking agent in the total mass of the ink, which can improve the storage stability of the ink while improving the wet rub fastness and washing fastness.

[0045] 1-2.Inkjet ink The ink according to this embodiment contains a pigment, a pigment dispersant, and a solvent.

[0046] 1-2-1. Pigments The pigment contained in the ink is not particularly limited, but is preferably an organic pigment or an inorganic pigment having the following numbers as described in the Color Index.

[0047] Examples of orange pigments include Pigment Orange 31 and 43.

[0048] Examples of red or magenta pigments include Pigment Red 3, 5, 19, 22, 31, 38, 43, 48:1, 48:2, 48:3, 48:4, 48:5, 49:1, 53:1, 57:1, 57:2, 58:4, 63:1, 81, 81:1, 81:2, 81:3, 81:4, 88, 104, 108, 112, 122, 123, 144, 146, 149, 166, 168, 169, 170, 177, 178, 179, 184, 185, 208, 216, 226, 257, Pigment Violet 3, 19, 23, 29, 30, 37, 50, 88, Pigment Orange 13, 16, 20, 36.

[0049] Examples of blue or cyan pigments include Pigment Blue 1, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17-1, 22, 27, 28, 29, 36, 60.

[0050] Examples of green or yellow pigments include Pigment Green 7, 26, 36, and 50. Examples of yellow pigments include Pigment Yellow 1, 3, 12, 13, 14, 15, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, 128, 137, 138, 139, 151, 153, 154, 155, 157, 166, 167, 168, 180, 185, 193, and 213.

[0051] Examples of black pigments include Pigment Black 7, 28, and 26.

[0052] Commercially available examples of pigments include: Chromofine Yellow 2080, 5900, 5930, AF-1300, 2700L, Chromofine Orange 3700L, 6730, Chromofine Scarlet 6750, Chromofine Magenta 6880, 6886, 6891N, 6790, 6887, Chromofine Violet RE, Chromofine Red 6820, 6830, Chromofine Blue HS-3, 5187, 5108, 5197, 5085N, SR-5020, 5026, 5050, 4920, 4927, 4937, 4824, 4933GN-EP, 4940, 4973, 5205, 5208, 5214, 5221, 5000P , Chrome Fine Green 2GN, 2GO, 2G-550D, 5310, 5370, 6830, Chrome Fine Black A-1103, Seika Fast Yellow 10GH, A-3, 2035, 2054, 2200, 2270, 2300, 2400(B), 2500, 2600, ZAY-260, 2700(B), 2770 , Seika Fast Red 8040, C405(F), CA120, LR-116, 1531B, 8060R, 1547, ZAW-262, 1537B, GY, 4R-4016, 3820, 3891, ZA-215, Seika Fast Carmine 6B1476T-7, 1483LT, 3840, 3870, Seika Fast Bordeaux 10B-430, Seika Light Rose R40, Seika Light Violet B800, 7805, Seika Fast Maroon 460N, Seika Fast Orange 900, 2900, Seika Light Blue C718, A612, Cyanine Blue 4933M, 4933GN-EP, 4940, 4973 (Dainichi Seika Chemicals); KET Yellow 401, 402, 403, 404, 405, 406, 416, 424, KET Orange 501, KET Red 301, 302, 303, 304, 305, 306, 307, 308, 309, 310, 336, 337, 338, 346, KET Blue 101, 102, 103, 104, 105, 106, 111, 118, 124, KET Green 201 (manufactured by Dainippon Ink & Chemicals);Colortex Yellow 301, 314, 315, 316, P-624, 314, U10GN, U3GN, UNN, UA-414, U263, Finecol Yellow T-13, T-05, Pigment Yellow1705, Colortex Orange 202, Colortex Red101, 103, 115, 116, D3B, P-625, 102, H-1024, 105C, UFN, UCN, UBN, U3BN, URN, UGN, UG276, U456, U457, 105C, USN, Colortex Maroon601, Colortex BrownB610N, Colortex Violet600, Pigment Red 122, Colortex Blue516, 517, 518, 519, A818, P-908, 510, Colortex Green 402, 403, Colortex Black 702, U905 (Sanyo Pigment); Lionol Yellow 1405G, Lionol Blue FG7330, FG7350, FG7400G, FG7405G, ES, ESP-S (Toyo Ink Co., Ltd.); Toner Magenta E02, Permanent Rubin F6B, Toner Yellow HG, Permanent Yellow GG-02, Hostapearm Blue B2G (Hoechst Industry); Novoperm P-HG, Hostaperm Pink E, Hostaperm Blue B2G (manufactured by Clariant); carbon black #2600, #2400, #2350, #2200, #1000, #990, #980, #970, #960, #950, #850, MCF88, #750, #650, MA600, MA7, MA8, MA11, MA100, MA100R, MA77, #52, #50, #47, #45, #45L, #40, #33, #32, #30, #25, #20, #10, #5, #44, CF9 (manufactured by Mitsubishi Chemical); REGAL (registered trademark) 250R, 330, 330R, 350R, 400, 400R, 660, 660R (manufactured by Cabot Corporation).

[0053] From the viewpoint of improving dispersibility in the ink, the pigment is preferably further dispersed with a pigment dispersant, which will be described later.

[0054] The pigment may also be a self-dispersing pigment. A self-dispersing pigment is a pigment particle whose surface is modified with a group having a hydrophilic group, and has a pigment particle and a group having hydrophilicity bonded to its surface. Examples of the hydrophilic group include a carboxy group, a sulfonic acid group, and a phosphorus-containing group. Examples of the phosphorus-containing group include a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a phosphite group, and a phosphate group.

[0055] Examples of commercially available self-dispersing pigments include Cabot Corporation's Cab-0-Jet (registered trademark) 200K, 250C, 260M, and 270V (sulfonic acid group-containing self-dispersing pigments), Cab-0-Jet (registered trademark) 300K (carboxylic acid group-containing self-dispersing pigments), and Cab-0-Jet (registered trademark) 400K, 450C, 465M, 470V, and 480V (phosphate group-containing self-dispersing pigments).

[0056] The pigment content is not particularly limited, but from the viewpoint of easily adjusting the viscosity of the ink to the range described below and forming a higher density image, it is preferably 0.3 to 12 mass % of the ink, and more preferably 0.5 to 8 mass %. If the pigment content is 0.3 mass % or more, the color of the obtained image tends to be vivid, and if it is 12 mass % or less, the viscosity of the ink does not become too high, so that the ejection stability is not easily impaired.

[0057] 1-2-2. Pigment dispersants The pigment dispersant is a block copolymer comprising a hydrophilic block A and a hydrophobic block B.

[0058] The hydrophilic block A enhances the affinity with the aqueous solvent contained in the ink and contains a portion that interacts or reacts with the coagulant attached to the fabric (hereinafter referred to as the "hydrophilic portion"), and is the block that has the greater affinity with water among the blocks constituting the copolymer.

[0059] The hydrophobic block B is a portion that adsorbs to the pigment (hereinafter referred to as the "hydrophobic portion"), and among the blocks that make up the copolymer, it is the block that has the smaller affinity for the aqueous solvent contained in the ink.

[0060] Conventionally, the pigment dispersant used was a random copolymer containing hydrophilic and hydrophobic portions randomly. Since the random copolymer contains hydrophobic portions randomly, it cannot be continuously bonded to the pigment, and the copolymer is easily peeled off from the pigment due to the shear force caused by the circulation of the ink. Therefore, even if the pigment dispersant is crosslinked with a crosslinking agent, it is difficult to improve the fastness of the image formed. However, by using a block copolymer as the pigment dispersant, the pigment dispersant is less likely to peel off from the pigment, and the crosslinking between the pigment dispersant and the crosslinking agent can further improve the wet friction fastness and washing fastness of the image formed.

[0061] Furthermore, the block copolymer can prevent crosslinking and aggregation between pigment dispersions in the ink while maintaining dispersibility in an aqueous solvent, resulting in good storage stability, ejection stability, and image quality. Also, since the pigment dispersant can be prevented from aggregating in the ink, the pigment dispersant is uniformly applied to the fabric surface even after the ink is applied. Therefore, localized reactions due to crosslinking reactions with the crosslinking agent are unlikely to occur, and localized deterioration of texture does not occur, making it easier to maintain the texture of the fabric.

[0062] The number of hydrophilic block A and hydrophobic block B contained in one molecule of the block copolymer may be one or more. That is, when the hydrophilic block is A and the hydrophobic block is B, examples of the structure of the block copolymer include ABA type, ABABA type, etc. Among them, ABA type block copolymers containing two hydrophilic blocks A arranged at both ends of the molecule and a hydrophobic block B arranged between them, which has a lower affinity for aqueous solvents than the hydrophilic block A, are more preferable. Since the ABA type block copolymer has hydrophilic sites at two positions at both ends of the molecule, it has many binding points that interact or react with the crosslinking agent and / or the coagulant attached to the fabric, and it is easy to improve the washing fastness and friction fastness. In addition, since the above-mentioned ABA type block copolymer can be intermittently bonded with multiple blocks, the fabric is less likely to become hard and the texture of the fabric is easily maintained compared to AB type block copolymers that are continuously bonded with one block.

[0063] The types and compositional ratios of monomers in the multiple blocks A contained in the block copolymer may be the same as or different from each other. In addition, when the block copolymer contains multiple blocks A, the types and compositional ratios of monomers in the multiple blocks A may be the same as or different from each other.

[0064] The hydrophilic block A and the hydrophobic block B will be described below.

[0065] The hydrophilic block A contains a structural unit derived from a monomer having a hydrophilic group (hereinafter referred to as "hydrophilic monomer"). Examples of the hydrophilic functional group include a hydroxyl group, a carboxyl group, an amino group, a ketone group, and a sulfonic acid group, as well as an oxyalkylene moiety of an alkylene oxide modified product. In order to undergo a crosslinking reaction with the crosslinking agent, the hydrophilic block A contains at least one functional group (such as a hydroxyl group, a carboxyl group, an amino group, and a sulfonic acid group) having a hydrogen atom bonded to a nitrogen atom or an oxygen atom.

[0066] Examples of the hydrophilic monomer constituting the hydrophilic block A include a monomer containing a carboxy group or an acid anhydride group, a monomer containing a sulfonic acid group, and an ethylene oxide-modified (meth)acrylic acid ester monomer. Examples of the monomer containing a carboxy group or an acid anhydride group include unsaturated polycarboxylic acids such as (meth)acrylic acid and maleic acid, and monomers containing a carboxy group or an acid anhydride such as maleic anhydride. Examples of the monomer containing a sulfonic acid group include styrene sulfonic acid and 4-(methacryloyloxy)butylsulfonic acid. Examples of the ethylene oxide-modified (meth)acrylic acid ester monomer include ethylene oxide-modified (meth)acrylic acid alkyl ester. Of these, the hydrophilic monomer is preferably (meth)acrylic acid from the viewpoint of imparting appropriate water solubility to the hydrophilic block A.

[0067] The content of the hydrophilic monomer-derived constitutional units in the hydrophilic block A is higher than the content of the hydrophilic monomer-derived constitutional units in the hydrophobic block B. Specifically, the content of the hydrophilic monomer-derived constitutional units in the hydrophilic block A is preferably 10% by mass or more with respect to the total mass of the hydrophilic block A. When the content of the hydrophilic monomer in the hydrophilic block A is 10% by mass or more, dispersibility in an aqueous solvent is likely to be further improved. From the same viewpoint, the content is more preferably 15% by mass to 80% by mass.

[0068] The content of constitutional units derived from hydrophilic monomers in the hydrophobic block B is lower than the content of constitutional units derived from hydrophilic monomers in the hydrophilic block A. For example, when a block copolymer contains two hydrophilic blocks A and one hydrophobic block B, the content of constitutional units derived from hydrophilic monomers in the hydrophobic block B is lower than that in either of the two hydrophilic blocks A. Specifically, the content of constitutional units derived from hydrophilic monomers in the hydrophobic block B is less than 10% by mass, and preferably 5% by mass or less, relative to the hydrophobic block B.

[0069] The hydrophilic block A may further contain a structural unit derived from a monomer other than the hydrophilic monomer. Examples of the other monomer include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate and tert-butyl (meth)acrylate, and monomers containing an aromatic ring group or an alicyclic hydrocarbon group, which will be described later.

[0070] The content of the hydrophobic block B in the ABA block copolymer is preferably 10% by mass to 80% by mass, and more preferably 20% by mass to 80% by mass, based on the total mass of the block copolymer. When the content is 10% by mass or more, the content of the hydrophilic block A is low (or the molecular weight is small), so that crosslinking aggregation is more easily suppressed. When the content is 80% by mass or less, the content of the hydrophilic block A is high (or the molecular weight is large), so that the affinity to aqueous solvents is more easily increased.

[0071] The content of the hydrophilic block A is preferably 150% by mass or less relative to the content of the hydrophobic block B. This allows the length of each hydrophilic block A to be appropriately shortened, making it more difficult for crosslinking aggregation to occur.

[0072] The hydrophobic block B preferably contains a structural unit derived from a monomer having a hydrophobic functional group (hereinafter referred to as "hydrophobic monomer"). Examples of the monomer having a hydrophobic functional group include a monomer containing an aromatic ring group or an alicyclic hydrocarbon group.

[0073] Examples of monomers having an aromatic ring group include (meth)acrylates having an aromatic ring group, such as benzyl (meth)acrylate, phenyl (meth)acrylate, and phenoxyethyl (meth)acrylate; and aromatic monomers, such as styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene, and 1-vinylnaphthalene, with monomers having an aromatic ring group having 6 to 15 carbon atoms being preferred.

[0074] Examples of monomers having an alicyclic alkyl group include (meth)acrylates having an alicyclic alkyl group such as cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, cyclododecyl (meth)acrylate, bornyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate, and monomers having an alicyclic alkyl group having 6 to 15 carbon atoms are preferred.

[0075] Of these, from the viewpoint of improving the adsorption to the pigment, the hydrophobic monomer is preferably a monomer having an aromatic ring group having 6 to 15 carbon atoms, such as benzyl (meth)acrylate.

[0076] The content of the structural unit derived from the hydrophobic monomer in the hydrophobic block B is preferably 10% by mass or more relative to the hydrophobic block B. When the content is 10% by mass or more, the adsorption to the pigment is likely to be improved. From the same viewpoint, the content is more preferably 15% by mass to 100% by mass.

[0077] The hydrophobic block B may further contain a structural unit derived from a monomer other than the hydrophobic monomer. Examples of the other monomer include the above-mentioned (meth)acrylic acid alkyl esters and the above-mentioned hydrophilic monomers.

[0078] From the viewpoint of further improving the dispersibility of the pigment, the molecular weight distribution (PDI) (weight average molecular weight (Mw) of the block copolymer) / (number average molecular weight (Mn) of the block copolymer) is preferably 2.0 or less. The weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined by gel permeation chromatography (GPC).

[0079] The weight average molecular weight of the block copolymer is preferably 7000 to 21000, more preferably 10000 to 20000. When the weight average molecular weight is 7000 or more, the dispersibility of the pigment in the aqueous solvent is more easily improved. When the molecular weight is 21000 or less, the bond points that interact or react with the crosslinking agent and / or the flocculant attached to the fabric are not too long. Therefore, the pigment dispersant can be intermittently bonded to the crosslinking agent and / or the flocculant, and the fabric is less likely to become hard, and the texture is easily improved. The weight average molecular weight of the block copolymer can be measured by the same method as described above.

[0080] The acid value of the block copolymer is, for example, preferably 40 mgKOH / g to 400 mgKOH / g, more preferably 40 mgKOH / g to 300 mgKOH / g, and even more preferably 40 mgKOH / g to 190 mgKOH / g. When the acid value is 40 mgKOH / g or more, the hydrophilicity of the pigment dispersant is increased, and the dispersibility of the pigment can be further increased. When the acid value is 400 mgKOH / g or less, the hydrophilicity of the pigment dispersant is further prevented from being excessively increased, and the water resistance of the resulting image-formed product can be further increased. The acid value can be measured according to the measurement method of JIS K0070:1992.

[0081] The content of the block copolymer is preferably 5% by mass to 90% by mass, and more preferably 15% by mass to 80% by mass, relative to the pigment. When the content is 5% by mass or more, the dispersibility of the pigment in the aqueous solvent can be further improved. When the content is 90% by mass or less, an excessive increase in the viscosity of the aqueous ink caused by an excessive content of the block copolymer can be further suppressed.

[0082] The method for synthesizing the block copolymer is not particularly limited, but for example, the block copolymer can be obtained by sequentially polymerizing monomers constituting the blocks by a living radical polymerization method.

[0083] 1-2-3.Solvent The solvent preferably contains water and further contains a water-soluble organic solvent. A solvent containing water is also called an "aqueous solvent", and an ink containing an aqueous solvent is also called an "aqueous ink" or "water-based ink".

[0084] The content of water in the ink is 20 to 70% by mass, and preferably 30 to 60% by mass.

[0085] The water-soluble organic solvent is not particularly limited as long as it is compatible with water, but from the viewpoint of making it easier for the ink to penetrate into the interior of the fabric and making it difficult for the ejection stability in the inkjet method to be impaired, it is preferable that the ink does not easily thicken due to drying. Therefore, it is preferable that the ink contains a high-boiling point solvent having a boiling point of 200° C. or more.

[0086] The high-boiling solvent having a boiling point of 200° C. or higher may be any water-soluble organic solvent having a boiling point of 200° C. or higher, and is preferably a polyol or a polyalkylene oxide.

[0087] Examples of polyols having a boiling point of 200° C. or higher include dihydric alcohols and trihydric or higher alcohols. Examples of dihydric alcohols include 1,3-butanediol (boiling point 208° C.), 1,6-hexanediol (boiling point 223° C.), polypropylene glycol, etc. Examples of trihydric or higher alcohols include glycerin (boiling point 290° C.) and trimethylolpropane (boiling point 295° C.).

[0088] Examples of polyalkylene oxides having a boiling point of 200° C. or higher include ethers of dihydric alcohols such as diethylene glycol monoethyl ether (boiling point 202° C.), triethylene glycol monomethyl ether (boiling point 245° C.), tetraethylene glycol monomethyl ether (boiling point 305° C.), tripropylene glycol monoethyl ether (boiling point 256° C.) and polypropylene glycol, and ethers of trihydric or higher alcohols such as glycerin (boiling point 290° C.) and hexanetriol.

[0089] The solvent may further include other solvents in addition to the high boiling point solvent. Examples of the other solvents include polyhydric alcohols having a boiling point of less than 200° C. (e.g., ethylene glycol, propylene glycol, hexanetriol, etc.); polyhydric alcohol ethers having a boiling point of less than 200° C. (e.g., ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether); monohydric alcohols (e.g., methanol, ethanol, propanol, pentanol, hexanol, cyclohexanol, butyl ether ... alcohol); amines (e.g., ethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, triethylenetetramine); amides (e.g., formamide, N,N-dimethylformamide, N,N-dimethylacetamide); heterocycles (e.g., 2-pyrrolidone, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidine), sulfoxides (e.g., dimethyl sulfoxide); and sulfones (e.g., sulfolane).

[0090] The content of the water-soluble organic solvent is 20 to 70% by mass, preferably 30 to 60% by mass, relative to the ink. By making it 20% by mass or more, thickening due to drying can be suppressed. By making it 70% by mass or less, the time required for drying the solvent after applying the ink to a fabric or the like is not too long.

[0091] 1-2-4.Other ingredients The ink may further contain other components as necessary, such as a neutralizing agent, a softener, a lubricant, a surfactant, a preservative, a pH adjuster, and a water-dispersible resin as a binder component.

[0092] (Water dispersible resin) The water-dispersible resin can have a function of fixing the pigment, etc. to the fabric. The water-dispersible resin can be contained in the ink as resin particles.

[0093] Examples of the water-dispersible resin include urethane resin, butadiene resin, (meth)acrylic resin, and polystyrene. Examples of the butadiene resin include styrene-butadiene copolymer and acrylonitrile-butadiene copolymer. Examples of the (meth)acrylic resin include (meth)acrylic acid ester copolymer, styrene-(meth)acrylic copolymer, silicone-(meth)acrylic copolymer, and acrylic modified fluororesin. Among them, urethane resin, (meth)acrylic acid ester copolymer as the (meth)acrylic resin, and styrene-(meth)acrylic copolymer are preferable. It is presumed that these are bound to the block copolymer by intermolecular hydrogen bonds, and thus the adhesion of the pigment to the fabric is more easily improved, and the friction fastness is more easily improved.

[0094] Examples of styrene-(meth)acrylic copolymers include styrene-(meth)acrylic acid copolymers and styrene-(meth)acrylic acid-(meth)acrylic acid ester copolymers. Examples of (meth)acrylic acid esters include benzyl (meth)acrylate, cyclohexyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylhexyl carbitol (meth)acrylate, phenol EO modified (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate.

[0095] The urethane resin is a polymer obtained by reacting a polyol with a polyisocyanate. Examples of the polyol include polypropylene glycol, polyethylene glycol, polytetramethylene glycol, poly(ethylene adipate), poly(diethylene adipate), poly(propylene adipate), poly(tetramethylene adipate), poly(hexamethylene adipate), poly-ε-caprolactone, poly(hexamethylene carbonate), and silicone polyol. Examples of the isocyanate include tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated 4,4-diphenylmethane diisocyanate, isophorone diisocyanate, and tetramethylxylylene diisocyanate.

[0096] The Tg of the water-dispersible resin is not particularly limited, but is preferably low from the viewpoint of preventing the fabric from becoming hard even after image formation and making it easier to maintain the texture. The Tg of the water-dispersible resin may be, for example, −30 to 100° C., and preferably −10 to 50° C.

[0097] The acid value of the water-dispersible resin is not particularly limited, but from the viewpoint of improving the dispersion stability, it is preferably 44 mgKOH / g or more, more preferably 60 mgKOH / g or more. The upper limit of the acid value can be, for example, 110 mgKOH / g. The acid value can be measured by the same method as above.

[0098] The average particle size of the water-dispersible resin is not particularly limited, but from the viewpoint of preventing nozzle clogging of the inkjet head, it is preferably 300 nm or less, and more preferably 130 nm or less. The average particle size of the water-dispersible resin can be measured by a laser diffraction / scattering type particle size distribution measurement.

[0099] The content of the water-dispersible resin is preferably 0 to 15% by mass, more preferably 0 to 7% by mass, more preferably 0 to 3% by mass, and most preferably 0 to 2% by mass, based on the ink. By setting the content of the water-dispersible resin to 7% by mass or less based on the ink, clogging of the filter in the circulation type inkjet ink head is prevented, and ejection stability is improved. In addition, the ink droplets are more likely to wet and spread, improving image quality.

[0100] (Additives) Examples of the additives include neutralizing agents, softening agents, lubricants, surfactants, preservatives, antifungal agents, pH adjusters, and the like.

[0101] In this embodiment, when the block copolymer has an anionic group such as a carboxy group or a sulfonic acid group, the ink may further contain a neutralizing agent. The neutralizing agent may be a known basic compound, such as sodium hydroxide, potassium hydroxide, ammonia, or triethylamine. When the pigment dispersion contains a neutralizing agent, the anionic group is appropriately promoted to dissociate in the pigment dispersion, and dispersibility can be further improved.

[0102] The content of the neutralizing agent is not particularly limited, but it is preferable that the neutralization rate is 30% or more and 100% or less. The neutralization rate can be calculated by the following formula (1).

[0103] Neutralization rate (%) = (mass of basic compound [g] / (equivalent of basic compound [g / mol] × valence of basic compound)) ÷ ((acid value of pigment dispersant [mgKOH / g] × mass of pigment dispersant [g]) / (56 [g / mol] × 1000)) (1)

[0104] As the softening agent, known softening agents can be used. Examples of the lubricant include silicone emulsion, diethylene glycol, wax, etc.

[0105] The wax can be selected from natural waxes such as animal waxes, vegetable waxes, petroleum waxes, and mineral waxes, or synthetic waxes, etc. Examples of commercially available waxes include AQUACER manufactured by Big Chemie Japan Co., Ltd., JONCRYL WAX26J manufactured by BASF Japan Co., Ltd., and the like.

[0106] The surfactant can reduce the surface tension of the ink and increase the wettability of the ink to the fabric. The type of surfactant is not particularly limited, and can be, for example, an acetylene glycol surfactant, a silicone surfactant, a fluorine surfactant, etc. Examples of commercially available acetylene glycol surfactants include the Olfin series manufactured by Nissin Chemical Industry Co., Ltd.

[0107] Examples of preservatives or antifungal agents include aromatic halogen compounds (eg, Preventol CMK), methylene dithiocyanate, halogen-containing nitrogen-sulfur compounds, 1,2-benzisothiazolin-3-one (eg, PROXEL GXL), and the like.

[0108] Examples of pH adjusters include citric acid, sodium citrate, hydrochloric acid, sodium hydroxide, and the like.

[0109] 1-2-5. Ink properties The viscosity of the ink of the present invention at 25°C is not particularly limited as long as it provides good ejection properties by the inkjet method, but is preferably within the range of 3 to 20 mPa s, and more preferably within the range of 4 to 12 mPa s. The viscosity of the ink can be measured at 25°C using an E-type viscometer.

[0110] 1-3. Processing solution From the viewpoint of improving image quality, the treatment liquid preferably contains a flocculant.

[0111] 1-3-1. Flocculant The type of aggregating agent may be any agent that can aggregate the pigments contained in the ink, etc. Aggregation may be achieved by utilizing a change in pH or by utilizing an electrical effect.

[0112] Examples of flocculants that cause flocculation by changing the pH include organic acids, such as carboxylic acids having 6 or less carbon atoms, saturated fatty acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, and hexanoic acid, and hydroxy acids such as lactic acid, malic acid, and citric acid.

[0113] Examples of the flocculant that causes flocculation by electrical action include compounds having ionic groups and polyvalent metal salts.

[0114] When an aggregating agent is added to the pretreatment liquid, it is preferably a compound having an ionic group that forms a pair with the pigment dispersant contained in the ink. In other words, when the pigment dispersant is an anionic compound, it is preferable to use a compound having a cationic group as the aggregating agent added to the pretreatment liquid, because this allows the pigment dispersant and the aggregating agent to interact or react with each other.

[0115] In addition, an embodiment using two or more kinds of aggregating agents is also preferably used. In this case, two treatment liquids are used, and a compound having an ionic group that forms a pair with the ionic group imparted to the first treatment liquid is added to the second treatment liquid, so that the aggregating agent imparted to the first treatment liquid and the aggregating agent imparted to the second treatment liquid interact or react with each other after image formation. Therefore, the electrostatic repulsion between the aggregating agents imparted to the first treatment liquid is suppressed, the aggregating property of the pigment or the like is enhanced, and the water resistance of the image formed product is improved. Specifically, it is preferable that the aggregating agent imparted to the first treatment liquid has an anionic group and the aggregating agent imparted to the second treatment liquid has a cationic property; or that the aggregating agent imparted to the first treatment liquid has a cationic group and the aggregating agent imparted to the second treatment liquid has an anionic group. Among them, when the pigment dispersant contained in the ink is an anionic compound, it is preferable that the first treatment liquid is used as a pretreatment liquid to impart a compound having a cationic group, and the second treatment liquid is used as a posttreatment liquid to impart a compound having an anionic group.

[0116] The coagulant may be contained in either the pre-treatment liquid or the post-treatment liquid, but it is preferable from the viewpoint of improving image quality that the coagulant is contained in the pre-treatment liquid.

[0117] Examples of the cationic group in the compound having a cationic group include a secondary amino group, a tertiary amino group, a quaternary ammonium base, etc. Examples of the compound having a cationic group include a cationic resin and a cationic surfactant, and preferably a cationic resin.

[0118] Examples of cationic resins include cationic urethane resins, cationic olefin resins, and cationic alkylamine resins. Examples of commercially available products include MPT-60 manufactured by Mitsubishi Pencil Co., Ltd., Unisense KHE100L manufactured by Senka Co., Ltd., and urethane resin MZ477 manufactured by Takamatsu Oil Co., Ltd. Among them, cationic alkylamine resins MPT-60 and Unisense KHE100L are preferred from the viewpoint of more easily generating interaction or reaction with the block copolymer.

[0119] Examples of anionic resins include (meth)acrylic resins, urethane resins, polyolefin resins, polyester resins, polyvinyl chloride resins, epoxy resins, polysiloxane resins, fluororesins, styrene copolymers, and vinyl acetate copolymers. The resins can be appropriately selected from the following. Examples of polyvinyl chloride resins include polyvinyl chloride polymers, vinyl chloride-vinylidene chloride copolymers, and the like. Examples of styrene copolymers include styrene-butadiene copolymers, styrene-(meth)acrylic acid ester copolymers, and the like. Examples of vinyl acetate copolymers include ethylene-vinyl acetate copolymers, and the like. From the viewpoint of further increasing the water resistance of the formed image, the anionic resin is preferably selected from (meth)acrylic resins, urethane resins, polyolefin resins, polyvinyl chloride resins, epoxy resins, polysiloxane resins, fluororesins, styrene copolymers, and vinyl acetate copolymers, and is preferably selected from urethane resins and (meth)acrylic resins. Examples of commercially available products include EMN-325E manufactured by Nippon Shokubai Co., Ltd., HA-207 manufactured by Nicca Kagaku Co., Ltd., A-1127 manufactured by Kusumoto Chemical Industries Co., Ltd., and the Aniset series manufactured by Osaka Organic Chemical Industry Co., Ltd.

[0120] Polyvalent metal salts can be water-soluble compounds having a divalent or higher polyvalent metal ion and an anion associated therewith. Examples of polyvalent metal ions include Ca 2+ , Cu 2+ , Ni 2+ , Mg 2+ , Zn 2+ , B.A. 2+ Divalent metal ions such as Al 3+ , Fe 3+ , Cr 3+ Examples of anions include trivalent metal ions such as Cl. - , I - , Br - , SO4 2- , ClO3 - , NO3 - , and H.C.O.O. - , CH3COO - Examples of such polyvalent metal salts include zinc acetate dihydrate, magnesium nitrate, calcium chloride, magnesium chloride, aluminum chloride, magnesium sulfate, and metal salts of organic acids such as calcium salts, magnesium salts, nickel salts, and aluminum salts, such as acetic acid. Among these, calcium salts and magnesium salts are preferred, and calcium nitrate and calcium chloride are preferred.

[0121] Among these, compounds having a cationic group or organic acids are preferred, and compounds having a cationic group are more preferred.

[0122] The content of the flocculant in the treatment liquid is not particularly limited, but is preferably 0.1 to 15% by mass, and more preferably 0.5 to 10% by mass, based on the pretreatment liquid.

[0123] 1-3-2.Other ingredients The treatment liquid may further contain additives such as a solvent, a surfactant, a pH adjuster, a preservative, etc. The solvent, surfactant, pH adjuster, and preservative may be the same as those used in the ink.

[0124] 2. Image forming method The image-formed product according to one embodiment of the present invention can be manufactured through a step of applying the treatment liquid and a step of applying the ink by an inkjet method. The step of applying the treatment liquid may be performed before or after the step of applying the ink.

[0125] 2-1. Ink application process In this step, the ink is applied onto the fabric by an inkjet method. The fabric may be a fabric that has been subjected to a step of applying a treatment liquid.

[0126] The type of fiber contained in the fabric is not particularly limited, and examples thereof include natural fibers such as cotton (cellulose fiber), hemp, wool, and silk; chemical fibers such as rayon, vinylon, nylon, acrylic, polyurethane, polyester, and acetate, and blended fibers thereof. Of these, cotton fabric is preferred. The fabric may be any form of woven fabric, nonwoven fabric, knitted fabric, etc., made from these fibers. The fabric may also be a blended woven fabric or blended nonwoven fabric of two or more types of fibers.

[0127] In this embodiment, the ink contains a block copolymer as a pigment dispersant. The block copolymer is less likely to cause cross-linking aggregation with other pigment dispersants than a random copolymer. This makes it easier to suppress aggregation of the pigment dispersion, and high ejection stability can be obtained.

[0128] 2-2. Step of applying processing liquid In this step, the treatment liquid is applied onto the fabric. The fabric may be a fabric that has been subjected to a step of applying an ink.

[0129] The method for applying the treatment liquid is not particularly limited and may be, for example, a pad method, a coating method, a spray method, an inkjet method, etc. Among these, the inkjet method is preferred from the viewpoint of increasing production efficiency.

[0130] The fabric that has been contacted with the treatment liquid may be heated and dried using hot air, a hot plate, or a heat roller.

[0131] The amount of treatment liquid to be applied is not particularly limited, and can be adjusted depending on the type of fabric, the amount of ink to be applied, and the like.

[0132] In particular, when the treatment liquid contains a crosslinking agent, the crosslinking agent content in the treatment liquid and the amount of pigment dispersant in the ink are determined based on the crosslinking agent content per unit area of ​​the fabric, X1g / m 2 and the amount of pigment dispersant applied to the fabric per unit area Y1g / m 2 The amount of the treatment liquid applied is preferably adjusted so that the ratio X1 / Y1 is in the range of 0.05 to 10.0, more preferably adjusted to be in the range of 0.10 to 5.0, even more preferably adjusted to be in the range of 0.10 to 1.0, and most preferably adjusted to be in the range of 0.10 to 0.50. By making X1 / Y1 0.05 or more, the crosslinking agent can sufficiently form a crosslinked structure with the pigment dispersing agent, and wet friction fastness can be improved. In addition, by making X1 / Y1 10.0 or less, the crosslinking agent does not react too much, and the texture can be maintained, and both the texture and the wet friction fastness can be achieved. By making X1 / Y1 1.0 or less, it is possible to more easily achieve both the texture and the wet friction fastness. By making X1 / Y1 0.50 or less, it is possible to more easily achieve both the texture and the wet friction fastness.

[0133] 3. Image formation The resulting image-formed product has a fabric and an image area. The image area includes a pigment and a pigment dispersant crosslinked by a crosslinking agent.

[0134] When an ABA type block copolymer is used as a pigment dispersant, the block copolymer can be bonded to the fabric at multiple bonding points, including two bonding points at both ends of the molecule. Therefore, compared with a conventional AB type block copolymer that is bonded to the fabric at only one end of the molecule, the pigment can be better adhered to the fabric. As a result, the image formed has high washing fastness and friction fastness. In addition, since the ABA type block copolymer is bonded to the fabric at multiple points, the fabric is less likely to become hard than a conventional AB type block copolymer that is bonded to the fabric at only one point.

[0135] The amount of crosslinking agent per unit area contained in the image area is X2g / m 2 and the amount of pigment dispersant per unit area contained in the image area is Y2g / m 2 The ratio X2 / Y2 is preferably in the range of 0.05 to 10.0. It is more preferable that X2 / Y2 is adjusted to be in the range of 0.10 to 5.0, more preferably in the range of 0.10 to 1.0, and most preferably in the range of 0.10 to 0.50. By making X2 / Y2 0.05 or more, the crosslinking agent can sufficiently form a crosslinked structure with the pigment dispersing agent. The crosslinking agent can sufficiently form a crosslinked structure with the pigment dispersing agent. By making X2 / Y2 10.0 or less, the crosslinking agent does not react too much, and the texture can be maintained, and both the texture and the wet friction fastness can be achieved. By making X2 / Y2 1.0 or less, it is possible to more easily achieve both the texture and the wet friction fastness. By making X2 / Y2 0.50 or less, it is even easier to achieve both.

[0136] The amounts of the crosslinking agent and the pigment dispersant contained in the image area were measured by the ATR method (Attenuated Total Reflection) using a Nicolet FT-IR Magna 860-NIC plan IR-Microscope. -1The amount of pigment dispersant applied can be confirmed by comparing the peak intensity of the image area with the peak intensity of the image area where the amount of pigment dispersant applied is known. In addition, the amount of crosslinking agent included in the image area can be confirmed by comparing the peak intensity of the image area with the peak intensity of the image area where the amount of pigment dispersant applied is known. -1 , and epoxy compounds, 850-950cm -1 , and carbodiimide compounds, 2100-2200cm -1 For oxazoline compounds, 1650-1750cm -1 For isocyanate compounds, it is 2200-2300 cm -1 For aziridine compounds, 1300-1400cm -1 The amount of crosslinking agent applied can be confirmed by comparing the peak intensity with the peak intensity of an image portion having a known amount of crosslinking agent applied. EXAMPLES

[0137] The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. In the following examples, unless otherwise specified, the operations were performed at room temperature (25°C). Furthermore, unless otherwise specified, "%" and "parts" mean "% by mass" and "parts by mass", respectively.

[0138] 1. Preparation of Pretreatment Solution 1-1. Preparation of pretreatment solution <Preparation of pretreatment solution 1-1> The following components were mixed to prepare pretreatment solution 1-1. ------------------------------------------------------------------ Composition of pretreatment solution 1-1 ------------------------------------------------------------------ MPT-60 (manufactured by Mitsubishi Pencil Co., Ltd., cationic resin): 6.8 parts by mass Triethylene glycol divinyl ether (Tokyo Chemical Industry Co., Ltd., vinyl ether crosslinking agent): 0.50 parts by mass Ethylene glycol (solvent): 20 parts by weight Propylene glycol (solvent): 10 parts by weight Olfin E1010 (manufactured by Nissin Chemical Industry Co., Ltd., surfactant): 0.1 parts by mass Proxel GXL(S) (Lonza, preservative): 0.5 parts by weight Ion-exchanged water: 62.1 parts by mass ------------------------------------------------------------------

[0139] <Preparation of pretreatment liquids 1-2 to 1-9> Pretreatment liquids 1-2 to 1-9 were prepared in the same manner, except that the type and content of the crosslinking agent was changed as shown in Table 1 and the amount of ion-exchanged water was adjusted so that the total amount was 100 parts by mass.

[0140] Table 1 shows the compositions of pretreatment liquids 1-1 to 1-9. [Table 1] (Crosslinking agent) Denacol EX-313: Epoxy crosslinking agent manufactured by Nagase ChemteX Corporation Carbodilite (registered trademark) V-02: Nisshinbo Chemical Co., Ltd., carbodiimide crosslinking agent WS-700: Nippon Shokubai Co., Ltd., oxazoline crosslinking agent Meikanate CX: Isocyanate crosslinking agent manufactured by Meisei Chemical Industry Co., Ltd. DZ-22E: Aziridine-based crosslinking agent manufactured by Nippon Shokubai Co., Ltd.

[0141] 2. Ink Preparation 2-1. Preparation of copolymer (pigment dispersant) <Preparation of Block Copolymer P-1 (ABA Type)> A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube was charged with tripropylene glycol monomethyl ether (207 parts by mass), benzyl methacrylate (hereinafter referred to as "BzMA") (17.6 parts by mass), 2-ethylhexyl methacrylate (hereinafter referred to as "2EHMA") (29.7 parts by mass), methacrylic acid (hereinafter referred to as "MAA") (1.0 part by mass), iodine (2.0 parts by mass), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (hereinafter referred to as "AMDV") (4.0 parts by mass), and diphenylmethane (hereinafter referred to as "DPM") (0.08 parts by mass), and polymerized at 40°C for 5 hours to obtain polymer chain B, which becomes a hydrophobic block.

[0142] To the reaction solution, cyclohexyl methacrylate (hereinafter referred to as "CHMA") (25.2 parts by mass), methyl methacrylate (hereinafter referred to as "MMA") (10.0 parts by mass), and MAA (8.6 parts by mass) were added. After that, polymerization was carried out for 3 hours to form polymer chain A1 which becomes a hydrophilic block, and an AB type block copolymer consisting of polymer chain A1 and polymer chain B was obtained.

[0143] To the above reaction solution, BzMA (4.3 parts by mass) and MAA (8.6 parts by mass) were added and polymerized for 2 hours to form polymer chain A2, which becomes a hydrophilic block, thereby obtaining an ABA type block copolymer consisting of polymer chain A1, polymer chain B, and polymer chain A2.

[0144] After cooling to room temperature, a homogenized aqueous solution of sodium hydroxide (8.0 parts by mass) and ion-exchanged water (199 parts by mass) was added to neutralize. The solid content was adjusted by adding ion-exchanged water to obtain an aqueous solution of an ABA type block copolymer with a solid content of 30%. The weight-average molecular weight of the obtained block copolymer was 12000, the PDI was 1.36, and the acid value was 113 mgKOH / g.

[0145] <Preparation of Block Copolymer P-2 (AB Type)> In a nitrogen-substituted glove box, a flask equipped with a stirrer was charged with BzMA (90 g, 511 mmol), ethyl-2-methyl-2-n-butyltellanyl-propionate (hereinafter referred to as "BTEE") (2.00 g, 6.67 mmol) as a polymerization initiator, dibutyl ditelluride (hereinafter referred to as "DBDT") (1.22 g, 3.33 mmol), 2,2'-azobis-isobutyronitrile (manufactured by Otsuka Chemical Co., Ltd., hereinafter referred to as "AIBN") (0.33 g, 2.00 mmol), and methoxypropanol (90 g), and the mixture was allowed to react at 60°C for 16 hours.

[0146] Butyl methacrylate (hereinafter referred to as "n-BMA") (45 g, 317 mmol), MAA (25 g, 290 mmol), AIBN (0.22 g, 1.33 mmol), and methoxypropanol (70 g) were added to the above reaction solution, and the mixture was reacted at 60° C. for 22 hours. In this way, polymer chain A was formed.

[0147] After the reaction was completed, the reaction solution was poured into 5 L of heptane, and the precipitate was filtered by suction and dried to obtain a white powdery block copolymer. Then, a homogenized aqueous solution of sodium hydroxide (8.0 parts by mass) and ion-exchanged water (199 parts by mass) was added to neutralize. The solid content was adjusted by adding ion-exchanged water to obtain an aqueous solution of an AB-type block copolymer with a solid content of 30%. The weight-average molecular weight of the obtained block copolymer was 11,000, the PDI was 1.49, and the acid value was 104 mgKOH / g.

[0148] <Preparation of random copolymer P-3> Ion-exchanged water (100 parts by mass) was placed in a reaction vessel equipped with a dropping device, a thermometer, a water-cooled reflux condenser and a stirrer, and ammonium persulfate (0.4 parts by mass) as a polymerization initiator was added at 70°C in a nitrogen atmosphere while stirring. A monomer solution containing styrene (70 parts by mass), methyl acrylate (19 parts by mass), MMA (31 parts by mass), and n-butyl acrylate (20 parts by mass) was dropped into the reaction vessel and reacted to polymerize and produce a polymer. Then, the mixture was filtered through a 0.3 μm filter, and ion-exchanged water was added to adjust the solid content, and resin particles in an emulsion state with a solid content of 30% were obtained. The weight-average molecular weight of the resulting random copolymer was 8800.

[0149] <Preparation of Block Copolymer P-4 (ABA Type)> An aqueous solution of block copolymer P-4 was obtained in the same manner as block copolymer P-1, except that AMDV was changed from 4.0 parts by mass to 1.6 parts by mass. The weight average molecular weight of the obtained block copolymer was 30000, the PDI was 1.69, and the acid value was 113 mgKOH / g.

[0150] 2-2. Preparation of pigment dispersion <Preparation of Pigment Dispersion A-1> REGAL330R (Cabot, black pigment) (18.0 parts by mass) was mixed with a 30% solid content aqueous solution (45.0 parts by mass) of block copolymer P-1 (pigment dispersant), propylene glycol (20 parts by mass), and ion-exchanged water (17.0 parts by mass).Then, the mixture was dispersed using a sand grinder filled with 50% by volume of zirconia beads having an average particle size of 0.5 mm to prepare pigment dispersion A-1 with a pigment content of 18.0% by mass.

[0151] <Preparation of Pigment Dispersions A-2, A-3, and A-4> Pigment dispersions A-2, A-3, and A-4 were prepared in the same manner except that the type of copolymer (pigment dispersant) was changed as shown in Table 2.

[0152] [Table 2]

[0153] 2-3. Preparation of ink <Preparation of Ink 2-1> The following ingredients were mixed to give Ink 2-1. ------------------------------------------------------------------ Composition of Ink 2-1 ------------------------------------------------------------------ Pigment dispersion A-1 (pigment concentration 18.0% by mass): 10 parts by mass Glycerin: 10 parts by weight Ethylene glycol: 25 parts by weight Proxel GXL(S) (Lonza, preservative): 0.1 parts by weight Sodium citrate hydrate (pH adjuster): 2.0 parts by mass Ion exchange water: remaining amount ------------------------------------------------------------------ The amount of ion-exchanged water was adjusted so that the total amount of ink was 100 parts by mass.

[0154] <Preparation of Inks 2-2 to 2-32> Inks 2-2 to 2-32 were prepared in the same manner as Ink 2-1, except that the type of pigment dispersion, the type and amount of crosslinking agent, and the binder components and amounts added were changed as shown in Table 3, and the amount of ion-exchanged water added was adjusted so that the total was 100 parts by mass.

[0155] [Table 3] (Binder) Superflex 300: Manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

[0156] 3. Preparation of post-treatment solution 3-1. Preparation of post-treatment solution <Preparation of post-processing solution 3-1> Post-treatment solution 3-1 was prepared by mixing the following components. The completed post-treatment liquid 3-1 had a viscosity of 4.8 mPa·s at 25°C. ------------------------------------------------------------------ Composition of post-processing solution 3-1 ------------------------------------------------------------------ HA-207 (manufactured by Nicca Chemical Co., Ltd., anionic urethane resin): 10 parts by mass Ethylene glycol (solvent): 20 parts by weight Glycerin (solvent): 10 parts by weight Olfin E1010 (manufactured by Nissin Chemical Industry Co., Ltd., surfactant): 0.10 parts by mass Proxel GXL(S) (Lonza, preservative): 0.05 parts by weight Ion-exchanged water: 59.85 parts by mass ------------------------------------------------------------------

[0157] 4. Image Formation and Evaluation 4-1.Image formation <Test 1: Preparation of an image-formed article including a fabric and an image area disposed on the fabric> The pre-treatment liquid 1-1, ink 2-3, and post-treatment liquid 3-1 prepared above were set in a simple printing tester equipped with a KM1024i head as an inkjet head.

[0158] Cotton broadcloth 40 (100% cotton) was prepared as the fabric. A pre-treatment liquid, ink, and post-treatment liquid were applied to the surface of this fabric using a simple printing tester in the following process order to form an image. The application of the pre-treatment liquid, ink, and post-treatment liquid was all performed wet-on-wet. In addition, all of these applications were performed using an inkjet method and a multi-pass method with a main scanning speed of 540 dpi and a sub-scanning speed of 720 dpi. "dpi" represents the number of ink droplets (dots) per 2.54 cm. The ejection frequency was 22.4 kHz. The image formed was an image (total size 200 mm x 200 mm) that included a fine line grid, gradation, and solid areas.

[0159] First, pretreatment liquid 1-1 was applied at a rate of 30 g / m 2 Next, the voltage was adjusted so that ink 2-3 was applied in an amount of 3.75 g / m 2 Next, post-treatment liquid 3-1 was applied in an amount of 3.75 g / m 2 The ink and post-treatment liquid application steps were repeated so that the applied ink and post-treatment liquid overlapped each other, and the ink and post-treatment liquid were each applied eight times.

[0160] Thereafter, the fabric was dried at 130° C. for 10 minutes to obtain an image-formed product including the fabric and the image portion disposed on the fabric.

[0161] <Test 1: Preparation of an image-formed product including coated paper and an image area arranged on the coated paper> A solid image was formed in the same manner as above using the same simple printing tester as above, except that the printing method was a printing width of 100 nm x 100 nm, a resolution of 720 dpi x 720 dpi, and the printing substrate was coated paper (OK Topcoat, Oji Paper Co., Ltd.).

[0162] Thereafter, the coated paper was dried at 75° C. for 10 minutes to obtain an image-formed product including the coated paper and the image portion disposed on the coated paper.

[0163] <Tests 2-51> Image formation was performed in the same manner as in Test 1, except that at least one of the type of pretreatment liquid and the type of ink was changed as shown in Tables 4 and 5, and an image-formed product including a fabric and an image area disposed on the fabric, and an image-formed product including a coated paper and an image area disposed on the coated paper were obtained.

[0164] 4-2.Evaluation The following evaluations were carried out for the obtained image-formed products. Among the following, image quality, texture, wet friction fastness, and washing fastness were evaluated for the image-formed products including the fabric and the image area arranged on the fabric. Meanwhile, fixability was evaluated for the image-formed products including the coated paper and the image area arranged on the coated paper.

[0165] (image quality) The solid quality of the entire solid image formed was visually observed and evaluated according to the following criteria: C or higher was considered to be acceptable. A: A good image with a uniform density and no visible ink voids. B: Although there are some areas with different shading, no ink loss is observed, and the image is acceptable for practical use. C: This image has some areas where the ink has fallen out and there are slight white areas. D: There are many areas in the image where ink has fallen out, and white spaces are noticeable.

[0166] (Fixation) A cross-cut tape peeling test was carried out on the solid image thus formed. The fixability of the image was evaluated according to the following criteria. A to D were judged to be good. A: The area of ​​the image peeled off by the tape is less than 1% of the area of ​​the solid image. B: The area of ​​the image peeled off by the tape is 1% or more and less than 3% of the area of ​​the solid image. C: The area of ​​the image peeled off by the tape is 3% or more and less than 5% of the area of ​​the solid image. D: The area of ​​the image peeled off by the tape is 5% or more and less than 10% of the area of ​​the solid image. E: The area of ​​the image peeled off by the tape is 10% or more of the area of ​​the solid image.

[0167] (Texture) The texture of the obtained image-formed product and the fabric was evaluated sensorily by touching with the fingers. The evaluation was made based on the following criteria. If it was △ or better, it was considered acceptable. ◯: The original softness of the fabric is maintained, and the texture of the fabric is unchanged or almost unchanged compared to before the image formation. Δ: The fabric is slightly harder than before the image formation, but the texture of the fabric is not impaired and there is no problem in practical use. ×: The fabric is harder than before the image formation, the texture of the fabric is impaired, and the level is problematic for practical use.

[0168] (Wet friction fastness) The wet friction fastness of the obtained image-formed product was evaluated using a crock meter (rubbing tester type I) in accordance with JIS L 0849. Specifically, an image of the surface of the image-formed product was captured by a scanner, and the image was processed to quantify the staining level of the white cloth, which was then evaluated according to the following criteria. An evaluation of 3 or higher was considered acceptable. 5: Compared to when no post-treatment is performed, contamination of white cloth is reduced by more than 90%. 4: Compared to when no post-treatment is used, contamination of white cloth is reduced by 60% or more but less than 90%. 3: Compared to when no post-treatment is used, contamination of white cloth is reduced by 30% or more but less than 60%. 2: Compared to when no post-treatment is used, contamination of white cloth is reduced by 10% or more but less than 30%. 1: Compared to no post-treatment, the staining of white fabric is improved by less than 10%.

[0169] (Washing fastness) The washing fastness of the image-formed product was evaluated by comparing the color fading of the image-formed product after one wash (washing with water) in a home washing machine with that of the image-formed product that had not been washed. The evaluation was based on the following evaluation criteria. If it was △ or higher, it was considered acceptable. ◎: No color fading after rinsing. ◯: There is slight or almost no discoloration after rinsing, and the level is completely acceptable for practical use. △: Color fades after rinsing, but is not a problem for practical use. ×: Discoloration after rinsing is significant, to a level that is problematic for practical use.

[0170] The evaluation results of the image formations in Tests 1 to 51 are shown in Tables 4 and 5.

[0171] [Table 4]

[0172] [Table 5]

[0173] Further, the storage stability and ejection stability of some of the inks prepared above were examined.

[0174] (Storage stability) Inks 2-1 to 2-3 and 2-5 to 2-26 were placed in polyethylene terephthalate containers, sealed, and stored in a thermostatic chamber at 50°C for 14 days. The viscosity and dispersed particle size after storage were measured, and storage stability was evaluated based on the rate of change in viscosity and dispersed particle size after storage compared to the viscosity and dispersed particle size before storage. The viscosity was measured using an R100 viscometer (manufactured by Toki Sangyo Co., Ltd.) at 25°C and a cone rotation speed of 20 to 100 rpm. The dispersed particle size was measured by measuring the dispersed particle size (Z average) of polymer particles in the polymer particle dispersion using a Zataizer NanoS90 manufactured by Melvern. The rate of change in spectral absorption was calculated using the following formula, and storage stability was evaluated based on the following evaluation criteria. Rate of change (%) = 100 x {absolute value of [(measured value after saving) - (measured value before saving)]} / (measured value before saving) A: The rate of change in both viscosity and dispersed particle size is less than 10%. B: The rate of change in either viscosity or dispersed particle size is 10% or more C: The rate of change in both viscosity and dispersed particle size is 10% or more

[0175] (Discharge stability) Among the inks prepared above, inks 2-1, 2-2, 2-27 to 2-32 were ejected using a line method with a droplet volume of 13 pL on a Konica Minolta KM1024iMHE. After confirming that the filled ink was ejected from all 60 nozzles at the start of ejection, the ink was ejected continuously for 60 minutes. After the 60 minutes of continuous ejection was completed, the number of nozzles that had been able to eject to the end (the number of ejecting nozzles after the 60 minutes of continuous ejection) was counted. The number of ejecting nozzles after the 60 minutes of continuous ejection was applied to the following evaluation criteria to evaluate the ejection properties of the ink. A: The number of nozzles ejecting after 60 minutes of continuous ejection is 60 or more. B: After 60 minutes of continuous discharge, the number of discharge nozzles is 57-59 C: After 60 minutes of continuous discharge, the number of discharge nozzles is 54 to 56 D: The number of nozzles discharged after 60 minutes of continuous discharge is 53 or less.

[0176] The evaluation results of the storage stability of the ink are shown in Table 6, and the evaluation results of the ejection stability of the ink are shown in Table 7.

[0177] [Table 6]

[0178] [Table 7]

[0179] Regarding the evaluation of image formation, as shown in Table 4, the image-formed products obtained in Tests 1 to 8, 24 to 31, 46, and 47 (comparison) were not able to achieve acceptable levels in image quality, texture, wet rub fastness, and washing fastness. In contrast, the image-formed products obtained in Tests 9 to 23, 32 to 45, and 48 to 51 (present invention) were able to achieve acceptable levels in image quality, texture, wet rub fastness, and washing fastness.

[0180] From the above results, it is believed that by using a block copolymer as a pigment dispersant, the pigment dispersant is less likely to peel off from the pigment, improving image quality, and further, crosslinking between the pigment dispersant and the crosslinking agent can further improve the wet rub fastness and washing fastness of the image-formed product.

[0181] Furthermore, comparing Test 3 and Test 11, it is believed that the use of a block copolymer made it possible to maintain dispersibility in aqueous solvents while making crosslinking and aggregation between pigment dispersions less likely to occur, which allowed the crosslinking reaction to proceed uniformly and made it easier to maintain the texture of the fabric.

[0182] Comparing Tests 9 to 14, it is evident that by using an epoxy compound (Test 10), an oxazoline compound (Test 12), and an isocyanate compound (Test 13) as crosslinking agents, they are able to form a crosslinked structure with the pigment dispersant as well as with the hydrophilic functional groups contained in the fabric, forming a highly dimensional crosslinked structure. This is believed to have improved wet friction fastness.

[0183] As can be seen from the results of Tests 1 to 8, when a random copolymer is used as a pigment dispersant, there is a problem that the wetting and spreading is insufficient when an ink set containing a crosslinking agent is used, resulting in a decrease in image quality. On the other hand, as can be seen from the results of Tests 9 to 20, it was found that when a block copolymer is used as a pigment dispersant, image quality is improved even with an ink set containing a crosslinking agent. The reason for this is thought to be as follows. Block copolymers have high pigment dispersibility in aqueous solvents, so the pigment can be applied uniformly to the fabric. This makes it possible to obtain high-quality images with high sharpness and little color unevenness.

[0184] Furthermore, comparing Tests 15 to 20, epoxy compounds and isocyanate compounds have high compatibility with water-soluble resins and resins such as coagulants, and are less likely to impede the wetting and spreading of the ink. Therefore, it is believed that unevenness in the pigment concentration can be suppressed, resulting in better image quality.

[0185] In addition, the results of storage stability show that inks 2-1 to 2-3, which do not contain a crosslinking agent, have high storage stability regardless of whether the pigment dispersant is a random copolymer or a block copolymer. Furthermore, even if a crosslinking agent is added to the ink, if a block copolymer is used as the pigment dispersant, thickening due to long-term storage can be prevented and storage stability including ejection stability can be improved. The reason is considered as follows. In a block copolymer, a hydrophilic block that increases affinity to water and a hydrophobic block that adsorbs to the pigment are localized. When a pigment is dispersed in an aqueous solvent, the crosslinking agent is hydrophobic and therefore likely to exist on the hydrophobic block side of the pigment dispersant (inside the pigment dispersion). Therefore, the crosslinking agent is unlikely to exist on the hydrophilic block side of the pigment dispersant (outside the pigment dispersion), and the hydrophilic block of the pigment dispersant and the crosslinking agent are unlikely to crosslink and aggregate. As a result, even if a crosslinking agent is added to the ink, thickening due to long-term storage is prevented and storage stability is improved. [Industrial Applicability]

[0186] According to the present invention, it is possible to provide an ink set for ink-jet textile printing that can form an image having good texture and high wet rub fastness and washing fastness.

Claims

1. An inkjet printing ink set comprising an inkjet ink and at least one treatment liquid, The ink-jet ink comprises a pigment, a pigment dispersant, and a solvent; The pigment dispersant is a block copolymer including a hydrophilic block A and a hydrophobic block B, At least one of the treatment liquid and the ink-jet ink contains a crosslinking agent, the crosslinking agent contains at least one compound selected from the group consisting of vinyl ether compounds, epoxy compounds, carbodiimide compounds, oxazoline compounds, isocyanate compounds, and aziridine compounds; Ink set for inkjet textile printing.

2. The pigment dispersant is It is an ABA type block copolymer containing two hydrophilic blocks A and one hydrophobic block B. The ink set for ink-jet textile printing according to claim 1 .

3. the crosslinking agent is contained in at least the treatment liquid, The content of the crosslinking agent in the treatment liquid is The content is 0.1% by mass or more based on the total mass of the treatment liquid. The ink set for ink-jet textile printing according to claim 1 .

4. The content of the crosslinking agent in the inkjet ink is 3.0% by mass or less relative to the total mass of the inkjet ink, The ink set for ink-jet textile printing according to claim 3.

5. On the surface of the fabric, The method includes a step of applying a treatment liquid and a step of applying an inkjet ink by an inkjet method, The ink-jet ink comprises a pigment, a pigment dispersant, and a solvent; The pigment dispersant is a block copolymer including a hydrophilic block A and a hydrophobic block B, At least one of the treatment liquid and the ink-jet ink contains a crosslinking agent, the crosslinking agent contains at least one compound selected from the group consisting of vinyl ether compounds, epoxy compounds, carbodiimide compounds, oxazoline compounds, isocyanate compounds, and aziridine compounds; Image forming method.

6. The amount of the crosslinking agent applied to the fabric per unit area is X1 g / m ２ and, The amount of the pigment dispersant applied to the fabric per unit area Y1g / m ２ and the ratio X1 / Y1 is in the range of 0.05 to 10; The image forming method according to claim 5 .

7. A fabric and an image portion disposed on the fabric, the image portion includes a pigment and a pigment dispersant crosslinked by a crosslinking agent, The pigment dispersant is a block copolymer including a hydrophilic block A and a hydrophobic block B, the crosslinking agent contains at least one compound selected from the group consisting of vinyl ether compounds, epoxy compounds, carbodiimide compounds, oxazoline compounds, isocyanate compounds, and aziridine compounds; Image formation.

8. The amount of the crosslinking agent per unit area contained in the image area is X2 g / m ２ and, The amount of the pigment dispersant per unit area contained in the image portion is Y2 g / m ２ and the ratio X2 / Y2 is in the range of 0.05 to 10; The image-formed product according to claim 7.

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