Treatment liquid composition and ink set

Abstract

To provide a treatment liquid composition that is applied to an area of cloth printed with a colorant-containing ink composition, improving the color development and also improving the friction fastness.SOLUTION: A treatment liquid composition is applied to an area of cloth printed with a colorant-containing ink composition, the treatment liquid composition containing cationic acrylic resin particles and resin particles having cross-linkable groups.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a treatment liquid composition and an ink set. [Background technology]

[0002] Inkjet recording methods are capable of recording high-resolution images using relatively simple equipment and have been rapidly developing in various fields. Among these methods, various studies have been conducted on textile printing methods. For example, Patent Document 1 discloses a dark color processing method for textile printing, in which a dark color processing liquid containing a film-forming resin with a lower refractive index than the surface of the fabric is applied to an image recorded on a fabric with an ink containing a coloring material, with the aim of providing an inkjet textile printing method that is excellent in deep color, economy, transportability, slippage (unevenness), suitability for overprinting, and lightfastness. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2006-124855 Summary of the Invention [Problem to be solved by the invention]

[0004] However, the film formed by the dark color processing solution described in Patent Document 1 has a problem of poor resistance to friction. [Means for solving the problem]

[0005] The present invention relates to a treatment liquid composition to be applied to an area of ​​a fabric on which a colorant-containing ink composition has been printed, the treatment liquid composition containing cationic acrylic resin particles and resin particles having crosslinkable groups.

[0006] The present invention is an ink set comprising the treatment liquid composition and a colorant-containing ink composition. DETAILED DESCRIPTION OF THE INVENTION

[0007] The following describes in detail an embodiment of the present invention (hereinafter referred to as "the present embodiment"); however, the present invention is not limited to this embodiment, and various modifications are possible without departing from the spirit of the present invention.

[0008] In this specification, "(meth)acrylic" means either acrylic or its corresponding methacrylic.

[0009] 1. Treatment liquid composition The treatment liquid composition of this embodiment is a treatment liquid composition to be applied to an area of ​​a fabric on which a colorant-containing ink composition has been printed, and contains cationic acrylic resin particles and resin particles having crosslinkable groups.

[0010] Since recorded materials obtained by inkjet textile printing tend to have lower color development compared to recorded materials obtained by analog textile printing, methods of applying an overcoat liquid have been investigated. By applying an overcoat liquid, specular reflection of light on the fabric surface is reduced and diffuse reflection is increased, which can further improve the color development of dark colors. However, such overcoat liquids have the problem of poor rubbing fastness.

[0011] In contrast to this, in this embodiment, by using cationic acrylic resin particles and resin particles having crosslinkable groups in combination, when the colorant-containing ink composition is applied to an area of ​​a fabric on which printing has been performed, it is possible to improve color development, particularly black density, and also improve rub fastness.

[0012] 1.1. Cationic acrylic resin particles The cationic acrylic resin particles are not particularly limited as long as they are (meth)acrylic resin particles having a cationic functional group. The monomer constituting such resin particles is not particularly limited, but may include, for example, a polymerized (meth)acrylic monomer, a copolymerized (meth)acrylic monomer and a styrene monomer such as styrene or α-methylstyrene, or a copolymerized (meth)acrylic monomer and a vinyl monomer.

[0013] The cationic functional group is not particularly limited, but examples thereof include an amino group, a quaternary ammonium cation group, an amide group, and a nitrogen-containing heterocyclic group, such as a pyridine ring group, a pyrazine ring group, a pyridazine ring group, a pyrimidine ring group, and a triazine ring group.

[0014] The cationic acrylic resin particles may be prepared from the above materials using a cationic surfactant as an emulsion stabilizer, such as laurylamine salt, stearyltrimethylenediamine salt, octadecylamine salt, laurylpyridinium chloride, stearylammonium chloride, dioleylammonium chloride, or octylbenzyltrimethylammonium chloride.

[0015] Furthermore, cationic acrylic resin particles may be prepared by emulsion polymerization of the above materials using a nonionic surfactant, followed by the post-addition of a cationic substance, such as a cationic surfactant, polyoxyethylene alkylamine, or polyethyleneimine.

[0016] Such cationic acrylic resin particles are not particularly limited, but may be prepared, for example, by radical copolymerizing an N-substituted aminoalkyl (meth)acrylate such as dimethylaminoethyl (meth)acrylate or diethylaminoethyl (meth)acrylate, or an N-substituted aminoalkyl (meth)acrylamide such as dimethylaminopropyl (meth)acrylamide with another (meth)acrylic monomer, styrene, α-methylstyrene, or the like, followed by quaternization with an alkylating agent.

[0017] The average particle diameter of the cationic acrylic resin particles is preferably 50 to 300 nm, more preferably 60 to 250 nm, and even more preferably 70 to 200 nm. When the average particle diameter is within the above range, color development tends to be further improved. In this embodiment, the average particle diameter refers to the median diameter.

[0018] The content of the cationic acrylic resin particles is preferably 0.01 to 3.0% by mass, more preferably 0.01 to 2.0% by mass, and even more preferably 0.01 to 1.0% by mass, relative to the total amount of the treatment liquid composition. When the content of the cationic acrylic resin particles is 0.01% by mass or more, the resulting coating film tends to exhibit more diffused reflection, and color development, particularly that of dark colors, tends to be further improved. When the content of the cationic acrylic resin particles is 3.0% by mass or less, the resulting coating film tends to have more improved rub fastness.

[0019] The content of cationic acrylic resin particles relative to the content of resin particles having crosslinkable groups is preferably 1.0 to 30, more preferably 2.0 to 25, and even more preferably 3.0 to 20, in mass ratio. When the content of cationic acrylic resin particles relative to the content of resin particles having crosslinkable groups is 1.0 or more, color development and texture tend to be further improved, and yellowing tends to be less likely to occur. Furthermore, when the content of cationic acrylic resin particles relative to the content of resin particles having crosslinkable groups is 30 or less, rub fastness tends to be further improved.

[0020] 1.2. Resin particles having crosslinkable groups The crosslinkable group may be one that forms a crosslinked structure by reacting with another crosslinkable group, or one that forms a crosslinked structure by reacting with a different functional group. By using resin particles having such crosslinkable groups, the abrasion resistance of the resulting coating film tends to be further improved.

[0021] The content of the resin particles having crosslinkable groups is preferably 0.01 to 0.50% by mass, more preferably 0.01 to 0.30% by mass, and even more preferably 0.02 to 0.20% by mass, relative to the total amount of the treatment liquid composition. When the content of the resin particles having crosslinkable groups is 0.01% by mass or more, the rub fastness tends to be further improved. When the content of the resin particles having crosslinkable groups is 0.50% by mass or less, the color development and texture tend to be further improved, and yellowing tends to be more unlikely to occur.

[0022] The crosslinkable group is not particularly limited, but examples thereof include an isocyanate crosslinkable group, an oxazoline crosslinkable group, or a carbodiimide crosslinkable group. The presence of such a crosslinkable group tends to further improve the friction resistance and color development, and to further reduce the occurrence of yellowing.

[0023] Examples of the isocyanate-based crosslinking agent include aromatic polyisocyanates, alicyclic polyisocyanates, aliphatic polyisocyanates, adducts of these with various polyols, and polyisocyanates multifunctionalized with isocyanurate bonds, biuret bonds, allophanate bonds, etc.

[0024] More specifically, for example, lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; alicyclic polyisocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and 1,3-bis(isocyanatomethyl)cyclohexane; 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, tetramethylxylylene diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, polymethylene One or more selected from aromatic polyisocyanates such as polyphenyl isocyanate; isocyanate adducts such as a trimethylolpropane / tolylene diisocyanate trimer adduct, a trimethylolpropane / hexamethylene diisocyanate trimer adduct, and an isocyanurate of hexamethylene diisocyanate; a trimethylolpropane adduct of xylylene diisocyanate; a trimethylolpropane adduct of hexamethylene diisocyanate; polyether polyisocyanates, polyester polyisocyanates, and adducts of these with various polyols; and polyisocyanates multifunctionalized with an isocyanurate bond, a biuret bond, an allophanate bond, or the like can be used. Of these, it is preferable to use an aliphatic polyisocyanate, and an isocyanurate of an aliphatic diisocyanate (for example, an isocyanurate of hexamethylene diisocyanate) is more preferable.

[0025] The isocyanate crosslinking agent may be a blocked isocyanate. A blocked isocyanate is one in which an isocyanate group is blocked with a blocking agent. The blocking agent blocks and inactivates the isocyanate group, while regenerating or activating the isocyanate group after deblocking. Examples of blocking agents include imidazole compounds, imidazoline compounds, pyrimidine compounds, guanidine compounds, alcohol compounds, phenol compounds, active methylene compounds, amine compounds, imine compounds, oxime compounds, carbamic acid compounds, urea compounds, acid amide (lactam) compounds, acid imide compounds, triazole compounds, pyrazole compounds, mercaptan compounds, and bisulfites. When the resin contains a crosslinkable group, a crosslinked structure is formed between resins, etc., resulting in good abrasion resistance.

[0026] More specifically, examples of the blocking agent include phenol-based blocking agents such as phenol, cresol, and xylenol; lactam-based blocking agents such as ε-caprolactam, δ-valerolactam, and γ-butyrolactam; alcohol-based blocking agents such as methanol, ethanol, n-, i-, or t-butyl alcohol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, and benzyl alcohol; and oxime-based blocking agents such as formamidoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, benzophenone oxime, butanone oxime, and cyclohexane oxime. Blocking agents include active methylene-based blocking agents such as dimethyl malonate, diethyl malonate, ethyl acetoacetate, and acetylacetone; pyrazole-based blocking agents such as dimethylpyrazole, 3-methylpyrazole, 3,5-dimethylpyrazole, and 3,5-di-tertiarybutylpyrazole; imidazole-based blocking agents such as 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, benzimidazole, and 5-methylbenzimidazole; and 1,2,4-triazole, 3-methyl-1,2,4-triazole, 3-ethyl-1,2,4-triazole, and 1,2,3-benzotriazole-based blocking agents.

[0027] Among these, pyrazole-based blocking agents or oxime-based blocking agents are preferred, pyrazole-based blocking agents are more preferred, and dimethylpyrazole blocking agents are even more preferred. This tends to further improve rub fastness and color development, and to further reduce yellowing. In particular, dimethylpyrazole blocking agents can be dissociated at low temperatures, which tends to improve rub fastness of the resulting recorded matter, suppress yellowing, and reduce harmfulness. Furthermore, they also have superior storage stability compared to other blocking agents with low dissociation temperatures.

[0028] The resin particles having an oxazoline-based crosslinking group are not particularly limited, but examples thereof include a polymer having an oxazoline group obtained by copolymerizing a polymerizable unsaturated monomer having an oxazoline group together with other polymerizable unsaturated monomers as needed by a conventionally known method (e.g., solution polymerization, emulsion polymerization, etc.).

[0029] The polymerizable unsaturated monomer having an oxazoline group is not particularly limited, but examples thereof include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, and 2-isopropenyl-5-ethyl-2-oxazoline.

[0030] The resin particles having a carbodiimide-based crosslinking group are not particularly limited, but examples thereof include polycarbodiimides obtained by a condensation reaction of diisocyanate accompanied by the elimination of carbon dioxide.

[0031] Examples of diisocyanates that are raw materials for synthesizing polycarbodiimide compounds include isomers of toluylene diisocyanate, aromatic diisocyanates such as 4,4-diphenylmethane diisocyanate, aromatic aliphatic diisocyanates such as xylylene diisocyanate, alicyclic diisocyanates such as isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate, and 1,3-bis(isocyanatomethyl)cyclohexane, and aliphatic diisocyanates such as hexamethylene diisocyanate and 2,2,4-trimethylhexamethylene diisocyanate.

[0032] The diisocyanates may be used by controlling the degree of polymerization of the molecules to an appropriate level using a compound that reacts with terminal isocyanates, such as monoisocyanates. Examples of monoisocyanates used to cap the ends of polycarbodiimides and control their degree of polymerization include phenyl isocyanate, toluylene isocyanate, dimethylphenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, and naphthyl isocyanate. In addition to these, compounds having an OH group, a -NH2 group, a COOH group, or a SO3H group can also be used as end-capping agents.

[0033] The condensation reaction of diisocyanate accompanied by decarbonation proceeds in the presence of a carbodiimidization catalyst. Examples of the catalyst include phospholene oxides such as 1-phenyl-2-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1-oxide, 3-methyl-1-phenyl-2-phospholene-1-oxide, and 3-phospholene isomers thereof, with 3-methyl-1-phenyl-2-phospholene-1-oxide being preferred in terms of reactivity. The amount of the catalyst used can be a catalytic amount.

[0034] 1.3.Water The content of water is preferably 90 to 99.7 mass %, more preferably 92.5 to 99.5 mass %, and even more preferably 95 to 99 mass %, relative to the total amount of the treatment liquid composition.

[0035] 1.4.Surfactants The treatment liquid composition used in this embodiment preferably contains a surfactant. The surfactant is not particularly limited, but is preferably at least one of an acetylene glycol-based surfactant, a fluorine-based surfactant, and a silicone-based surfactant.

[0036] The acetylene glycol surfactant is not particularly limited, but is preferably at least one selected from the group consisting of 2,4,7,9-tetramethyl-5-decyne-4,7-diol, alkylene oxide adducts of 2,4,7,9-tetramethyl-5-decyne-4,7-diol, and alkylene oxide adducts of 2,4-dimethyl-5-decyne-4-ol and alkylene oxide adducts of 2,4-dimethyl-5-decyne-4-ol.

[0037] The fluorine-based surfactant is not particularly limited, but examples thereof include perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl phosphates, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl betaines, and perfluoroalkyl amine oxide compounds.

[0038] Examples of silicone surfactants include polysiloxane compounds and polyether-modified organosiloxanes.

[0039] Among these, nonionic surfactants are preferred. Examples of nonionic surfactants include silicone surfactants, polyoxyethylene alkyl ether surfactants, polyoxypropylene alkyl ether surfactants, polycyclic phenyl ether surfactants, sorbitan derivatives, and fluorine-containing surfactants.

[0040] The content of the surfactant is preferably 0.1 to 1.0 mass %, more preferably 0.2 to 0.7 mass %, and even more preferably 0.3 to 0.5 mass %, relative to the total amount of the treatment liquid composition.

[0041] 1.5.Other Ingredients The treatment liquid composition may further contain a water-soluble organic solvent, etc., as necessary.

[0042] 2. Ink set The ink set of this embodiment comprises the treatment liquid composition and a colorant-containing ink composition. The colorant-containing ink composition may be a pigment ink or a dye ink.

[0043] 2.1. Colorant-containing ink composition The components contained in the colorant-containing ink composition are not particularly limited, but may contain, for example, a colorant, water, a water-soluble organic solvent, a fixing resin, resin particles having a crosslinkable group, and a surfactant.

[0044] 2.1.1.Colorants Examples of the coloring material include dyes and pigments. Although dyes and pigments are exemplified below, the coloring material of this embodiment is not limited thereto.

[0045] The inorganic pigment is not particularly limited, but examples thereof include carbon blacks (CI Pigment Black 7) such as furnace black, lamp black, acetylene black, and channel black, iron oxide, and titanium oxide.

[0046] The organic pigment is not particularly limited, but examples thereof include quinacridone pigments, quinacridonequinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, diketopyrrolopyrrole pigments, perinone pigments, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, isoindolinone pigments, azomethine pigments, and azo pigments.

[0047] The pigment may be a pigment dispersion obtained by dispersing the pigment in water with a dispersant, or may be a self-dispersing surface-treated pigment in which hydrophilic groups are introduced onto the pigment particle surface by utilizing a chemical reaction.

[0048] The dye is not particularly limited, but examples thereof include acid dyes such as CI Acid Yellow, CI Acid Red, CI Acid Blue, CI Acid Orange, CI Acid Violet, and CI Acid Black; basic dyes such as CI Basic Yellow, CI Basic Red, CI Basic Blue, CI Basic Orange, CI Basic Violet, and CI Basic Black; direct dyes such as CI Direct Yellow, CI Direct Red, CI Direct Blue, CI Direct Orange, CI Direct Violet, and CI Direct Black; reactive dyes such as CI Reactive Yellow, CI Reactive Red, CI Reactive Blue, CI Reactive Orange, CI Reactive Violet, and CI Reactive Black; and disperse dyes such as CI Disperse Yellow, CI Disperse Red, CI Disperse Blue, CI Disperse Orange, CI Disperse Violet, and CI Disperse Black.

[0049] The content of the coloring material is preferably 1.0 to 12 mass %, more preferably 2.0 to 10 mass %, and even more preferably 3.0 to 7.5 mass %, in terms of solid content, relative to the total amount of the ink composition.

[0050] 2.1.2.Water, The water content is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, and even more preferably 65 to 85% by mass, relative to the total amount of the ink composition.

[0051] 2.1.3. Water-soluble organic solvents The water-soluble organic solvent is not particularly limited, but examples thereof include polyols, glycol ether-based organic solvents, cyclic amides, acyclic amides, acyclic esters, and cyclic esters. Among these, nitrogen-containing organic solvents, glycol ether-based organic solvents, and polyols are preferred. The water-soluble organic solvents may be used alone or in combination of two or more.

[0052] The polyol is not particularly limited, but examples thereof include ethylene glycol, propylene glycol, 1,2-propanediol, 1,2-butanediol, 1,3-propanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, dipropylene glycol, trimethylolpropane, glycerin, 1,2-pentanediol, 1,2-hexanediol, 1,2-octanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 2-ethyl-2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 3-methyl-1,3-butanediol, 2-ethyl-1,3-hexanediol, 3-methyl-1,5-pentanediol, and 2-methylpentane-2,4-diol.

[0053] The glycol ether organic solvent is not particularly limited, but examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol mono-t-butyl ether, triethylene glycol monobutyl ether, 1-methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, 3-methoxy-3-methyl-1-butanol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether.

[0054] The content of the water-soluble organic solvent is preferably 1 to 40% by mass, more preferably 2 to 30% by mass, and even more preferably 5 to 20% by mass, relative to the total amount of the ink composition.

[0055] 2.1.4. Fixing resin The fixing resin is not particularly limited, but examples thereof include urethane resins, acrylic resins, fluorene resins, polyolefin resins, rosin-modified resins, terpene resins, polyester resins, polyamide resins, epoxy resins, vinyl chloride resins, ethylene vinyl acetate resins, etc. The fixing resins may be used alone or in combination of two or more.

[0056] At least a portion of the fixing resin may be resin particles having a crosslinkable group, as exemplified in the treatment liquid composition, and the crosslinkable group of the resin particles contained in the colorant-containing ink composition may be capable of crosslinking with the crosslinkable group of the resin particles contained in the treatment liquid composition. For example, if the resin particles contained in the treatment liquid composition and the fixing resin contained in the ink composition have the same type of crosslinkable group, such as an isocyanate group, they will be capable of crosslinking with each other. This tends to further improve the abrasion resistance of the resulting recorded matter.

[0057] The content of the fixing resin is preferably 1.0 to 15 mass %, more preferably 3.0 to 12 mass %, and even more preferably 5.0 to 10 mass %, in terms of solid content, relative to the total amount of the ink composition.

[0058] Surfactants The surfactant is not particularly limited, but examples thereof include acetylene glycol surfactants, fluorine-based surfactants, and silicone-based surfactants. More specifically, examples thereof include the same surfactants as those exemplified in the treatment liquid composition.

[0059] The content of the surfactant is preferably 0.1 to 3.0% by mass, and more preferably 0.5 to 2.0% by mass, relative to the total mass of the ink composition.

[0060] 3. Stamping method The printing method of the present embodiment includes a recording step of applying an ink composition containing a dye to the surface of a fabric by an inkjet method, and a treatment liquid application step of applying the treatment liquid composition to the area of ​​the fabric to which the ink composition has been applied after the recording step, and may also include a heating step and a washing step as necessary.

[0061] 3.1. Recording process The recording process is a process of applying an ink composition containing a dye to the surface of the fabric by an inkjet method. The inkjet method is not particularly limited, but examples thereof include a charge deflection method, a continuous method, and an on-demand method (piezo method, bubble jet (registered trademark) method).

[0062] 3.2. Treatment liquid application process The treatment liquid application step is a step of applying the treatment liquid composition to the area of ​​the fabric to which the ink composition has been applied after the recording step. The means for applying the treatment liquid composition is not particularly limited, but examples thereof include a roller method, a spray method, and an inkjet method. Among these, the inkjet method is preferred from the viewpoint of being able to selectively apply the treatment liquid composition. In the treatment liquid application step, the treatment liquid composition may be applied before or after the ink composition applied to the fabric has dried.

[0063] 3.3.Heating process The inkjet printing method may further include a heating step of heating the fabric after the recording step and the treatment liquid application step. By including the heating step, the dye can be more effectively dyed into the fibers that make up the fabric. The heating method is not particularly limited, but examples thereof include the HT method (high-temperature steaming method), the HP method (high-pressure steaming method), and the thermosol method.

[0064] Furthermore, in the heating step, the ink composition-adhering surface of the fabric may or may not be pressurized. Examples of heating methods that do not pressurize the ink composition-adhering surface of the fabric include oven drying (a method that does not involve pressing, such as a conveyor oven or batch oven). By including such a heating step, the productivity of recorded materials is further improved. Examples of heating methods that also pressurize the ink composition-adhering surface of the fabric include, but are not limited to, heat pressing and wet-on-drying. Note that "pressurizing" refers to applying pressure to the fabric by contacting a solid object.

[0065] The temperature during the heat treatment is preferably 80 to 150° C., more preferably 90 to 110° C. When the temperature during the heat treatment is within the above range, the dye tends to be more effectively dyed into the fibers that make up the fabric.

[0066] 3.4. Cleaning process The inkjet printing method may further include a washing step of washing the fabric after the heating step. The washing step can effectively remove dye that has not adhered to the fiber. The washing step can be carried out using, for example, water, and a soaping treatment may be carried out as needed. The soaping method is not particularly limited, but examples thereof include a method of washing off unfixed pigment with a hot soapy solution or the like.

[0067] 3.5.Fabric The fibers constituting the fabric are not particularly limited, but examples thereof include natural fibers such as silk, cotton, linen, and wool; synthetic fibers such as polyester fibers, nylon fibers, triacetate fibers, diacetate fibers, and polyamide fibers; and regenerated fibers such as rayon. The fabric may be made of a single type of fiber or a blend of two or more types of fibers. The fabric may be made of the above-mentioned fibers in any form, such as woven fabric, knitted fabric, or nonwoven fabric. [Example]

[0068] The present invention will be described in more detail below using examples and comparative examples, but the present invention is not limited to the following examples.

[0069] 1. Ink composition The following materials were mixed and thoroughly stirred to obtain each ink composition. The polyurethane resin used in the pigment ink was manufactured by Mitsui Chemicals, Inc., under the product name Takelac WS6021, and had an isocyanate-based crosslinking group as the crosslinkable group.

[0070] 1.1.Pigment ink Pigment: Self-dispersing carbon black pigment (solid content 15%): 30.0% by mass Fixing resin: Polyurethane resin (solid content 30%): 20.0% by mass Organic solvent: Glycerin: 10.0% by mass Organic solvent: Triethylene glycol: 5.0% by mass Surfactant: Olfine E1010 (manufactured by Nissin Chemical Industry Co., Ltd.): 1.0% by mass Water: remainder

[0071] 1.2.Dye ink Dye: Reactive Black 39 (20% solids): 10.0% by mass Organic solvent: propylene glycol: 10.0% by mass Surfactant: Olfine PD002W (manufactured by Nissin Chemical Industry Co., Ltd.): 0.5% by mass Water: remainder

[0072] 2. Treatment liquid composition Each treatment liquid composition was obtained by mixing and thoroughly stirring the materials as shown in Tables 1 and 2. Table 1 shows the evaluation results using the treatment liquid composition and pigment ink, and Table 2 shows the evaluation results using the treatment liquid composition and dye ink.

[0073] [Table 1]

[0074] [Table 2]

[0075] (cationic acrylic resin particles) Luster AB-8K (Kotani Chemical Industry Co., Ltd., acrylic resin particles, average particle size 80-120 nm, solid content 11%) (Resin particles having crosslinkable groups) PHOBOL EXTENDER XAN (Huntsman, 2-butanone oxime blocked isocyanate resin, solids content 10%) PHOBOL EXTENDER UXN (Huntsman, dimethylpyrazole blocked isocyanate resin, solids content 10%) Polyurethane resin (Mitsui Chemicals, product name: Takelac WS6021) (surfactant) Olfin E1010 (product name, manufactured by Nissin Chemical Industry Co., Ltd., nonionic surfactant)

[0076] 2. Evaluation 2.1.Color development Each ink composition was printed on a fabric (Print Star Heavy Weight (white) 5.6 oz) using a Seiko Epson Corporation printer (SC-F200) at a resolution of 1440 dpi x 1440 dpi and a coating amount of 200 mg / inch. 2 Thereafter, the treatment liquid composition was applied to the area where the ink composition had been applied at a resolution of 1440 dpi x 1440 dpi and a coating amount of 200 mg / inch. 2 The printed fabric was then heat-treated at 165°C for 5 minutes in a conveyor oven (hot air drying method) to fix the printed fabric. The OD value of each printed fabric was measured using a colorimeter (trade name "Gretag Macbeth Spectrolino", manufactured by X-RITE), and the color development was evaluated based on the obtained OD value according to the following evaluation criteria. A rating of C or higher can be said to have achieved a good effect. (Evaluation criteria) A:OD value is 1.70 or more B: OD value is 1.60 or more and less than 1.70 C:OD value is 1.50 or more and less than 1.60 D:OD value is less than 1.50

[0077] 2.2. Evaluation of friction durability The printed fabrics obtained by the above color development evaluation were subjected to a color fastness test under dry and wet rub conditions using a type I (crock meter) tester in accordance with the method specified in ISO-105 X12. Based on the results, the dry and wet rub properties of the printed fabrics were evaluated according to the following evaluation criteria. A rating of B or higher can be said to indicate good results.

[0078] (Evaluation criteria: dry friction) A: Level 4 or above B: Less than 4th grade, 3rd-4th grade or above C: Below 3-4 grade

[0079] (Evaluation criteria: wet friction) A: Level 3-4 or higher B: Less than 3-4 grade, 3 grade or above C: Below level 3

[0080] 2.3.Texture The texture of the printed fabric obtained by the above color development evaluation was evaluated according to the following evaluation criteria, based on the feel of touching the printed portion directly with the palm of the hand. The evaluation of texture was carried out by three people, and the most popular opinion was taken as the judgment result. In addition, when the judgment was divided between two people, the middle opinion between them was taken as the judgment result. (Evaluation criteria) A: The hardness and feel of the printed area are almost the same as the original fabric, and are good. B: The hardness or feel of the printed area is slightly different from the original fabric, but there is no problem in practical use. C: The hardness or feel of the printed area is worse than that of the original fabric.

[0081] 2.4.Yellowing The printed matter obtained by the above color development evaluation was observed and judged according to the following criteria. The judgement was made by three people, and the opinion with the most support was taken as the judgement result. If the judgement was split between two people, the intermediate opinion was taken as the judgement. A: No yellowing observed, good condition B: Some yellowing is observed, but there is no problem in practical use. C: Yellowing is observed, but within the acceptable range.

Claims

1. A treatment liquid composition to be applied to an area of ​​a fabric on which a colorant-containing ink composition has been printed, comprising: cationic acrylic resin particles; Resin particles having a crosslinkable group, the resin particles having a crosslinkable group have an isocyanate-based crosslinkable group, an oxazoline-based crosslinkable group, or a carbodiimide-based crosslinkable group blocked with a pyrazole-based blocking agent; Treatment liquid composition.

2. the resin particles having a crosslinkable group have an isocyanate-based crosslinkable group blocked with a dimethylpyrazole blocking agent; The treatment liquid composition according to claim 1 .

3. the content of the cationic acrylic resin particles is 0.01% by mass or more and 1.0% by mass or less with respect to the total amount of the treatment liquid composition; The treatment liquid composition according to claim 1 or 2.

4. the content of the resin particles having a crosslinkable group is 0.01% by mass or more and 0.50% by mass or less with respect to the total amount of the treatment liquid composition; The treatment liquid composition according to any one of claims 1 to 3.

5. The average particle diameter of the cationic acrylic resin particles is 50 nm or more and 300 nm or less. The treatment liquid composition according to any one of claims 1 to 4.

6. the content of the cationic acrylic resin particles relative to the content of the resin particles having a crosslinkable group is 1.0 to 30 in terms of mass ratio; The treatment liquid composition according to any one of claims 1 to 5.

7. A composition further comprising a surfactant and water. The treatment liquid composition according to any one of claims 1 to 6.

8. The treatment liquid composition according to any one of claims 1 to 7, a colorant-containing ink composition; Ink set.

9. the colorant-containing ink composition contains resin particles having a crosslinkable group, the crosslinkable groups of the resin particles contained in the colorant-containing ink composition are crosslinkable with the crosslinkable groups of the resin particles contained in the treatment liquid composition; The ink set according to claim 8.

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