Treatment liquid composition, combination thereof with inkjet ink composition, and treatment method

Abstract

Provided are a treatment liquid composition, a combination thereof with an inkjet ink composition, and a treatment method, wherein the treatment liquid composition can have both excellent color development and excellent wet friction fastness that is not easy to fade even when wet friction occurs. The treatment liquid composition of the present invention contains: a polyamide epihalohydrin polymer; and a quaternary ammonium salt polymer other than the polyamide epihalohydrin polymer.

Description

Technical Field

[0001] The present invention relates to a treatment liquid composition, an inkjet ink composition, a combination of the treatment liquid composition and a treatment method. Background Art

[0002] The inkjet recording method is a method of recording by ejecting droplets of an inkjet ink composition (hereinafter referred to as "ink") from a fine nozzle and attaching it to a recording medium. Conventionally, there is a known technique of pre-treating the recording medium using a treatment liquid composition containing a coagulant in order to improve the color development of the recorded matter when ejecting ink onto the recording medium to form an image by the inkjet recording method.

[0003] For example, Patent Document 1 describes a treatment liquid composition containing a water-soluble cationic polymer obtained by reacting monomers containing an amine and an epihalohydrin, a nonionic resin, an organic solvent, and water.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2021-020394 Summary of the invention

[0007] However, it is difficult to achieve both excellent color development and excellent wet rubbing fastness that does not easily fade even when rubbed wet.

[0008] In one embodiment of the treatment liquid composition according to the present invention, the treatment liquid composition comprises:

[0009] Polyamide epihalohydrin polymers; and

[0010] A quaternary ammonium salt polymer other than the polyamide epihalohydrin polymer.

[0011] In one embodiment of the set of the inkjet ink composition and the treatment liquid composition according to the present invention,

[0012] A combination of an inkjet ink composition and the treatment liquid composition of one embodiment above,

[0013] The inkjet ink composition is a water-based pigment inkjet ink containing pigment particles and resin particles. The pH of the ink composition exceeds 8 and contains particle components having a volume average particle size of 20 to 500 nm.

[0014] In one embodiment of the processing method of the present invention, there is:

[0015] an attachment step of attaching the treatment liquid composition of one embodiment to a fabric; and

[0016] a heating step of heating the fabric to which the treatment liquid composition is attached,

[0017] The surface temperature of the fabric in the heating step is 100° C. or higher. DETAILED DESCRIPTION

[0018] Hereinafter, embodiments of the present invention will be described. In the embodiments described below, examples of the present invention will be described. The present invention is not limited to the following embodiments, and various modifications of the embodiments are also included without changing the gist of the present invention. In addition, all structures described below are not necessarily necessary structures of the present invention.

[0019] 1. Treatment liquid composition

[0020] A treatment liquid composition according to one embodiment of the present invention contains:

[0021] Polyamide epihalohydrin polymers; and

[0022] A quaternary ammonium salt polymer other than the polyamide epihalohydrin polymer.

[0023] According to the above structure, it is possible to obtain excellent color development and excellent wet rubbing fastness that is not easily discolored even when rubbed wet.

[0024] In the past, when an image is formed on a recording medium such as cloth by ink, it is difficult to achieve both high color development and fastness (especially fading or washing resistance during wet friction). This is because in order to achieve good color development, the solid components of the ink need to remain near the surface of the recording medium. On the other hand, when the solid components of the ink are located near the surface of the recording medium, the ink is easily peeled off due to friction, etc., and the fastness is easily deteriorated. In addition, since the coagulation reactivity of the polyvalent metal salt used as a coagulant in the past with the components in the ink increases according to its amount, it is easy to control the color development, but sometimes crystals are formed near the surface of the recorded object. Such crystals are easily dissolved in water. When the recorded object is wetted with water, the crystals located near the surface are dissolved, and the parts where the crystals exist form cavities. The parts where cavities are formed like this are easy to become the starting point for the ink to peel off, so the wet friction fastness of the treatment liquid using the polyvalent metal salt is easy to deteriorate. In addition, when there are crystals on the recorded object, since they appear as white spots on the printed surface, the whitening phenomenon also becomes a problem.

[0025] In contrast, in the treatment fluid composition involved in the present embodiment, the quaternary ammonium salt polymer other than the polyamide epihalohydrin polymer is used to form without using a polyvalent metal salt. For such a quaternary ammonium salt polymer, for example, when the recording medium is a cloth, it is coated on the fiber surface of the cloth, the cohesive reactivity of the ink contacted with the fiber surface is excellent, has high color development performance, and can not produce crystals such as polyvalent metal salts, is therefore easy to maintain wet rubbing fastness. And, the treatment fluid composition involved in the present embodiment uses the polyamide epihalohydrin polymer to form. For the polyamide epihalohydrin polymer, the amide part in its structure etc. is bonded to the hydroxyl group of the fiber of the cloth, has the function of improving water resistance of the swelling that can reduce the fiber because of water, the function of improving structural strength because of the crosslinking of the epihalohydrin part etc., can improve wet rubbing fastness. As mentioned above, the treatment fluid composition involved in the present embodiment can realize the compatibility of excellent color development and excellent wet rubbing fastness according to the structure containing the quaternary ammonium salt polymer other than the polyamide epihalohydrin polymer and the polyamide epihalohydrin polymer.

[0026] Hereinafter, each component contained in the treatment liquid composition according to the present embodiment and components that may be contained will be described.

[0027] 1.1 Polyamide epihalohydrin polymer

[0028] The treatment liquid composition according to the present embodiment contains a polyamide epihalohydrin polymer.

[0029] Polyamide epihalohydrin polymer refers to, makes the polymer formed by the monomer polymerization containing amine and epihalohydrin.As polyamide epihalohydrin polymer, for example, polyamine-epihalohydrin copolymer, polyamide-epihalohydrin copolymer, polyamide polyamine-epihalohydrin copolymer, amine-epihalohydrin copolymer etc. can be listed.These polymers can obtain by known method, for example, by the method for the monomer polymerization containing amine and epihalohydrin, the monomer containing epihalohydrin and by the method for the polyamide graft polymerization obtained by the monomer polymerization containing amine and carboxylic acid etc.

[0030] Epihalohydrin contains halogen atom in structure.As halogen atom, can enumerate out for example F, Cl, Br, I etc.Epihalohydrin is preferred Cl among these halogen atoms, therefore is preferably epichlorohydrin.Therefore, as polyamide epihalohydrin polymer, preferably polyamide epichlorohydrin polymer, specifically, preferably polyamine-epichlorohydrin copolymer, polyamide-epichlorohydrin copolymer, polyamide polyamine-epichlorohydrin copolymer, amine-epichlorohydrin copolymer.Among these, more preferably polyamide-epichlorohydrin copolymer.

[0031] Commercially available products of the polyamide epihalohydrin polymer include WS-4020, 4030, 4027, and TS-4070 (manufactured by Seikyo PMC Co., Ltd., polyamide-epichlorohydrin polymer), WS-4011 (manufactured by Seikyo PMC Co., Ltd., polyamine-epichlorohydrin polymer), AF-100, 251S, 255, 255LOX, and 2500 (manufactured by Arakawa Kogyo Chemical Co., Ltd., polyamide polyamine-epichlorohydrin polymer), CATIONMASTER PE-30 (manufactured by Yokkaichi Kogyo Co., Ltd., dimethylamine-ethylenediamine-epichlorohydrin condensate), and EPA-SK01 (manufactured by Yokkaichi Kogyo Co., Ltd., polyamide polyamine-epichlorohydrin condensate).

[0032] The polyamide epihalohydrin polymer may be used alone or in combination of two or more.

[0033] The weight average molecular weight of the polyamide epihalohydrin polymer is preferably 10,000 to 5,000,000, more preferably 100,000 to 5,000,000, further preferably 500,000 to 5,000,000, and particularly preferably 1,000,000 to 5,000,000. When the weight average molecular weight of the polyamide epihalohydrin polymer is within the above range, the wet rubbing fastness may be further improved.

[0034] The content of polyamide epihalohydrin polymer is preferably more than 0.10 mass % relative to the gross mass of the treatment fluid composition, more preferably more than 0.30 mass %, further preferably more than 0.50 mass %, especially preferably more than 0.70 mass %.In addition, the content of polyamide epihalohydrin polymer is preferably less than 5.0 mass % relative to the gross mass of the treatment fluid composition, more preferably less than 3.0 mass %, further preferably less than 1.5 mass %, especially preferably less than 1.2 mass %.When the content of polyamide epihalohydrin polymer is within the above range, there is a good tendency to balance the rubbing fastness, texture, and lightfastness of color development, dry rubbing fastness and wet rubbing fastness.

[0035] 1.2 Specific quaternary ammonium salt polymers

[0036] The treatment liquid composition according to the present embodiment contains a quaternary ammonium salt polymer other than the polyamide epihalohydrin polymer (hereinafter referred to as a "specific quaternary ammonium salt polymer").

[0037] Examples of the specific quaternary ammonium salt polymer include polymers that are soluble in water, have one or more quaternary ammonium salts in the chain of repeating units constituting the polymer, and do not have a halohydrin structure such as a chlorohydrin structure.

[0038] Specific examples of the specific quaternary ammonium salt polymer include poly(2-hydroxy-3-methacryloxypropyltrimethylammonium chloride), poly(2-hydroxy-3-methacryloxypropyltriethylammonium chloride), poly(2-hydroxy-3-acryloxypropyltrimethylammonium chloride), poly(2-hydroxy-3-acryloxypropyltriethylammonium chloride), poly(2-methacryloxyethyltrimethylammonium chloride), poly(2-methacryloxyethyltriethylammonium chloride), poly(2-acryloxyethyltrimethylammonium chloride), poly( 2-acryloyloxyethyltriethylammonium chloride), salts of poly(dimethylaminoethyl methacrylate), salts of poly(diethylaminoethyl methacrylate), salts of poly(diethylaminoethyl acrylate), salts of poly(dimethylaminoethyl methacrylate), salts of poly(dimethylaminoethyl acrylate), poly(4-vinyl-N-methylpyridinium chloride), N,N-dimethyl-substituted 3,5-methylpiperidinium chloride resin, poly(dimethyldiallylammonium chloride) and poly(diethyldiallylammonium chloride) polyethyleneimine hydrochloride, etc.

[0039] Specific quaternary ammonium salt polymers can also be commercially available products, for example, PAS-H-1L, PAS-H-5L, PAS-H-10L; PAS-24; PAS-2401; PAS-A-1, PAS-A-5; PAS-J-81L, PAS-J-81, PAS-J-41 (manufactured by Nittobo Medical Co., Ltd.), EP-1137 (manufactured by Takamatsu Oil and Fats Co., Ltd.), PAPYOGEN P-105, MILLIOGEN P-20 (manufactured by SENKA Co., Ltd.), etc.

[0040] The specific quaternary ammonium salt polymer may be used alone or in combination of two or more.

[0041] The content of specific quaternary ammonium salt polymer is preferably more than the 0.10 mass % with respect to the gross mass of the treatment fluid composition, more preferably more than the 0.30 mass %, further preferably more than the 0.50 mass %, especially preferably more than the 0.70 mass %.In addition, the content of specific quaternary ammonium salt polymer is preferably below the 5.0 mass % with respect to the gross mass of the treatment fluid composition, more preferably below the 3.0 mass %, further preferably below the 1.5 mass %, especially preferably below the 1.2 mass %.When the content of specific quaternary ammonium salt polymer is in the above-mentioned scope, there is the good tendency of the balance of rubbing fastness, texture, lightfastness that can make color developing property, dry rubbing fastness and moist rubbing fastness.

[0042] 1.3 Cationic polymers other than those mentioned above

[0043] The treatment fluid composition involved in the present embodiment can contain the cationic polymers beyond the above-mentioned polyamide epihalohydrin polymer and the specific quaternary ammonium salt polymer.As such cationic polymer, can list out the halohydrin structures such as quaternary ammonium salt and chlorohydrin structures in polymer structure, have the polymer of the cationic functional group selected from primary amino group, secondary amino group, tertiary amino group, imino group and amide group.

[0044] 1.4 Solvent

[0045] <Water>

[0046] The treatment liquid composition involved in this embodiment preferably contains water as a solvent. Water can be the main solvent of the treatment liquid composition and is a component that evaporates and disperses by drying. As water, pure water such as ion exchange water, ultrafiltration water, reverse osmosis water and distilled water, and water such as ultrapure water that has ionic impurities removed as much as possible can be listed. In addition, when water is sterilized by ultraviolet irradiation or addition of hydrogen peroxide, the generation of mold or bacteria can be prevented when the treatment liquid composition is stored for a long time.

[0047] The water content is not particularly limited, but can be, for example, 50% by mass or more, further 60% by mass or more, or 70% by mass or more relative to the total mass of the treatment liquid composition. In addition, the upper limit of the water content contained in the treatment liquid composition can be 99% by mass or less, 98% by mass or less, or 97% by mass or less.

[0048] <Water-soluble organic solvent>

[0049] The treatment liquid composition according to the present embodiment may contain a water-soluble organic solvent as a solvent.

[0050] Examples of the water-soluble organic solvent include polyol compounds, glycol ethers, and betaine compounds.

[0051] Examples of the polyol compound include polyol compounds (preferably diol compounds) having a carbon number of 2 to 6 in the molecule and optionally having one ether bond in the molecule. Specific examples include 1,2-pentanediol, methyl triglycol (triethylene glycol monomethyl ether), butyl triglycol (triethylene glycol monobutyl ether), trimethylolpropane, butyl diglycol (diethylene glycol monobutyl ether), dipropylene glycol monopropyl ether, glycerol, 1,2-hexanediol, 1,2-heptanediol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-3-phenoxy- 1,2-propylene glycol, 3-(3-methylphenoxy)-1,2-propylene glycol, 3-hexyloxy-1,2-propylene glycol, 2-hydroxymethyl-2-phenoxymethyl-1,3-propylene glycol, 3-methyl-1,3-butanediol, 1,3-propylene glycol, 1,2-butanediol, 1,2-pentanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, and the like.

[0052] As the glycol ether, for example, monoalkyl ethers of glycols selected from ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, and polyoxyethylene polyoxypropylene glycol are preferred. More preferred examples include triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, and dipropylene glycol monopropyl ether.

[0053] Betaine compounds refer to compounds having positive and negative charges at non-adjacent positions in the same molecule, wherein the dissociable hydrogen atom is not bonded to the atom having the positive charge, and the molecule as a whole is a compound having no charge (intramolecular salt). As a preferred betaine compound, it is an N-alkyl substitution of an amino acid, and more preferably an N-trialkyl substitution of an amino acid. As betaine compounds, for example, trimethylglycine (also referred to as "glycine betaine"), γ-butyrylbetaine, hominisine, trigonelline, carnitine, homoserine betaine, valine betaine, lysine betaine, ornithine betaine, alanine betaine, stachydrine and glutamic acid betaine can be listed, and preferably trimethylglycine can be exemplified.

[0054] In addition, as the water-soluble organic solvent, a pyrrolidone derivative can be used. Examples of the pyrrolidone derivative include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-pyrrolidone, N-butyl-2-pyrrolidone, and 5-methyl-2-pyrrolidone.

[0055] A plurality of water-soluble organic solvents may be mixed and used. When a water-soluble organic solvent is contained, its content is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less relative to the total mass of the treatment liquid composition.

[0056] 1.5 Surfactants

[0057] The treatment liquid composition according to the present embodiment may contain a surfactant. The surfactant has functions such as reducing the surface tension of the treatment liquid composition and improving wettability with a recording medium.

[0058] Among the surfactants, for example, acetylene glycol surfactants, silicone surfactants, and fluorine surfactants can be preferably used. Among these, acetylene glycol surfactants are more preferably contained.

[0059] Examples of the acetylene glycol surfactant include, but are not particularly limited to, SURFYNOL 104 (HLB value = 4), 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 104S, 420, 440, 465, 485 (HLB value = 17), SE, SE-F, 504, 61, DF37, CT111, CT121, CT131, CT136, TG, GA, DF110D (all trade names, manufactured by Air Products and Chemicals, Inc.), OLFINE B, Y, P, A, STG, SPC, E1004, E1010 (HLB value = 14), PD-001, PD-002W, PD-003, PD-004, EXP.4001, EXP.4036, EXP.4051, AF-103, AF-104, AK-02, SK-14, AE-3 (all of the above are trade names, manufactured by Nissin Chemical Industry Co., Ltd.), ACETYLENOL E00, E00P, E40, E100 (all of the above are trade names, manufactured by Kawaken Fine Chemicals Co., Ltd.).

[0060] The silicone-based surfactant is not particularly limited, but preferably a polysiloxane-based compound is used. The polysiloxane-based compound is not particularly limited, but for example, a polyether-modified silicone is used. Commercially available products of the polyether-modified organosiloxane include, for example, BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, and BYK-348 (these are trade names, manufactured by BYK Japan Co., Ltd.), KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-6020, X-22-4515, KF-6011, KF-6012, KF-6015, and KF-6017 (these are trade names, manufactured by Shin-Etsu Chemical Co., Ltd.).

[0061] As the fluorine-based surfactant, a fluorine-modified polymer is preferably used, and a specific example thereof includes BYK-340 (manufactured by BYK Japan Ltd.).

[0062] The surfactant may be used alone or in combination of two or more.

[0063] The lower limit of the content of the surfactant is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and further preferably 0.5% by mass or more, relative to the total mass (100% by mass) of the treatment liquid composition. In addition, the upper limit of the content of the surfactant is preferably 10% by mass or less, more preferably 7% by mass or less, further preferably 5% by mass or less, particularly preferably 2% by mass or less, and most preferably 1% by mass or less, relative to the total mass (100% by mass) of the treatment liquid composition.

[0064] When selecting a surfactant, the HLB value is preferably considered. The lower limit of the HLB value of the surfactant is preferably 6 or more, more preferably 8 or more, and further preferably 10 or more. In addition, the upper limit of the HLB value is preferably 18 or less, more preferably 16 or less, and further preferably 14 or less. When the HLB value is within the above range, the color rendering property may be further improved.

[0065] In addition, the HLB value in this specification refers to a value calculated by the following formula (1) based on the ratio of the non-polar value (I) to the polar value (O) in the organic concept diagram (hereinafter simply referred to as "I / O value").

[0066] HLB value = (non-polar value (I) / polar value (O)) × 10···(1)

[0067] Specifically, the I / O value can be calculated based on the literature such as "Systematic Qualitative Analysis of Organic Mixtures" by Mu Fujita, Kazama Shobo, 1974; "Theoretical Chemistry of Dyeing" by Nobuhiko Kuroki, Maki Shoten, 1966; and "Separation Methods of Organic Compounds" by Hiroo Inoue, Soukabo, 1990.

[0068] 1.6 Water-insoluble ingredients

[0069] The treatment liquid composition according to the present embodiment may contain a water-insoluble component. The water-insoluble component refers to a component that is insoluble or almost insoluble in water, and examples thereof include water-insoluble colorants, water-insoluble resins, waxes, and water-insoluble organic solvents.

[0070] 〔Water-insoluble color materials〕

[0071] As the water-insoluble color material, oil-soluble dyes, pigment particles, etc. can be cited. As the oil-soluble dye, although not particularly limited, for example, disperse dyes, vat dyes, or organic solvent-soluble dyes can be used. As the pigment particles, the same pigment particles as those contained in the inkjet ink composition described later can be used.

[0072] 〔Water-insoluble resin〕

[0073] Examples of water-insoluble resins include polyurethane resins, acrylic resins, styrene acrylic resins, fluorene resins, polyolefin resins, rosin-modified resins, terpene resins, polyester resins, polyamide resins, epoxy resins, vinyl chloride resins, vinyl chloride-vinyl acetate copolymers, and ethylene vinyl acetate resins. Water-insoluble resins are preferably used in the form of resin particles such as resin emulsions or powders, and more preferably resin particles of resin emulsions. Water-insoluble resins may be used alone or in combination of two or more.

[0074] Polyurethane resin is a general term for resins having urethane bonds. In addition to urethane bonds, polyether polyurethane resins having ether bonds in the main chain, polyester polyurethane resins having ester bonds in the main chain, polycarbonate polyurethane resins having carbonate bonds in the main chain, etc. can also be used as polyurethane resins.

[0075] Acrylic resin is a general term for polymers obtained by polymerizing at least one acrylic monomer such as (meth)acrylic acid and (meth)acrylic acid ester, and includes, for example, resins obtained from acrylic monomers or copolymers of acrylic monomers and other monomers. For example, acrylic-vinyl resins, which are copolymers of acrylic monomers and vinyl monomers, can be included. In addition, copolymers with vinyl monomers such as styrene can be included.

[0076] As the acrylic monomer, acrylic acid amide, acrylonitrile, etc. can also be used. As the acrylic resin, a commercially available product can also be used. In addition, in this specification, the acrylic resin can be a styrene acrylic resin described later. In addition, in this specification, the expression of (meth) acrylic acid refers to at least one of acrylic acid and methacrylic acid.

[0077] The styrene acrylic resin is a copolymer obtained from a styrene monomer and an acrylic monomer, and examples thereof include styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-methacrylic acid-acrylate copolymers, styrene-α-methylstyrene-acrylic acid copolymers, styrene-α-methylstyrene-acrylic acid-acrylate copolymers, etc. Commercially available styrene acrylic resins can be used.

[0078] The polyolefin resin has an olefin such as ethylene, propylene, or butene in its structural skeleton, and any known polyolefin resin can be appropriately selected and used. As the olefin resin, a commercially available product can be used.

[0079] Examples of commercially available products of the resin particle emulsion that can be used in the present embodiment are as follows.

[0080] <Polyurethane resin emulsion>

[0081] SUPERFLEX870, 800, 150, 420, 460, 470, 610, 620, 700, 460s, 840, E-4000 (trade name of Daiichi Kogyo Seiyaku Co., Ltd.), PERMARIN UA-150 (trade name of Sanyo Chemical Industries, Ltd.), SANCURE2710 (trade name of Nippon Lubrizol), NeoRez R-9660, R-9637, R-940 (trade name of Kusumoto Chemicals Co., Ltd.), ADEKA BONTIGHTER HUX-380, 290K (trade name of ADEKA Co., Ltd.), RESAMINED-1060, D-2020, D-4080, D-4200, D-6300, D-6455 (trade name of Dainichi Seika Industries, Ltd.), TAKELAC W-6020, W-635, W-6061, W-605, W-635, W-6021, W-512-A-6 (trade names manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.).

[0082] <Acrylic resin emulsion>

[0083] VONCOAT4001 (trade name manufactured by DIC Corporation), POLYSOL AM-710, AM-920, AM-2300, AP-4735, AT-860, PSASE-4210E (trade name manufactured by Showa Denko K.K.), SAIVINOL SK-200 (trade name manufactured by Saiden Chemical Co., Ltd.), AE-120A (trade name manufactured by JSR Corporation), VINYBLAN 2682 (trade name manufactured by Nissin Chemical Industry Co., Ltd.), MOWINYL952B, 718A (trade name manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), K-854 (trade name manufactured by Chuo Rika Industry Co., Ltd.), Nipol LX852, LX874 (trade name manufactured by Nippon Zeon Co., Ltd.).

[0084] <Styrene acrylic resin emulsion>

[0085] MICROGEL E-1002, E-5002 (trade name of Nippon Paint Co., Ltd.), VONCOAT5454 (trade name of DIC Co., Ltd.), POLYSOLAP-7020, SAE1014 (trade name of Showa Denko Co., Ltd.), VINYBLAN2586 (trade name of Nissin Chemical Industry Co., Ltd.), ARROWBASE CB-1200, CD-1200 (trade names manufactured by UNITICA Co., Ltd.), MOWINYL 966A, 7320, 975N (trade names manufactured by Nippon Synthetic Chemical Co., Ltd.), JONCRYL 62J, 7100, 390, 711, 511, 7001, 632, 741, 450, 840, 74J, HRC-1645J, 734, 852, 7600, 775, 537J, 1535, PDX-7630A, 352J, 352D, PDX-7145, 538J, 7640, 7641, 631, 790, 780, 7610 (trade names manufactured by BASF).

[0086] <Other resin emulsions>

[0087] ELITEL KA-5071S, KT-8803, KT-9204, KT-8701, KT-8904, KT-0507 (trade name manufactured by UNITICA, polyester resin emulsion), HITECH SN-2002 (trade name manufactured by Toho Chemical Co., Ltd., polyester resin emulsion), POLYSOL SH-502 (trade name manufactured by Showa Denko Co., Ltd., vinyl acetate resin emulsion), POLYSOL AD-13, AD-2, AD-10, AD-96, AD-17, AD-70 (trade name manufactured by Showa Denko Co., Ltd., ethylene-vinyl acetate resin emulsion), POLYSOL PSASE-6010 (trade name manufactured by Showa Denko K.K., ethylene-vinyl acetate resin emulsion), AE373D (trade name manufactured by E-TEC, carboxyl-modified styrene-acrylic resin emulsion), SEIKADYNE 1900W (trade name manufactured by Dainichi Seika Industries, ethylene-vinyl acetate resin emulsion), VINYBLAN 2886 (trade name manufactured by Nissin Chemical Industries, Ltd., vinyl acetate-acrylic resin emulsion), VINYBLAN 5202 (trade name manufactured by Nissin Chemical Industries, Ltd., vinyl acetate acrylic resin emulsion), NK BINDER R-5HN (trade name manufactured by Shin-Nakamura Chemical Industries, Ltd.), and HYDRAN WLS-210 (trade name manufactured by DIC Corporation, non-cross-linking polyurethane emulsion).

[0088] 〔wax〕

[0089] The wax is not particularly limited, but examples thereof include hydrocarbon waxes and ester waxes which are condensates of fatty acids and monohydric alcohols or polyhydric alcohols. The hydrocarbon wax is not particularly limited, but examples thereof include paraffin waxes and polyolefin waxes such as polyethylene wax and polypropylene wax. These waxes may be used alone or in combination of two or more.

[0090] Examples of commercially available paraffin wax include AQUACER 497 and AQUACER 539 (these are product names, manufactured by BYK).

[0091] Examples of commercially available polyolefin waxes include CHEMIPEARL S120, S650, and S75N (product names, manufactured by Mitsui Chemicals, Inc.), AQUACER 501, AQUACER 506, AQUACER 513, AQUACER 515, AQUACER 526, AQUACER 593, and AQUACER 582 (product names, manufactured by BYK).

[0092] The water-insoluble components may be used alone or in combination of two or more.

[0093] In the treatment liquid composition involved in the present embodiment, it is preferred that the non-water-soluble component does not exceed 1.0 mass % relative to the total mass of the treatment liquid composition, more preferably does not contain more than 0.70 mass %, further preferably does not contain more than 0.50 mass %, particularly preferably does not contain more than 0.30 mass %, and more particularly preferably does not contain more than 0.10 mass %, or may not contain. By containing non-water-soluble components, there is a tendency to improve friction fastness, etc., but sometimes the coating stability is deteriorated. In contrast, even if the content of the non-water-soluble component of the treatment liquid composition involved in the present embodiment is within the above range, there is a tendency to make the friction fastness good and the coating stability good. In addition, from the viewpoint of being able to further obtain the effect achieved by the present invention, it is preferred that the non-water-soluble component is a resin particle.

[0094] 1.7 Other ingredients

[0095] The treatment liquid composition according to the present embodiment may contain a pH adjuster, an antiseptic / antifungal agent, a rust preventive, a chelating agent, a viscosity adjuster, a solubilizing agent, an antioxidant, and the like, as necessary.

[0096] 〔pH adjuster〕

[0097] Examples of pH adjusters include amines such as diethanolamine, triethanolamine, propanolamine, morpholine, and their modified products; organic acids such as acetic acid, citric acid, phthalic acid, oxalic acid, succinic acid, adipic acid, and amino acids; inorganic salts such as sodium hydroxide and potassium hydroxide; ammonium hydroxide, quaternary ammonium hydroxide (tetramethylammonium), and the like.

[0098] 〔Preservatives / antifungal agents〕

[0099] Examples of the preservative / antifungal agent include sodium benzoate, sodium pentachlorophenol, 2-pyridinethiol-1-oxide sodium salt, sodium sorbate, sodium dehydroacetate, and 1,2-dibenzothiazoline-3-one (PROXEL CRL, PROXEL BND, PROXEL GXL, PROXEL XL-2, and PROXEL TN manufactured by ICI).

[0100] 〔Chelating agent〕

[0101] The chelating agent has the property of capturing ions. Examples of such chelating agents include ethylenediaminetetraacetate (EDTA), ethylenediamine nitrilotriacetate, hexametaphosphate, pyrophosphate, and metaphosphate.

[0102] 1.8 Manufacturing method

[0103] The treatment liquid composition involved in this embodiment can be obtained by mixing the above components in any order and filtering to remove impurities as needed. As a mixing method for each component, it is preferred to use a method in which the materials are added in sequence in a container having a stirring device such as a mechanical stirrer or a magnetic stirrer and stirred and mixed. As a filtering method, centrifugal filtration, filter filtration, etc. can be performed as needed.

[0104] 1.9 Physical Properties of Treatment Liquid Composition

[0105] As the physical properties of the treatment liquid composition according to the present embodiment, pH, surface tension, viscosity, etc. can be adjusted to a desired range.

[0106] The pH of the treatment liquid composition according to the present embodiment is preferably less than 7. The pH is more preferably less than 6, further preferably less than 5, and particularly preferably less than 4. The inkjet ink composition described below that can be used together with the treatment liquid composition according to the present embodiment stabilizes the dispersion when the pH exceeds 8. When the pH of the treatment liquid composition is within the above range, the ink dispersion is easily destabilized when mixed with the inkjet ink composition, aggregation is promoted, and the reactivity with the ink becomes good, thereby sometimes further improving the color development.

[0107] The surface tension of the treatment liquid composition according to the present embodiment is preferably 10 mN / m or more and 40 mN / m or less, more preferably 25 mN / m or more and 40 mN / m or less at 25° C. The surface tension can be measured, for example, by using an automatic surface tensiometer CBVP-Z (trade name, manufactured by Kyowa Interface Science Co., Ltd.) to confirm the surface tension when a platinum plate is wetted with the treatment liquid composition in an environment of 25° C.

[0108] The treatment liquid composition involved in this embodiment preferably has a viscosity of 2 mPa·s or more and 15 mPa·s or less at 20° C., more preferably 2 mPa·s or more and 5 mPa·s or less, and more preferably 2 mPa·s or more and 3.6 mPa·s or less. The viscosity can be measured, for example, using a viscoelasticity tester MCR-300 (trade name, manufactured by Pysica) to measure the viscosity in an environment of 40° C. or 20° C.

[0109] 1.10 Purpose

[0110] The treatment liquid composition according to the present embodiment is preferably used for a water-based pigment inkjet ink. In addition, as the water-based pigment inkjet ink, an inkjet ink composition described below can be preferably used.

[0111] In addition, the treatment liquid composition involved in this embodiment is preferably applied to cloth for use. When forming an image on cloth with ink, high quality is required in terms of color development, wet rubbing fastness, texture, etc. According to the treatment liquid composition involved in this embodiment, there is a tendency that both excellent color development and excellent wet rubbing fastness required for forming an image on cloth can be achieved, and the texture is also good.

[0112] Examples of the raw materials constituting the fabric include natural fibers such as cotton, linen, wool, and silk, synthetic fibers such as polypropylene, polyester, acetate, triacetate, polyamide, and polyurethane, and biodegradable fibers such as polylactic acid. Blended fibers thereof are also possible.

[0113] In addition, the amide part in the structure of the polyamide epihalohydrin polymer contained in the treatment liquid composition of the present embodiment is bonded to the hydroxyl group of the fiber of the fabric, and has the function of improving water resistance by reducing the swelling of the fiber caused by water, the function of improving the structural strength by cross-linking of the epihalohydrin part, etc., and at least one function works independently of the raw material constituting the fabric. Therefore, regardless of whether the raw material constituting the fabric is natural fiber such as cotton or synthetic fiber such as polyester, the treatment liquid composition of the present embodiment has an excellent effect of improving wet friction fastness.

[0114] The whiteness of the fabric is preferably 70 or more, more preferably 80 or more, and even more preferably 90 or more. Whiteness refers to CIE / L ＊ a ＊ b ＊ L in the color system ＊ Value. Whiteness can be measured using a colorimeter "GretagMacbeth Spectrolino" (product name, manufactured by X-Rite). Fabrics with whiteness within the above range are relatively white fabrics, and therefore have a problem of being particularly prone to yellowing. However, since the treatment liquid composition involved in this embodiment is not prone to yellowing, even such fabrics can be used without causing the problem of yellowing.

[0115] 2. Composition of inkjet ink composition and treatment liquid composition

[0116] In the set of the inkjet ink composition and the treatment liquid composition according to one embodiment of the present invention,

[0117] A combination of an inkjet ink composition and the above-mentioned treatment liquid composition,

[0118] The inkjet ink composition is a water-based pigment inkjet ink containing pigment particles and resin particles. The pH of the ink composition exceeds 8 and contains particle components having a volume average particle size of 20 to 500 nm.

[0119] In addition, the set of inkjet ink composition and treatment liquid composition refers to the ink composition and treatment liquid composition of the set as long as the ink composition and treatment liquid composition of the set are used for recording as a set. That is, the ink composition and treatment liquid composition used for recording as a set are referred to as the set of inkjet ink composition and treatment liquid composition.

[0120] The inkjet ink composition of the set of the inkjet ink composition and the treatment liquid composition (hereinafter referred to as the "ink treatment liquid set") according to the present embodiment has an inkjet ink composition that stabilizes dispersion when the pH exceeds 8. When such an inkjet ink composition is mixed with the above-mentioned treatment liquid composition, the ink dispersion is easily unstable and the aggregation of the particle components is promoted, so the reactivity of the ink and the treatment liquid becomes good, and there is a tendency that the color development property is particularly excellent. Therefore, according to the ink treatment liquid set according to the present embodiment, it is possible to achieve both particularly excellent color development and excellent wet friction fastness.

[0121] Since the components of the treatment liquid composition of the ink treatment liquid set according to the present embodiment are as described above, the description thereof will be omitted. Hereinafter, the components contained in the inkjet ink composition of the ink treatment liquid set according to the present embodiment will be described.

[0122] 2.1 Inkjet Ink Composition

[0123] The inkjet ink composition included in the ink treatment liquid set according to the present embodiment is an aqueous pigment inkjet ink containing pigment particles and resin particles.

[0124] 2.1.1 Pigment particles

[0125] Examples of the pigment particles include organic pigments such as cyan, magenta, yellow, and black, and specialty pigments such as white pigments and bright pigments.

[0126] Examples of the organic pigment include quinacridone pigments, quinacridonequinone pigments, dioxane pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, anthrone pigments, indanthrone pigments, flavanone pigments, perylene pigments, diketopyrrolopyrrole pigments, perinone pigments, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, thioindigo pigments, isoindolinone pigments, azomethine pigments, dye chelates, dye lakes, nitro pigments, nitroso pigments, aniline black, and azo pigments such as insoluble azo pigments, condensed azo pigments, azo lakes, and chelated azo pigments.

[0127] Specific examples of the organic pigment include the following pigments.

[0128] Examples of pigments for cyan ink include CI Pigment Blue 1, 2, 3, 15:3, 15:4, 16, 22, 60, etc.; CI Vat Blue 4, 60, etc., preferably one selected from the group consisting of CI Pigment Blue 15:3, 15:4 and 60, or a mixture of two or more thereof.

[0129] As pigments for magenta ink, CI Pigment Red 5, 7, 12, 48 (Ca), 48 (Mn), 57 (Ca), 57:1, 112, 122, 123, 168, 184, 202, CI Pigment Violet 19, etc. can be listed, and preferably one or a mixture of two or more selected from the group consisting of CI Pigment Red 122, 202 and 209, and CI Pigment Violet 19.

[0130] As the pigment used for the yellow ink, CI Pigment Yellow 1, 2, 3, 12, 13, 14C, 16, 17, 73, 74, 75, 83, 93, 95, 97, 98, 119, 110, 114, 128, 129, 138, 150, 151, 154, 155, 180, 185 and the like are listed, and one or a mixture of two or more selected from the group consisting of CI Pigment Yellow 74, 109, 110, 128 and 138 is preferred.

[0131] The pigment used for the orange ink is CI Pigment Orange 36 or 43 or a mixture thereof.

[0132] The pigment used for the green ink is CI Pigment Green 7 or 36 or a mixture thereof.

[0133] Specific examples of carbon black include furnace black, lamp black, acetylene black, channel black (CI Pigment Black 7), and commercially available products include No. 2300, 900, MCF88, No. 20B, No. 33, No. 40, No. 45, No. 52, MA7, MA8, MA100, No2200B, etc. (trade names, manufactured by Mitsubishi Chemical Corporation), coloring black FW1, FW2, FW2V, FW18, FW200, etc. , S150, S160, S170, PRINTEX35, U, V, 140U, Special Black 6, 5, 4A, 4, 250, etc. (trade names, manufactured by Degussa), CONDUCTEXSC, RAVEN1255, 5750, 5250, 5000, 3500, 1255, 700, etc. (all trade names, manufactured by Columbia Carbon Company), REGAL400R, 330R, 660R, MOGUL L, MONARCH700, 800, 880, 900, 1000, 1100, 1300, 1400, ELFTEX12, etc. (trade names, manufactured by CABOT). These carbon blacks may be used alone or as a mixture of two or more.

[0134] As the bright pigment, there is no particular limitation as long as it is a pigment that can show brightness when attached to a medium, and examples thereof include metal particles of one or more alloys (also referred to as metal pigments) selected from the group consisting of aluminum, silver, gold, platinum, nickel, chromium, tin, zinc, indium, titanium and copper, or pearlescent pigments having pearl luster. Representative examples of pearlescent pigments include titanium dioxide coated mica, fish scale foil, bismuth oxychloride and other pigments having pearl luster or interference luster. In addition, the bright pigment may also be subjected to a surface treatment for inhibiting reaction with water.

[0135] In addition, as white pigment, metal compounds such as metal oxides, barium sulfate, and calcium carbonate can be listed. As metal oxides, for example, titanium dioxide, zinc oxide, silicon dioxide, aluminum oxide, and magnesium oxide can be listed. In addition, white pigment can also use particles with a hollow structure.

[0136] The above-mentioned pigment particles may be used alone or in combination of two or more. From the viewpoint of storage stability such as light resistance, weather resistance, and gas resistance, the pigment particles are preferably organic pigments.

[0137] The pigment particles are preferably able to be stably dispersed in the ink. For example, the pigment particles can be used as self-dispersible pigment particles by oxidizing or sulfonating the surface of the pigment particles using ozone, hypochlorous acid, fuming sulfuric acid, etc., or by dispersing them using a resin dispersant.

[0138] Examples of the resin dispersant include polyvinyl alcohols, polyacrylic acid, acrylic acid-acrylonitrile copolymers, vinyl acetate-acrylate copolymers, acrylic acid-acrylate copolymers, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-methacrylic acid-acrylate copolymers, styrene-α-methylstyrene-acrylic acid copolymers, styrene-α-methylstyrene-acrylic acid-acrylate copolymers, styrene-maleic acid copolymers, styrene-maleic anhydride copolymers, vinylnaphthalene-acrylic acid copolymers, vinylnaphthalene-maleic acid copolymers, vinyl acetate-maleic acid copolymers, vinyl acetate-crotonic acid copolymers, vinyl acetate-acrylic acid copolymers, and the like, and salts thereof.

[0139] Among these, copolymers of monomers having hydrophobic functional groups and monomers having hydrophilic functional groups, and polymers composed of monomers having both hydrophobic functional groups and hydrophilic functional groups are preferred. As the form of the copolymer, any form of random copolymers, block copolymers, alternating copolymers, and graft copolymers can be used.

[0140] The resin dispersant described here has the function of improving the dispersibility of the pigment particles. The resin dispersant is, for example, water-soluble. And / or the resin dispersant is attached to the pigment and exists around the pigment particles.

[0141] The content of the resin dispersant can be appropriately selected according to the pigment particles to be dispersed, but is preferably 5 parts by mass or more and 200 parts by mass or less, and more preferably 20 parts by mass or more and 120 parts by mass or less, based on 100 parts by mass of the content of the pigment particles in the ink.

[0142] The content of the pigment particles in the ink is preferably 0.3% by mass or more and 20% by mass or less relative to the total mass of the ink, more preferably 0.5% by mass or more and 15% by mass or less, further preferably 1 to 10% by mass, and particularly preferably 1.5 to 5% by mass. If the content of the pigment particles is within the above range, it is not easy to cause nozzle clogging of the inkjet recording device, and the color concentration can be fully satisfied. In addition, if the content of the pigment particles is above the above range, it is further easy to form an image with excellent color development.

[0143] 2.1.2 Resin particles

[0144] As the resin particles, the same resin particles as those in the water-insoluble component which may be contained in the above-mentioned treatment liquid composition can be used.

[0145] 2.1.3 Physical properties of particle components

[0146] The volume average particle size of the particle components such as the above-mentioned pigment particles and resin particles contained in the inkjet ink composition is 20 to 500 nm.

[0147] The volume-based average particle size (D50) (also referred to as "volume average particle size") of the particle component (before ink mixing) is 20 nm or more, preferably 50 nm or more, more preferably 80 nm or more, further preferably 110 nm or more, and particularly preferably 150 nm or more. In addition, the volume average particle size of the particle component is 500 nm or less, preferably 400 nm or less, more preferably 300 nm or less, further preferably 250 nm or less, and particularly preferably 200 nm or less. If the volume average particle size is within this range, it is easy to obtain or easy to become a preferred characteristic. In addition, if the volume average particle size of the particle component is within the range, the particle component is not easy to settle, the dispersion stability can be good, and when applied to an inkjet recording device, there is a tendency that nozzle clogging, etc., is not easy to occur.

[0148] The volume average particle size of the particle component can be measured by a particle size distribution measuring device based on the laser diffraction scattering method. As a particle size distribution measuring device, for example, a particle size distribution meter based on the dynamic light scattering method (for example, "MICROTRAC UPA" manufactured by Nikkiso Co., Ltd.) can be listed.

[0149] The content of the particle component is 0.2 mass % to 40 mass % in terms of solid content relative to the total mass of the inkjet ink composition, preferably 2 mass % to 30 mass % or less, more preferably 4 mass % to 20 mass % or less, and further preferably 6 mass % to 15 mass % or less.

[0150] The above-mentioned pigment particles or resin particles contained in the inkjet ink composition preferably have anionic properties. The above-mentioned treatment liquid composition contains a polyamide epihalohydrin polymer or a specific quaternary ammonium salt polymer as a cationic polymer. Therefore, if the pigment particles or resin particles of the ink have anionic properties, a cohesion reaction effectively occurs when the treatment liquid composition is mixed with the ink, and there is a tendency to obtain more excellent color development.

[0151] As the anionic pigment particles, preferably there are pigments having a dispersant having an anionic group on the surface. Examples of the dispersant having an anionic group include -COO - or -SO3 - Acts as a dispersant for anionic groups.

[0152] As the anionic resin particles, there can be listed resin particles having anionic functional groups such as carboxyl, sulfonic, and hydroxyl groups, and preferably anionic polyurethane resins. Among the commercially available polyurethane resins mentioned above, as anionic polyurethane resins, there can be listed SUPERFLEX 460, 460s, 840, etc. manufactured by Daiichi Kogyo Seiyaku Co., Ltd.; TAKELAC WS-5000, WS-6021, W-512-A-6, etc. manufactured by Mitsui Chemicals Polyurethane Co., Ltd.

[0153] 2.1.4 Water

[0154] The inkjet ink composition of the ink treatment liquid set according to the present embodiment is a water-based pigment inkjet ink and contains water. "Water-based" means containing water as a main solvent. The water is the same as the water that can be contained in the treatment liquid composition described above.

[0155] The water content is not particularly limited, but may be, for example, 40% by mass or more, further 50% by mass or more, or 60% by mass or more, relative to the total mass of the inkjet ink composition. The upper limit of the water content in the inkjet ink composition may be 90% by mass or less, 80% by mass or less, or 70% by mass or less.

[0156] 2.1.5 Organic solvents

[0157] The inkjet ink composition of the ink treatment liquid set according to the present embodiment may contain an organic solvent. As the organic solvent, a water-soluble organic solvent is preferred. Such a water-soluble organic solvent may be the same as the water-soluble organic solvent that may be contained in the treatment liquid composition described above.

[0158] When a water-soluble organic solvent is contained, the content thereof is preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less, relative to the total mass of the inkjet ink composition. In addition, the content of the water-soluble organic solvent is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more, relative to the total mass of the inkjet ink composition.

[0159] 2.1.6 Surfactants

[0160] The inkjet ink composition included in the ink treatment liquid set according to the present embodiment may contain a surfactant. The surfactant may be the same as the surfactant that may be contained in the treatment liquid composition described above, and the content thereof may be the same.

[0161] 2.1.7 Other ingredients

[0162] The inkjet ink composition of the ink treatment liquid set according to the present embodiment may contain wax, pH adjuster, preservative / mildewproof agent, rust inhibitor, chelating agent, viscosity modifier, cosolvent, antioxidant, etc. as required. These components are the same as those that may be contained in the above-mentioned treatment liquid composition, and therefore, description thereof is omitted.

[0163] 2.1.8 Manufacturing method

[0164] The inkjet ink composition of the ink treatment liquid set according to the present embodiment can be obtained by mixing the above components in any order and removing impurities by filtering as needed. As a method for mixing the components, it is preferred to use a method in which the materials are added sequentially in a container having a stirring device such as a mechanical stirrer or a magnetic stirrer and stirred and mixed. As a filtering method, centrifugal filtration, filter filtration, etc. can be performed as needed.

[0165] 2.1.9 Physical Properties of Inkjet Ink Compositions

[0166] As the physical properties of the inkjet ink composition possessed by the ink treatment liquid set according to the present embodiment, pH, surface tension, viscosity, etc. can be adjusted to a desired range.

[0167] The pH of the inkjet ink composition exceeds 8. Preferably, the pH exceeds 9, more preferably, the pH exceeds 10, and further preferably, the pH exceeds 11. When the pH of the inkjet ink composition is within the above range, the ink dispersion is easily unstable when mixed with the treatment liquid composition, and aggregation of the particle components is promoted, which tends to further improve the color development property.

[0168] The physical properties such as surface tension and viscosity may be the same as those of the above-mentioned treatment liquid composition.

[0169] 3. Treatment methods

[0170] A processing method according to one embodiment of the present invention comprises:

[0171] an attachment step of attaching the above-mentioned treatment liquid composition to the fabric; and

[0172] a heating step of heating the fabric to which the treatment liquid composition is attached,

[0173] The surface temperature of the fabric in the heating step is 100° C. or higher.

[0174] In the treatment method involved in this embodiment, the fabric to which the above-mentioned treatment liquid composition is attached is treated by a process including heating the fabric so that its surface temperature is 100° C. or higher. By implementing this treatment method, both excellent color development and excellent wet rubbing fastness can be achieved.

[0175] Hereinafter, each step of the processing method according to the present embodiment will be described.

[0176] 3.1 Attachment process

[0177] The treatment method according to the present embodiment includes an attachment step of attaching the above-mentioned treatment liquid composition to the fabric. The treatment liquid composition and the fabric are as described above, and therefore, description thereof will be omitted.

[0178] As a method for attaching the treatment liquid composition to the fabric (coating method), for example, a method of immersing the fabric in the treatment liquid composition (immersion coating), a method of coating the treatment liquid composition with a roller coater or the like (roller coating), a method of spraying the treatment liquid composition by a spray device or the like (spray coating), a method of spraying the treatment liquid composition by an inkjet method (inkjet coating), etc., can be cited, and any method can be used. When the treatment liquid composition is applied by inkjet coating, it is easy to control the treatment liquid composition to be uniformly attached to the fabric, so it is preferred. In addition, when the treatment liquid composition is applied by immersion coating or spray coating, the treatment liquid composition can be applied to the fabric in a short time, so it is preferred.

[0179] The coating amount of the treatment liquid composition is preferably 50 to 200 g / m2 per unit area of ​​the fabric. 2 , more preferably 70 to 170 g / m 2 , more preferably 90 to 140 g / m 2 , especially preferably 100 to 120 g / m 2 When the coating amount of the treatment liquid composition is within the above range, the effects achieved by the present invention may be more easily obtained.

[0180] 3.2 Heating process

[0181] The treatment method according to this embodiment has a heating step of heating the fabric to which the treatment liquid composition is attached after the above-mentioned attachment step. The heating method is not particularly limited, but examples thereof include convection heat drying, radiation heat drying, and conduction heat drying. In addition, as a heat source used for heating, heat generated by a combustible gas burner, a carbon heater / ceramic heater / halogen lamp, or an infrared lamp can be used.

[0182] The lower limit of the surface temperature of the fabric in the heating process is preferably 40°C or more, more preferably 80°C or more, and further preferably 100°C or more. In addition, the upper limit of the surface temperature of the fabric in the heating process is preferably 180°C or less. By setting the heating temperature to 180°C or less, damage caused by thermal stress on the fabric during heating and drying can be suppressed. In addition, by setting the heating temperature to a value above the lower limit, the water or solvent contained in the treatment liquid composition can be efficiently evaporated, thereby promoting the drying of the treated fabric. Moreover, when cotton is contained in the raw material constituting the fabric, the cross-linking reaction between the polyamide epihalohydrin polymer contained in the treatment liquid composition and the cellulose fiber in the kapok fabric can be promoted by setting the heating temperature to 100°C or more.

[0183] 4. Examples

[0184] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. Hereinafter, "%" is based on mass unless otherwise specified.

[0185] 4.1 Preparation of treatment liquid composition

[0186] The components were mixed in the amounts shown in Tables 1 and 2 below, stirred at room temperature for two hours, and then filtered using a membrane filter with a pore size of 5 μm to obtain each treatment liquid composition. In addition, the units of the contents of the components shown in Tables 1 and 2 below are mass %, which are expressed as "wt %" in the table.

[0187] 4.2 Preparation of inkjet ink composition

[0188] The components are mixed in the amounts shown in the following black ink component examples, stirred at room temperature for two hours, and then filtered using a membrane filter with a pore size of 5 μm to obtain an inkjet ink composition (black ink). In addition, in the following black ink component examples, the content of the pigment is the pigment solid content, and the content of the resin emulsion is the resin solid content. In addition, the carbon black pigment used for the preparation of the inkjet ink composition is preliminarily mixed with a pigment dispersant (not described in the following component examples) as a water-soluble styrene acrylic resin in water at a mass ratio of 1:1 (pigment: pigment dispersant), and fully stirred to prepare a black pigment dispersion for use.

[0189] [Example of black ink composition]

[0190]

[0191]

[0192] The above-mentioned black ink will be supplementally described.

[0193] Carbon black pigment: CI Pigment Black 7

[0194] WS6021: TAKELAC WS-6021, trade name of Mitsui Chemicals, solid content 30% by mass, polyurethane resin

[0195] EDTA: Ethylenediaminetetraacetic acid, metal chelating agent

[0196] ·OLFINE E1010: a trade name manufactured by Nissin Chemical Industry Co., Ltd., an acetylene glycol-based surfactant, HLB=14

[0197] SURFYNOL 104: Trade name of Nissin Chemical Industry Co., Ltd., acetylene glycol surfactant, HLB = 4

[0198] The pH of the black ink was more than 8. The pH was measured by immersing an electrode portion in the inkjet ink composition using a benchtop pH meter Model F-72 (manufactured by Horiba, Ltd.).

[0199] 4.3 Recording Media

[0200] As the recording medium, the following fabrics were used.

[0201] 〔Kapok cloth〕

[0202] Fiber: Cotton

[0203] Type: Taffeta

[0204] Composition: Cotton 100%

[0205] Weight: 8.04~8.55(g / m 2 )

[0206] Specifications: 145~150(cm)

[0207] Manufacturing company: A.FERRARIO

[0208] Whiteness L ＊ Value: 91.5

[0209] In addition, the L of the cloth ＊ The value is measured using a colorimeter "Gretag Macbeth Spectrolino" (product name, manufactured by X-Rite Corporation).

[0210] [Table 1]

[0211]

[0212] [Table 2]

[0213]

[0214] Supplementary explanation is given for the records in the above-mentioned Tables 1 and 2.

[0215] <Ingredients>

[0216] Supplementary explanations on the polyamide epihalohydrin polymer, the quaternary ammonium salt polymer, the resin particles, the surfactant, and the preservative are as follows.

[0217] 〔Polyamide epihalohydrin polymer〕

[0218] Polyamide-epichlorohydrin polymer A: trade name "WS4020", manufactured by Starlight PMC

[0219] Polyamide polyamine-epichlorohydrin polymer: trade name "AF-255", manufactured by Arakawa Chemical Industries, Ltd.

[0220] Polyamide-epichlorohydrin polymer B: trade name "WS4030", manufactured by Starlight PMC

[0221] ·Dimethylamine-ethylenediamine-epichlorohydrin polycondensate: trade name "PE-30", manufactured by Yokkaichi Synthetic Co., Ltd.

[0222] 〔Quaternary ammonium salt polymer〕

[0223] Quaternary ammonium salt polymer A: trade name "PAS-J-41", manufactured by NITTOBO MEDICAL, diallyldimethylammonium chloride-acrylic acid amide copolymer, average molecular weight 10,000

[0224] Quaternary ammonium salt polymer B: trade name "PAS-J-81", manufactured by NITTOBO MEDICAL, diallyldimethylammonium chloride-acrylic acid amide copolymer, average molecular weight 180,000

[0225] ·Quaternary ammonium salt polymer C: Trade name "EP1137", manufactured by Takamatsu Oil & Fats Co., Ltd.

[0226] 〔Resin particles〕

[0227] Polyurethane resin: Trade name "SF-620", manufactured by Daiichi Pharmaceutical Industry Co., Ltd.

[0228] 〔Surfactant〕

[0229] · Acetylene glycol: trade name "SURFYNOL 485", manufactured by Nissin Chemical Industry Co., Ltd., HLB = 17

[0230] 〔preservative〕

[0231] PROXEL XL2: Trade name of Lonza

[0232] <Processing conditions>

[0233] The drying temperature after application of the pretreatment liquid composition (treatment liquid composition) and the drying temperature after ink printing are shown in the table below: The surface temperature of the fabric when the heat drying treatment is performed using a conveyor drying oven "Economax D" (trade name of M&R Co., Ltd.).

[0234] <Evaluation Items>

[0235] The spray coating stability evaluation test was conducted by combining the "1008 + The SPRAYSONTROLLER is used with a two-fluid nozzle that generates a flat spray pattern.

[0236] The pH was measured by using a tabletop pH meter Model F-72 (manufactured by Horiba, Ltd.) and immersing the electrode portion in the treatment liquid composition.

[0237] 4.4 Evaluation Method

[0238] As evaluation tests, spray coating stability, color development, rubbing fastness, texture and light fastness were evaluated. The evaluation method is as follows.

[0239] 4.4.1 Spray coating stability (two-fluid nozzle)

[0240] By combining the "1008 + The composition of each treatment liquid obtained above was adjusted to 110 g / m per unit area by using a "SPRAYSONTROLLER" and a two-fluid nozzle for generating a planar spray pattern. 2 The surface of the fabric described in the above "4.3 Recording Medium" is uniformly coated with a coating amount. At this time, the coating weight change consumed during the coating treatment time of the treatment liquid composition is monitored, and the spray coating stability is evaluated as the nozzle being free of clogging and being able to apply the prescribed consumption amount. The spray coating stability is determined as follows.

[0241] (Judgment Criteria)

[0242] A: The coating weight change rate at the end of coating is less than ±10% relative to the initial setting value.

[0243] B: The coating weight change rate at the end of coating is ±10% or more and less than 20% relative to the initial setting value.

[0244] C: The coating weight change rate at the end of coating is ±20% or more relative to the initial setting value.

[0245] 4.4.2 Color rendering (black ink_100% duty cycle)

[0246] The fabric coated with the treatment liquid composition by the above method was subjected to a heat drying treatment for 7 minutes at the drying temperature described in the table using a conveyor drying oven "Economax D" (manufactured by M&R Co., Ltd.), thereby completing the treatment of the fabric. The inkjet ink composition prepared as described above was attached to the fabric by an inkjet method using an inkjet printer (product name "PX-G930", manufactured by Seiko Epson Corporation) to print an image. The printed pattern (image) had a resolution of 1440×720 dpi, a printing area of ​​210 mm×297 mm, and a solid image was printed.

[0247] Here, the “solid image” refers to an image in which dots are recorded for all pixels that are pixels of the minimum recording unit area defined by the recording resolution.

[0248] The fabric to which the inkjet ink composition adhered was subjected to heat drying treatment at 160° C. for 5 minutes using a conveyor drying oven “Economax D” (manufactured by M&R Co.), and then returned to 25° C. to obtain a printed product.

[0249] The optical density (hereinafter also referred to as "OD value") of the image of the printed fabric was measured using a fluorescence spectrophotometer ("FD-7", manufactured by Konica Minolta Co., Ltd.) to evaluate the color development. The evaluation was as follows.

[0250] (Judgment Criteria)

[0251] S: OD value is 1.5 or more. (Particularly good)

[0252] A: OD value is 1.4 or more and less than 1.5. (Good)

[0253] B: OD value is 1.25 or more and less than 1.4.

[0254] C: OD value is less than 1.25.

[0255] 4.4.3 Rubbing fastness (discoloration)

[0256] The fabric printed with a duty cycle of 100% using the above method was tested for abrasion resistance by dry and wet methods using the test method based on ISO105-X12, and judged according to the following criteria. The abrasion resistance achieved by wet and dry methods was judged according to the following criteria as the difference in OD values ​​of discoloration before and after the abrasion resistance test.

[0257] (Dry friction strength criteria)

[0258] S: The difference in OD value before and after the abrasion resistance test is less than 0.15. (Extremely good)

[0259] A: The difference in OD value before and after the abrasion resistance test is 0.15 or more and less than 0.20. (Good)

[0260] B: The difference in OD value before and after the abrasion resistance test is 0.20 or more and less than 0.25.

[0261] C: The difference in OD value before and after the abrasion resistance test is 0.25 or more.

[0262] (Criteria for determination of wet friction strength)

[0263] S: The difference in OD value before and after the abrasion resistance test is less than 0.20. (Extremely good)

[0264] A: The difference in OD value before and after the abrasion resistance test is 0.20 or more and less than 0.25. (Good)

[0265] B: The difference in OD value before and after the abrasion resistance test is 0.25 or more and less than 0.30.

[0266] C: The difference in OD value before and after the abrasion resistance test is 0.30 or more.

[0267] 4.4.4 Texture (shear rigidity)

[0268] The shear rigidity of the fabric printed at a duty ratio of 100% by the above method was evaluated using a tensile shear tester KES-FB1-A manufactured by KATOTRCH Co., Ltd. The texture was evaluated according to the following criteria using the shear rigidity value.

[0269] (Judgment Criteria)

[0270] S: Shear rigidity is less than 6.0 gf / cm·deg.

[0271] A: Shear rigidity is 6.0 gf / cm·deg or more and less than 8.0 gf / cm·deg.

[0272] B: Shear rigidity is 8.0 gf / cm·deg or more and less than 10.0 gf / cm·deg.

[0273] C: Shear rigidity is 10.0 gf / cm·deg or more.

[0274] 4.4.5 Lightfastness (yellowing)

[0275] The fabric obtained by coating and drying the treatment liquid composition under the conditions described in "4.4.2 Color Development (Black Ink_100% Duty Cycle)" was irradiated with 20 MJ / m using SUGA Testing Machine XENON WEATHER METER: XL75s.2 The xenon light with a cumulative irradiance of . The degree of discoloration of the pretreated fabric before and after the irradiation was derived as a color difference ΔEab using a fluorescence spectrophotometer ("FD-7", manufactured by KONICA MINOLTA). The fabric used for evaluation was the white cotton described in "4.3 Recording Medium" above, L ＊ The value was expressed as 91.5. Using the color difference value, the light resistance was determined according to the following criteria.

[0276] (Judgment Criteria)

[0277] A: The color difference is less than 2.0.

[0278] B: The color difference is 2.0 or more and less than 4.0.

[0279] C: The color difference is 4.0 or more.

[0280] 4.5 Evaluation results

[0281] The evaluation results are shown in Tables 1 and 2 above.

[0282] Comparison between the examples and the comparative examples shows that the treatment liquid composition, the inkjet ink composition, the treatment liquid composition set, and the recording method according to the present embodiment can achieve both excellent color development and excellent wet rubbing fastness.

[0283] From the comparison between Example 2 and Comparative Example 1, it is understood that by using a specific quaternary ammonium salt polymer instead of a polyvalent metal salt, both excellent color development and wet rubbing fastness can be achieved.

[0284] In addition, as can be seen from the comparison between Example 2 and Comparative Examples 1 and 2, the treatment liquid composition according to the present embodiment is less likely to turn yellow.

[0285] Comparison between Example 2 and Comparative Examples 3 to 4 shows that the inclusion of a polyamide epihalohydrin polymer and a specific quaternary ammonium salt polymer enables both excellent color development and wet rubbing fastness to be achieved.

[0286] The results of Examples 1 to 3 show that various polyamide epihalohydrin polymers can achieve both excellent color development and wet rubbing fastness.

[0287] In addition, the results of Examples 2 and 4 to 5 show that various specific quaternary ammonium salt polymers can achieve both excellent color development and wet rubbing fastness.

[0288] The results of Examples 2 and 6 to 9 show that both excellent color development and wet rubbing fastness can be achieved within a predetermined wide range of the content of the polyamide epihalohydrin polymer.

[0289] In addition, the results of Examples 2 and 10 to 13 show that both excellent color development and wet rubbing fastness can be achieved at a content of a specific quaternary ammonium salt polymer within a predetermined wide range.

[0290] Furthermore, the results of Examples 2 and 14 to 15 show that both excellent color development and wet rubbing fastness can be achieved when the contents of both the polyamide epihalohydrin polymer and the specific quaternary ammonium salt polymer are within a predetermined wide range.

[0291] The results of Examples 2 and 16 to 17 show that spray coating stability can be maintained well even when a predetermined amount of a water-insoluble component is contained.

[0292] The results of Examples 4 and 18 show that the color development property is good when the pH of the treatment liquid composition is lower.

[0293] The results of Examples 2 and 19 to 20 show that the friction fastness can be improved by drying the fabric coated with the treatment liquid composition at a predetermined temperature or higher.

[0294] The following contents are derived from the above-mentioned embodiments.

[0295] In one embodiment of the treatment liquid composition,

[0296] Containing: polyamide epihalohydrin polymer; and

[0297] A quaternary ammonium salt polymer other than the polyamide epihalohydrin polymer.

[0298] In one embodiment of the above-mentioned treatment liquid composition,

[0299] It can be applied on fabric for use.

[0300] In any one of the above-mentioned treatment liquid compositions,

[0301] The L of the fabric ＊ The value can be above 90.

[0302] In any one of the above-mentioned treatment liquid compositions,

[0303] The pH of the treatment liquid composition may be less than 7.

[0304] In any one of the above-mentioned treatment liquid compositions,

[0305] The treatment liquid composition may not contain more than 1.0% by mass of water-insoluble components based on the total mass of the treatment liquid composition.

[0306] In one embodiment of the set of the inkjet ink composition and the treatment liquid composition,

[0307] A combination of an inkjet ink composition and a treatment liquid composition according to any one of the above aspects,

[0308] The inkjet ink composition is a water-based pigment inkjet ink containing pigment particles and resin particles. The pH of the ink composition exceeds 8 and contains particle components having a volume average particle size of 20 to 500 nm.

[0309] In one embodiment of the set of the inkjet ink composition and the treatment liquid composition,

[0310] The particle component may be anionic.

[0311] In one aspect of the processing method, there is:

[0312] an attachment step of attaching the treatment liquid composition of any one of the above aspects to the fabric; and

[0313] a heating step of heating the fabric to which the treatment liquid composition is attached,

[0314] The surface temperature of the fabric in the heating step is 100° C. or higher.

[0315] The present invention is not limited to the above-mentioned embodiments, and various modifications are possible. For example, the present invention includes a structure that is substantially the same as the structure described in the embodiments, such as a structure with the same function, method and result, or a structure with the same purpose and effect. In addition, the present invention includes a structure that replaces a non-essential part of the structure described in the embodiments. In addition, the present invention includes a structure that achieves the same effect as the structure described in the embodiments, or a structure that can achieve the same purpose. In addition, the present invention includes a structure in which a known technology is added to the structure described in the embodiments.

Claims

1. A treatment liquid composition, characterized in that Does not contain polyvalent metal salts, contains: Polyamide epihalohydrin polymers; and The quaternary ammonium salt polymer other than the polyamide epihalohydrin polymer, The polyamide epihalohydrin polymer is one or more selected from polyamine-epihalohydrin copolymers and amine-epihalohydrin copolymers, The quaternary ammonium salt polymer is a polymer that is soluble in water, has one or more quaternary ammonium salts in the chain of repeating units forming the polymer, and does not have a halohydrin structure.

2. The treatment liquid composition according to claim 1, characterized in that The treatment liquid composition is applied on a fabric for use.

3. The treatment liquid composition according to claim 2, characterized in that: The L of the fabric ＊ The value is above 90.

4. The treatment liquid composition according to any one of claims 1 to 3, characterized in that The pH of the treatment liquid composition is less than 7.

5. The treatment liquid composition according to any one of claims 1 to 3, characterized in that The treatment liquid composition does not contain more than 1.0% by mass of water-insoluble components based on the total mass of the treatment liquid composition.

6. A set of an inkjet ink composition and a treatment liquid composition, which is a set of an inkjet ink composition and a treatment liquid composition according to any one of claims 1 to 5, characterized in that: The inkjet ink composition is a water-based pigment inkjet ink containing pigment particles and resin particles. The pH of the ink composition exceeds 8 and contains particle components having a volume average particle size of 20 to 500 nm.

7. The set of inkjet ink composition and treatment liquid composition according to claim 6, characterized in that: The particle component is anionic.

8. A processing method, characterized in that: have: an attaching step of attaching the treatment liquid composition according to any one of claims 1 to 5 to a fabric; and a heating step of heating the fabric to which the treatment liquid composition is attached, The surface temperature of the fabric in the heating step is 100° C. or higher.

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