Treatment liquid composition, set of inkjet ink composition and treatment liquid composition, and treatment method

Abstract

To provide a treatment liquid composition that achieves both of excellent color development and excellent wet friction fastness with little discoloration even during wet friction.SOLUTION: A treatment liquid composition according to the present disclosure includes a polyamide epihalohydrin polymer, and a quaternary ammonium salt polymer other than the polyamide epihalohydrin polymer.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Inkjet recording is a method of ejecting droplets of an inkjet ink composition (hereinafter also referred to as "ink") from fine nozzles and depositing them on a recording medium to perform recording. Conventionally, when ejecting ink onto a recording medium by inkjet recording to form an image, a technique of pretreating the recording medium using a treatment liquid composition containing a flocculant has been known in order to improve the color development and other properties of the recorded matter.

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

[0004] [Patent Document 1] Japanese Patent Publication No. 2021-020394 Summary of the Invention [Problem to be solved by the invention]

[0005] However, it has been difficult to achieve both excellent color development and excellent wet friction fastness, which means that the color does not easily fade even when wet rubbed. [Means for solving the problem]

[0006] One aspect of the treatment liquid composition according to the present invention is a polyamide epihalohydrin polymer; and a quaternary ammonium salt polymer other than the polyamide epihalohydrin polymer.

[0007] One embodiment of the set of the inkjet ink composition and the treatment liquid composition according to the present invention comprises: A set of an inkjet ink composition and a treatment liquid composition of the above-described one embodiment, The inkjet ink composition is a water-based pigment inkjet ink containing pigment particles and resin particles, and has a pH of more than 8 and contains particle components with a volume average particle diameter of 20 to 500 nm.

[0008] One aspect of the processing method according to the present invention is to an application step of applying the treatment liquid composition of the above aspect to a fabric; 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. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, embodiments of the present invention will be described. The embodiments described below are examples of the present invention. The present invention is not limited to the following embodiments, and includes various modified forms that are implemented within the scope of the present invention. Note that not all of the configurations described below are necessarily essential configurations of the present invention.

[0010] 1. Treatment liquid composition The treatment liquid composition according to one embodiment of the present invention comprises: a polyamide epihalohydrin polymer; and a quaternary ammonium salt polymer other than the polyamide epihalohydrin polymer.

[0011] According to the above constitution, it is possible to obtain excellent color development and excellent wet friction fastness that is resistant to discoloration even when wet rubbed.

[0012] Conventionally, when forming images with ink on a recording medium such as fabric, it has been difficult to achieve both high color development and robustness (especially discoloration due to wet friction and washability). This is because, while maintaining ink solids near the surface of the recording medium is necessary to achieve good color development, the presence of ink solids near the surface of the recording medium makes the ink more susceptible to peeling due to friction and other factors, resulting in poor robustness. Furthermore, polyvalent metal salts, which have traditionally been used as flocculants, improve the aggregation reactivity with ink components depending on the amount, making it easy to control color development. However, they can sometimes form crystallized products near the surface of the recorded material. Such crystallized products are easily soluble in water, and when the recorded material is wetted with water, the crystallized products near the surface dissolve, leaving cavities where the crystallized products were located. These cavities are likely to be the starting point for ink peeling, and therefore treatment solutions using polyvalent metal salts tend to have poor wet friction robustness. Furthermore, when crystallized products are present on the recorded material, white spots appear on the printed surface, creating a problem of whitening.

[0013] In contrast, the treatment liquid composition according to this embodiment uses a quaternary ammonium salt polymer other than a polyamidoepihalohydrin polymer instead of a polyvalent metal salt. For example, when the recording medium is a fabric, such a quaternary ammonium salt polymer is coated on the fiber surface of the fabric, providing excellent aggregation reactivity of ink that comes into contact with the fiber surface, high color development performance, and, since it does not produce crystallized products like polyvalent metal salts, it is easy to maintain wet rub fastness. Furthermore, the treatment liquid composition according to this embodiment uses a polyamidoepihalohydrin polymer. The amide moieties in the polyamidoepihalohydrin polymer structure bond with hydroxyl groups in the fabric fibers, thereby improving water resistance by reducing swelling of the fibers due to water absorption, and the epihalohydrin moieties crosslink to improve structural strength, thereby improving wet rub fastness. As described above, the treatment liquid composition according to this embodiment is able to achieve both excellent color development and excellent wet rub fastness by containing a quaternary ammonium salt polymer other than a polyamide epihalohydrin polymer and a polyamide epihalohydrin polymer.

[0014] Hereinafter, each component contained in the treatment liquid composition according to this embodiment and components that may be contained therein will be described.

[0015] 1.1 Polyamide epihalohydrin polymers The treatment liquid composition according to this embodiment contains a polyamide epihalohydrin polymer.

[0016] A polyamide epihalohydrin polymer is a polymer obtained by polymerizing a monomer containing an amine and an epihalohydrin. Examples of polyamide epihalohydrin polymers include polyamine-epihalohydrin copolymers, polyamide-epihalohydrin copolymers, polyamidepolyamine-epihalohydrin copolymers, and amine-epihalohydrin copolymers. These polymers can be obtained by known methods, such as a method of polymerizing a monomer containing an amine and an epihalohydrin, or a method of graft polymerizing a monomer containing epihalohydrin onto a polyamide obtained by polymerizing a monomer containing an amine and a carboxylic acid.

[0017] Epihalohydrin contains a halogen atom in its structure. Examples of halogen atoms include F, Cl, Br, and I. Among these halogen atoms, Cl is preferred for epihalohydrin, so epichlorohydrin is preferred. Therefore, the polyamide-epihalohydrin polymer is preferably a polyamide-epichlorohydrin polymer, and specifically, polyamine-epichlorohydrin copolymer, polyamide-epichlorohydrin copolymer, polyamide-polyamine-epichlorohydrin copolymer, or amine-epichlorohydrin copolymer is preferred. Among these, polyamide-epichlorohydrin copolymer is more preferred.

[0018] Commercially available polyamide epihalohydrin polymers include WS-4020, 4030, 4027, and TS-4070 (manufactured by Seiko PMC Corporation, polyamide-epichlorohydrin polymers), WS-4011 (manufactured by Seiko PMC Corporation, polyamine-epichlorohydrin polymers), AF-100, 251S, 255, 255LOX, and 2500 (manufactured by Arakawa Industrial Chemical Industries, Ltd., polyamidepolyamine-epichlorohydrin polymers), Catiomaster PE-30 (manufactured by Yokkaichi Synthetic Co., Ltd., dimethylamine-ethylenediamine-epichlorohydrin condensate), and EPA-SK01 (manufactured by Yokkaichi Synthetic Co., Ltd., polyamidepolyamine-epichlorohydrin condensate).

[0019] The polyamide epihalohydrin polymers may be used singly or in combination of two or more.

[0020] The weight-average molecular weight of the polyamide epihalohydrin polymer is preferably from 10,000 to 5,000,000, more preferably from 100,000 to 5,000,000, even more preferably from 500,000 to 5,000,000, and particularly preferably from 1,000,000 to 5,000,000. When the weight-average molecular weight of the polyamide epihalohydrin polymer is within the above range, wet rub fastness may be further improved.

[0021] The content of the polyamide epihalohydrin polymer is preferably 0.10% by mass or more, more preferably 0.30% by mass or more, even more preferably 0.50% by mass or more, and particularly preferably 0.70% by mass or more, relative to the total mass of the treatment liquid composition. Furthermore, the content of the polyamide epihalohydrin polymer is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, even more preferably 1.5% by mass or less, and particularly preferably 1.2% by mass or less, relative to the total mass of the treatment liquid composition. When the content of the polyamide epihalohydrin polymer is within the above range, color development, dry rub fastness and wet rub fastness, texture, and light fastness tend to be well balanced.

[0022] 1.2 Certain Quaternary Ammonium Salt Polymers The treatment liquid composition according to this embodiment contains a quaternary ammonium salt polymer other than a polyamide epihalohydrin polymer (hereinafter also referred to as a "specific quaternary ammonium salt polymer").

[0023] Specific examples of quaternary ammonium salt polymers include polymers that are soluble in water, have one or more quaternary ammonium salts in the chain that constitutes the repeating unit of the polymer, and do not have a halohydrin structure such as a chlorohydrin structure.

[0024] Specific examples of specific quaternary ammonium salt polymers 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), and poly(2-acryloxyethyltrimethylammonium chloride). ), poly(2-acryloxyethyltriethylammonium 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.

[0025] Certain quaternary ammonium salt polymers may be commercially available, such as 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 Co., Ltd.), Papiogen P-105, and Myriogen P-20 (manufactured by Senka Co., Ltd.).

[0026] The specific quaternary ammonium salt polymers may be used alone or in combination of two or more.

[0027] The content of the specific quaternary ammonium salt polymer is preferably 0.10% by mass or more, more preferably 0.30% by mass or more, even more preferably 0.50% by mass or more, and particularly preferably 0.70% by mass or more, relative to the total mass of the treatment liquid composition. Furthermore, the content of the specific quaternary ammonium salt polymer is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, even more preferably 1.5% by mass or less, and particularly preferably 1.2% by mass or less, relative to the total mass of the treatment liquid composition. When the content of the specific quaternary ammonium salt polymer is within the above range, color development, dry rub fastness and wet rub fastness, texture, and light fastness tend to be well balanced.

[0028] 1.3 Cationic polymers other than those mentioned above The treatment liquid composition according to this embodiment may contain a cationic polymer other than the polyamide epihalohydrin polymer and the specific quaternary ammonium salt polymer described above. Examples of such cationic polymers include polymers that do not have a quaternary ammonium salt or a halohydrin structure such as a chlorohydrin structure in the polymer structure and that have a cationic functional group selected from a primary amino group, a secondary amino group, a tertiary amino group, an imino group, and an amide group.

[0029] 1.4 Solvent <Water> The treatment liquid composition according to this embodiment preferably contains water as a solvent. Water may be the main solvent of the treatment liquid composition and is a component that evaporates and dissipates upon drying. Examples of water include pure water such as ion-exchanged water, ultrafiltered water, reverse osmosis water, and distilled water, as well as ultrapure water, from which ionic impurities have been removed as much as possible. Furthermore, using water that has been sterilized by ultraviolet irradiation or the addition of hydrogen peroxide can prevent the growth of mold and bacteria when the treatment liquid composition is stored for a long period of time.

[0030] 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. The upper limit of the water content in the treatment liquid composition can be 99% by mass or less, 98% by mass or less, or 97% by mass or less.

[0031] <Water-soluble organic solvent> The treatment liquid composition according to this embodiment may contain a water-soluble organic solvent as a solvent.

[0032] Examples of the water-soluble organic solvent include polyol compounds, glycol ethers, and betaine compounds.

[0033] Examples of polyol compounds include polyol compounds (preferably diol compounds) having 2 to 6 carbon atoms 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, glycerin, 1,2-hexanediol, 1,2-heptanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl ether, ... methyl-3-phenoxy-1,2-propanediol, 3-(3-methylphenoxy)-1,2-propanediol, 3-hexyloxy-1,2-propanediol, 2-hydroxymethyl-2-phenoxymethyl-1,3-propanediol, 3-methyl-1,3-butanediol, 1,3-propanediol, 1,2-butanediol, 1,2-pentanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, and 3-methyl-1,5-pentanediol.

[0034] The glycol ether is preferably a monoalkyl ether of a glycol selected from ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, and polyoxyethylene polyoxypropylene glycol, more preferably triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, dipropylene glycol monopropyl ether, etc.

[0035] A betaine compound is a compound (internal salt) that has a positive charge and a negative charge at non-adjacent positions within the same molecule, with no dissociable hydrogen atoms bonded to the positively charged atom, resulting in an uncharged molecule as a whole. Preferred betaine compounds are N-alkyl-substituted amino acids, more preferably N-trialkyl-substituted amino acids. Examples of betaine compounds include trimethylglycine (also known as "glycine betaine"), γ-butyrobetaine, homarine, trigonelline, carnitine, homoserine betaine, valine betaine, lysine betaine, ornithine betaine, alanine betaine, stachydrine, and glutamic acid betaine, with trimethylglycine being preferred.

[0036] Furthermore, a pyrrolidone derivative may be used as the water-soluble organic solvent, such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-pyrrolidone, N-butyl-2-pyrrolidone, or 5-methyl-2-pyrrolidone.

[0037] A mixture of two or more water-soluble organic solvents may be used. When a water-soluble organic solvent is contained, the content thereof is, for example, preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less, relative to the total mass of the treatment liquid composition.

[0038] 1.5 Surfactants The treatment liquid composition according to this embodiment may contain a surfactant. The surfactant has functions such as reducing the surface tension of the treatment liquid composition and improving the wettability with a recording medium.

[0039] Among surfactants, for example, acetylene glycol surfactants, silicone surfactants, and fluorine surfactants can be preferably used, and among these, it is more preferable to contain an acetylene glycol surfactant.

[0040] The acetylene glycol surfactant is not particularly limited, but examples thereof include 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, and DF110D (all trade names, Air Products and Chemicals). Examples of suitable acrylic acid esters include 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, and AE-3 (all trade names, manufactured by Nissin Chemical Industry Co., Ltd.), and Acetylenol E00, E00P, E40, and E100 (all trade names, manufactured by Kawaken Fine Chemicals Co., Ltd.).

[0041] The silicone surfactant is not particularly limited, but a polysiloxane compound is preferred. The polysiloxane compound is not particularly limited, but for example, a polyether-modified organosiloxane is exemplified. Commercially available polyether-modified organosiloxanes include, for example, BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, and BYK-348 (all trade names, manufactured by BYK Japan KK), 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 (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.).

[0042] As the fluorine-based surfactant, it is preferable to use a fluorine-modified polymer, and a specific example is BYK-340 (manufactured by BYK Japan KK).

[0043] The surfactants may be used alone or in combination of two or more.

[0044] The lower limit of the surfactant content is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more, relative to the total mass (100% by mass) of the treatment liquid composition. The upper limit of the surfactant content is preferably 10% by mass or less, more preferably 7% by mass or less, even more preferably 5% by mass or less, particularly preferably 2% by mass or less, and even more preferably 1% by mass or less, relative to the total mass (100% by mass) of the treatment liquid composition.

[0045] When selecting a surfactant, it is preferable to consider the HLB value. The lower limit of the HLB value of the surfactant is preferably 6 or more, more preferably 8 or more, and even more preferably 10 or more. The upper limit of the HLB value is preferably 18 or less, more preferably 16 or less, and even more preferably 14 or less. When the HLB value is within the above range, color development may be further improved.

[0046] The HLB value in this specification is a value calculated from the ratio of the non-polar value (I) to the polar value (O) in the organic conceptual diagram (hereinafter simply referred to as the "I / O value") using the following formula (1). HLB value = (non-polar value (I) / polar value (O)) × 10 (1)

[0047] Specifically, the I / O value can be calculated based on the following literature: "Systematic Organic Qualitative Analysis Mixtures" by Atsushi Fujita, Kazama Shobo, 1974; "Theoretical Chemistry of Dyeing" by Nobuhiko Kuroki, Maki Shoten, 1966; and "Methods for Separating Organic Compounds" by Hiroo Inoue, Shokabo, 1990.

[0048] 1.6 Water-insoluble ingredients The treatment liquid composition according to this embodiment may contain a water-insoluble component. The water-insoluble component refers to a component that is insoluble or barely soluble in water, and examples of the water-insoluble component include a water-insoluble colorant, a water-insoluble resin, a wax, and a water-insoluble organic solvent.

[0049] [Water-insoluble coloring material] Examples of water-insoluble coloring materials include oil-soluble dyes and pigment particles. The oil-soluble dye is not particularly limited, but examples thereof include disperse dyes, vat dyes, and organic solvent-soluble dyes. The pigment particles may be the same as those contained in the inkjet ink composition described below.

[0050] [Water-insoluble resin] Examples of water-insoluble resins include urethane-based resins, acrylic-based resins, styrene-acrylic resins, fluorene-based resins, polyolefin-based resins, rosin-modified resins, terpene-based resins, polyester-based resins, polyamide-based resins, epoxy-based resins, vinyl chloride-based resins, vinyl chloride-vinyl acetate copolymers, and ethylene-vinyl acetate-based resins. The water-insoluble resin is preferably used in the form of resin particles such as a resin emulsion or powder, and more preferably resin particles of a resin emulsion. The water-insoluble resin may be used alone or in combination of two or more.

[0051] Urethane resin is a general term for resins having urethane bonds. In addition to urethane bonds, the urethane resin may be a polyether urethane resin containing ether bonds in the main chain, a polyester urethane resin containing ester bonds in the main chain, or a polycarbonate urethane resin containing carbonate bonds in the main chain.

[0052] Acrylic resin is a general term for polymers obtained by polymerizing at least an acrylic monomer such as (meth)acrylic acid or a (meth)acrylic acid ester as one component. Examples include resins obtained from acrylic monomers and copolymers of acrylic monomers with other monomers. Examples include acrylic-vinyl resins, which are copolymers of acrylic monomers and vinyl monomers. Further examples include copolymers with vinyl monomers such as styrene.

[0053] As the acrylic monomer, acrylamide, acrylonitrile, etc. can also be used. As the acrylic resin, commercially available products may be used. In this specification, the acrylic resin may be a styrene-acrylic resin, which will be described later. In this specification, the term "(meth)acrylic" means at least one of acrylic and methacrylic.

[0054] The styrene-acrylic resin is a copolymer obtained from a styrene monomer and an acrylic monomer, and examples thereof include a styrene-acrylic acid copolymer, a styrene-methacrylic acid copolymer, a styrene-methacrylic acid-acrylate copolymer, a styrene-α-methylstyrene-acrylic acid copolymer, a styrene-α-methylstyrene-acrylic acid-acrylate copolymer, etc. Commercially available styrene-acrylic resins may be used.

[0055] The polyolefin resin has an olefin such as ethylene, propylene, or butylene in its structural skeleton, and any known polyolefin resin can be appropriately selected and used. Commercially available olefin resins may also be used.

[0056] Examples of commercially available resin particle emulsions that can be used in this embodiment are listed below. <Urethane resin emulsion> Superflex 870, 800, 150, 420, 460, 470, 610, 620, 700, 460s, 840, E-4000 (trade names manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Parmarin UA-150 (trade name manufactured by Sanyo Chemical Industries, Ltd.), Sancure 2710 (trade name manufactured by The Lubrizol Chemical Company, Ltd.), NeoRez R-9660, R-9637, R-940 (trade names manufactured by Kusumoto Chemicals Co., Ltd.), Adeka Bontiter HUX-380, 290K (trade names manufactured by ADEKA Corporation), Rezamin D-1060, D-2020, D-4080, D-4200, D-6300, D-6455 (product names manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.), Takelac W-6020, W-635, W-6061, W-605, W-635, W-6021, W-512-A-6 (product names manufactured by Mitsui Chemicals Polyurethanes).

[0057] <Acrylic resin emulsion> Boncoat 4001 (trade name manufactured by DIC), 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), Vinyblanc 2682 (trade name manufactured by Nissin Chemical Industry Co., Ltd.), Mowinyl 952B, 718A (trade name manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), K-854 (trade name manufactured by Chuo Rika Kogyo Co., Ltd.), Nipol LX852, LX874 (trade name manufactured by Nippon Zeon Co., Ltd.).

[0058] <Styrene acrylic resin emulsion> Microgel E-1002, E-5002 (product names of Nippon Paint Co., Ltd.), Boncoat 5454 (product name of DIC Corporation), Polysol AP-7020, SAE1014 (product name of Showa Denko K.K.), Vinyblan 2586 (product name of Nissin Chemical Industry Co., Ltd.), Arrowbase CB-1200, CD-1200 (product names of Unitika Ltd.), Mowinyl 966A, 7320 , 975N (product name manufactured by Nippon Gosei Kagaku Co., Ltd.), Joncryl 62J, 7100, 390, 711, 511, 7001, 632, 741, 450, 840, 74J, HRC-16 45J, 734, 852, 7600, 775, 537J, 1535, PDX-7630A, 352J, 352D, PDX-7145, 538J, 7640, 7641, 631, 7 90, 780, 7610 (BASF product names).

[0059] <Other resin emulsions> Eliter KA-5071S, KT-8803, KT-9204, KT-8701, KT-8904, KT-0507 (trade name of Unitika Ltd., polyester resin emulsion), Hi-Tec SN-2002 (trade name of Toho Chemical Co., Ltd., polyester resin emulsion), Polysol SH-502 (trade name of Showa Denko K.K., vinyl acetate resin emulsion), Polysol AD-13, AD-2, AD-10, AD-96, AD-17, AD-70 (trade name of Showa Denko K.K., ethylene-vinyl acetate resin emulsion), Polysol PSASE-6010 (trade name of Showa Denko K.K., ethylene -vinyl acetate resin emulsion), AE373D (trade name of E-Tech Co., Ltd., carboxy-modified styrene-acrylic resin emulsion), Seikadyne 1900W (trade name of Dainichiseika Color & Chemicals Mfg. Co., Ltd., ethylene-vinyl acetate resin emulsion), Vinyblanc 2886 (trade name of Nissin Chemical Industry Co., Ltd., vinyl acetate-acrylic resin emulsion), Vinyblanc 5202 (trade name of Nissin Chemical Industry Co., Ltd., acetate-acrylic resin emulsion), NK Binder R-5HN (trade name of Shin-Nakamura Chemical Co., Ltd.), Hydran WLS-210 (trade name of DIC Corporation, non-crosslinkable polyurethane emulsion).

[0060] 〔wax〕 The wax is not particularly limited, but examples thereof include hydrocarbon waxes and ester waxes, which are condensates of fatty acids with monohydric alcohols or polyhydric alcohols. The hydrocarbon wax is not particularly limited, but examples thereof include paraffin waxes and polyolefin waxes such as polyethylene waxes and polypropylene waxes. These waxes may be used alone or in combination of two or more.

[0061] Commercially available paraffin waxes include, for example, AQUACER 497 and AQUACER 539 (both product names, manufactured by BYK).

[0062] Commercially available polyolefin waxes include, for example, 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).

[0063] The water-insoluble component may be used alone or in combination of two or more.

[0064] The treatment liquid composition according to this embodiment preferably contains no more than 1.0% by mass of a water-insoluble component relative to the total mass of the treatment liquid composition, more preferably no more than 0.70% by mass, even more preferably no more than 0.50% by mass, particularly preferably no more than 0.30% by mass, even particularly preferably no more than 0.10% by mass, and may not contain any water-insoluble component at all. The inclusion of a water-insoluble component tends to improve properties such as abrasion fastness, but may result in poor application stability. In contrast, the treatment liquid composition according to this embodiment tends to exhibit good abrasion fastness and good application stability even when the content of the water-insoluble component is within the above range. From the perspective of further enjoying the effects of the present invention, it is preferred that the water-insoluble component be resin particles.

[0065] 1.7 Other ingredients The treatment liquid composition according to this embodiment may contain, as necessary, a pH adjuster, an antiseptic / fungal agent, a rust inhibitor, a chelating agent, a viscosity adjuster, a dissolution aid, an antioxidant, and the like.

[0066] [pH adjuster] Examples of pH adjusters include amines such as diethanolamine, triethanolamine, propanolamine, and 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, and quaternary ammonium hydroxide (tetramethylammonium).

[0067] [Preservatives and antifungal agents] Examples of preservatives and antifungal agents include sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, and 1,2-dibenzinethiazolin-3-one (ICI's Proxel CRL, Proxel BND, Proxel GXL, Proxel XL-2, and Proxel TN).

[0068] [Chelating Agents] Chelating agents have the property of capturing ions, and examples of such chelating agents include ethylenediaminetetraacetate (EDTA), ethylenediamine nitrilotriacetate, hexametaphosphate, pyrophosphate, and metaphosphate.

[0069] 1.8 Manufacturing method The treatment liquid composition according to this embodiment can be obtained by mixing the above-described components in any order and, if necessary, removing impurities by filtration or the like. A suitable method for mixing the components is to sequentially add the materials to a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer and then stir and mix them. As a filtration method, centrifugal filtration, filter filtration, or the like can be used as necessary.

[0070] 1.9 Physical properties of processing liquid composition The physical properties of the treatment liquid composition according to this embodiment, such as pH, surface tension, and viscosity, may be adjusted to fall within desired ranges.

[0071] The treatment liquid composition according to this embodiment preferably has a pH of less than 7. More preferably, the pH is less than 6, even more preferably less than 5, and particularly preferably less than 4. The inkjet ink composition described below, which can be used together with the treatment liquid composition according to this embodiment, has a pH of more than 8 and is dispersion stabilized. When the pH of the treatment liquid composition is within the above range, the ink is likely to become dispersion unstable when mixed with the inkjet ink composition, promoting aggregation and improving reactivity with the ink, which may further improve color development.

[0072] The treatment liquid composition according to this embodiment preferably has a surface tension of 10 mN / m or more and 40 mN / m or less, and 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 check the surface tension when a platinum plate is wetted with the treatment liquid composition in an environment of 25° C.

[0073] The treatment liquid composition according to this embodiment preferably has a viscosity of 2 mPa·s or more and 15 mPa·s or less, more preferably 2 mPa·s or more and 5 mPa·s or less, and even more preferably 2 mPa·s or more and 3.6 mPa·s or less at 20° C. The viscosity can be measured using, for example, a viscoelasticity tester MCR-300 (trade name, manufactured by Pysica) at 40° C. or 20° C.

[0074] 1.10 Purpose The treatment liquid composition according to this embodiment is preferably used in a water-based pigment inkjet ink. As the water-based pigment inkjet ink, the inkjet ink composition described below can be preferably used.

[0075] Furthermore, the treatment liquid composition according to this embodiment is preferably used by applying it to fabric. When forming an image on fabric with ink, high quality is required in terms of color development, wet rub fastness, texture, etc. The treatment liquid composition according to this embodiment tends to be able to achieve both excellent color development and excellent wet rub fastness, which are required for forming an image on fabric, and also to achieve good texture.

[0076] Examples of materials that can be used to make fabrics 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. Blends of these fibers are also possible.

[0077] The polyamide epihalohydrin polymer contained in the treatment liquid composition according to this embodiment has the function of improving water resistance by reducing swelling of the fibers due to water absorption when the amide moieties in its structure bond with hydroxyl groups of the fibers in the fabric, and the function of improving structural strength by crosslinking of the epihalohydrin moieties, and at least one of these functions works regardless of the material constituting the fabric. Therefore, whether the material constituting the fabric is a natural fiber such as cotton or a synthetic fiber such as polyester, the treatment liquid composition according to this embodiment has the effect of improving excellent wet rub fastness.

[0078] The whiteness of the fabric is preferably 70 or more, more preferably 80 or more, and even more preferably 90 or more. Whiteness is expressed in CIE / L * a * b * In the color system, L * The whiteness can be measured using a colorimeter "Gretag Macbeth Spectrolino" (product name, manufactured by X-Rite). Fabrics having a whiteness within the above range are relatively white fabrics, and therefore have the problem that yellowing is particularly noticeable. However, the treatment liquid composition according to this embodiment is resistant to yellowing, and can therefore be used on such fabrics without causing the problem of yellowing.

[0079] 2. Set of inkjet ink composition and treatment liquid composition The set of the inkjet ink composition and the treatment liquid composition according to one embodiment of the present invention comprises: A set of an inkjet ink composition and the treatment liquid composition described above, The inkjet ink composition is a water-based pigment inkjet ink containing pigment particles and resin particles, and has a pH of more than 8 and contains particle components with a volume average particle diameter of 20 to 500 nm. The set of an inkjet ink composition and a treatment liquid composition may be any set as long as the ink composition and the treatment liquid composition provided in the set are used as a set for recording. In other words, the ink composition and the treatment liquid composition used as a set for recording are referred to as a set of an inkjet ink composition and a treatment liquid composition.

[0080] The inkjet ink composition provided in the set of inkjet ink composition and treatment liquid composition according to this embodiment (hereinafter also referred to as the "ink treatment liquid set") has a pH of greater than 8 and is dispersion stabilized. When such an inkjet ink composition is mixed with the treatment liquid composition described above, the ink dispersion is likely to become unstable and aggregation of the particle components is promoted, which tends to improve the reactivity between the ink and the treatment liquid and result in particularly excellent color development. Therefore, the ink treatment liquid set according to this embodiment can achieve both particularly excellent color development and excellent wet rub fastness.

[0081] The components of the treatment liquid composition included in the ink treatment liquid set according to this embodiment are as described above, and therefore will not be described further. Below, the components contained in the inkjet ink composition included in the ink treatment liquid set according to this embodiment will be described.

[0082] 2.1 Inkjet ink composition The inkjet ink composition included in the ink treatment liquid set according to this embodiment is a water-based pigment inkjet ink containing pigment particles and resin particles.

[0083] 2.1.1 Pigment particles Examples of pigment particles include organic pigments such as cyan, magenta, yellow, and black, and special color pigments such as white pigments and glitter pigments.

[0084] Examples of organic pigments include quinacridone pigments, quinacridonequinone pigments, dioxane 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, 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 chelate azo pigments.

[0085] Specific examples of organic pigments include the following: Pigments used in cyan inks include CI Pigment Blue 1, 2, 3, 15:3, 15:4, 16, 22, 60, etc.; CI Vat Blue 4, 60, etc., and preferably a single pigment selected from the group consisting of CI Pigment Blue 15:3, 15:4, and 60, or a mixture of two or more pigments.

[0086] Examples of pigments used in the magenta ink include CI Pigment Red 5, 7, 12, 48(Ca), 48(Mn), 57(Ca), 57:1, 112, 122, 123, 168, 184, 202, and CI Pigment Violet 19, and preferably a pigment selected from the group consisting of CI Pigment Red 122, 202, and 209, and CI Pigment Violet 19, either alone or in combination.

[0087] Examples of pigments used in the yellow ink include 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, and 185, and preferably a pigment selected from the group consisting of CI Pigment Yellow 74, 109, 110, 128, and 138, either alone or in combination.

[0088] The pigment used in the orange ink is CI Pigment Orange 36 or 43 or a mixture thereof.

[0089] The pigment used in the green ink is CI Pigment Green 7 or 36 or a mixture thereof.

[0090] 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, No. 2200B (trade names, manufactured by Mitsubishi Chemical Corporation), color black FW1, FW2, FW2V, FW18, FW200, S150, S160, S170, and Pretek. Examples of carbon blacks include Axus 35, U, V, 140U, Special Black 6, 5, 4A, 4, and 250 (trade names, manufactured by Degussa), Conductex SC, Raven 1255, 5750, 5250, 5000, 3500, 1255, and 700 (all trade names, manufactured by Columbia Carbon), Ligal 400R, 330R, and 660R, Mogul L, Monarch 700, 800, 880, 900, 1000, 1100, 1300, and 1400, and Elftex 12 (trade names, manufactured by Cabot). These carbon blacks may be used alone or in combination of two or more.

[0091] The luster pigment is not particularly limited as long as it can exhibit luster when attached to a medium, but examples include metal particles of one or more alloys (also called metal pigments) selected from the group consisting of aluminum, silver, gold, platinum, nickel, chromium, tin, zinc, indium, titanium, and copper, and pearl pigments with pearly luster. Representative examples of pearl pigments include pigments with pearly luster or interference luster, such as titanium dioxide-coated mica, fish scale foil, and bismuth oxychloride. The luster pigment may also be surface-treated to suppress reaction with water.

[0092] Examples of white pigments include metal oxides, barium sulfate, calcium carbonate, and other metal compounds. Examples of metal oxides include titanium dioxide, zinc oxide, silica, alumina, magnesium oxide, and the like. The white pigment may also be a particle having a hollow structure.

[0093] The pigment particles may be of one type alone or in combination of two or more types. From the viewpoint of storage stability such as light resistance, weather resistance, and gas resistance, the pigment particles are preferably organic pigments.

[0094] It is preferable that the pigment particles can be stably dispersed in the ink. For example, the pigment particle surface may be modified by oxidizing or sulfonating the pigment particle surface with ozone, hypochlorous acid, fuming sulfuric acid, or the like, and used as self-dispersing pigment particles, or the pigment particles may be dispersed using a resin dispersant.

[0095] Examples of the resin dispersant include polyvinyl alcohols, polyacrylic acid, acrylic acid-acrylonitrile copolymer, vinyl acetate-acrylic acid ester copolymer, acrylic acid-acrylic acid ester copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid-acrylic acid ester copolymer, styrene-α-methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene-acrylic acid-acrylic acid ester copolymer, styrene-maleic acid copolymer, styrene-maleic anhydride copolymer, vinylnaphthalene-acrylic acid copolymer, vinylnaphthalene-maleic acid copolymer, vinyl acetate-maleic acid ester copolymer, vinyl acetate-crotonic acid copolymer, vinyl acetate-acrylic acid copolymer, and the like, and salts thereof.

[0096] Among these, copolymers of a monomer having a hydrophobic functional group and a monomer having a hydrophilic functional group, and polymers composed of a monomer having both a hydrophobic functional group and a hydrophilic functional group are preferred. The copolymer may be in the form of a random copolymer, a block copolymer, an alternating copolymer, or a graft copolymer.

[0097] The resin dispersant described here functions to enhance the dispersibility of pigment particles. The resin dispersant is, for example, water-soluble, and / or the resin dispersant is present around the pigment particles by adhering to the pigment.

[0098] The content of the resin dispersant can be selected appropriately depending on 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, per 100 parts by mass of the pigment particle content in the ink.

[0099] The content of pigment particles in the ink is preferably 0.3% by mass or more and 20% by mass or less, more preferably 0.5% by mass or more and 15% by mass or less, even more preferably 1 to 10% by mass, and particularly preferably 1.5 to 5% by mass, based on the total mass of the ink. If the content of pigment particles is within the above range, nozzle clogging of the inkjet recording device is less likely to occur, and color density can be fully satisfied. Furthermore, if the content of pigment particles is above the above range, it is easier to form images with even better color development.

[0100] 2.1.2 Resin particles As the resin particles, the same resin particles as those in the water-insoluble component that may be contained in the above-mentioned treatment liquid composition can be used.

[0101] 2.1.3 Physical properties of particle components The particle components contained in the inkjet ink composition, such as the pigment particles and resin particles, have a volume average particle diameter of 20 to 500 nm.

[0102] The volume-based average particle diameter (D50) (also referred to as "volume average particle diameter") of the particle component (before mixing with the ink) is 20 nm or more, preferably 50 nm or more, more preferably 80 nm or more, even more preferably 110 nm or more, and particularly preferably 150 nm or more. Furthermore, the volume average particle diameter of the particle component is 500 nm or less, preferably 400 nm or less, more preferably 300 nm or less, even more preferably 250 nm or less, and particularly preferably 200 nm or less. A volume average particle diameter within this range is advantageous in terms of ease of availability and the ability to achieve desirable properties. Furthermore, a volume average particle diameter within the above range tends to prevent the particle component from settling, improve dispersion stability, and reduce nozzle clogging when used in an inkjet recording device.

[0103] The volume average particle size of the particle component can be measured using a particle size distribution analyzer that uses laser diffraction scattering as its measurement principle, such as a particle size distribution analyzer that uses dynamic light scattering as its measurement principle (e.g., "Microtrac UPA" manufactured by Nikkiso Co., Ltd.).

[0104] The content of the particle component, as solid content, relative to the total mass of the inkjet ink composition is 0.2% by mass or more and 40% by mass or less, preferably 2% by mass or more and 30% by mass or less, more preferably 4% by mass or more and 20% by mass or less, and even more preferably 6% by mass or more and 15% by mass or less.

[0105] The particle components, such as the pigment particles and resin particles, contained in the inkjet ink composition are preferably anionic. The treatment liquid composition contains a cationic polymer, such as a polyamide epihalohydrin polymer or a specific quaternary ammonium salt polymer. Therefore, if the particle components, such as the pigment particles and resin particles, of the ink are anionic, an aggregation reaction occurs effectively when the treatment liquid composition and the ink are mixed, and better color development tends to be achieved.

[0106] A suitable example of anionic pigment particles is a pigment having a dispersant with an anionic group present on the surface thereof. The dispersant with an anionic group is a pigment having an anionic group such as -COO - Ya-SO3 - Examples of dispersants include those having the formula:

[0107] Examples of anionic resin particles include resin particles having anionic functional groups such as carboxyl groups, sulfo groups, and hydroxyl groups, and anionic urethane resins are preferred. Among the commercially available urethane resins mentioned above, examples of anionic urethane resins include Superflex 460, 460s, and 840 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.; and Takelac WS-5000, WS-6021, and W-512-A-6 manufactured by Mitsui Chemicals Polyurethanes, Inc.

[0108] 2.1.4 Water The inkjet ink composition included in the ink treatment liquid set according to this embodiment is an aqueous pigment inkjet ink, and contains water. "Aqueous" means that the ink contains water as the main solvent. The water may be the same as that which can be contained in the treatment liquid composition described above. 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.

[0109] 2.1.5 Organic solvents The inkjet ink composition included in the ink treatment liquid set according to this embodiment may contain an organic solvent. The organic solvent is preferably a water-soluble organic solvent. Such a water-soluble organic solvent may be the same as those that may be contained in the treatment liquid composition described above. When a water-soluble organic solvent is contained, its content is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less, relative to the total mass of the inkjet ink composition, and preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, relative to the total mass of the inkjet ink composition.

[0110] 2.1.6 Surfactants The inkjet ink composition included in the ink treatment liquid set according to this embodiment may contain a surfactant. The surfactant may be the same as those that may be contained in the treatment liquid composition described above, and the content thereof may also be the same.

[0111] 2.1.7 Other ingredients The inkjet ink composition provided in the ink treatment liquid set according to this embodiment may contain, as necessary, wax, pH adjuster, preservative / fungicide, rust inhibitor, chelating agent, viscosity adjuster, solubilizing agent, antioxidant, etc. These components are the same as those that can be contained in the treatment liquid composition described above, and therefore further description will be omitted.

[0112] 2.1.8 Manufacturing method The inkjet ink composition included in the ink treatment liquid set according to this embodiment can be obtained by mixing the components described above in any order and, if necessary, removing impurities by filtration or the like. A suitable method for mixing the components is to sequentially add the materials to a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer and then stir and mix them. As a filtration method, centrifugal filtration, filter filtration, or the like can be used as necessary.

[0113] 2.1.9 Physical properties of inkjet ink composition The physical properties of the inkjet ink composition included in the ink treatment liquid set according to this embodiment, such as pH, surface tension, and viscosity, may be adjusted to fall within desired ranges.

[0114] The inkjet ink composition has a pH of greater than 8. Preferably, the pH is greater than 9, more preferably greater than 10, and even more preferably greater than 11. When the pH of the inkjet ink composition is within the above range, the ink tends to be easily destabilized when mixed with the treatment liquid composition, promoting aggregation of the particle components and further improving color development.

[0115] The physical properties such as surface tension and viscosity can be the same as those of the above-mentioned treatment liquid composition.

[0116] 3. Processing Method A processing method according to one embodiment of the present invention includes: an application step of applying the treatment liquid composition to a fabric; 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.

[0117] The treatment method according to the present embodiment involves a step of heating a fabric to which the treatment liquid composition has been applied so that the surface temperature of the fabric reaches 100°C or higher. By applying this treatment method, it is possible to achieve both excellent color development and excellent wet rub fastness.

[0118] Each step of the processing method according to this embodiment will be described below.

[0119] 3.1 Adhesion process The treatment method according to this embodiment includes a step of applying the treatment liquid composition to a fabric. The treatment liquid composition and the fabric are as described above, and therefore further description will be omitted.

[0120] Examples of methods for applying the treatment liquid composition to a fabric (coating methods) include a method of immersing a fabric in the treatment liquid composition (dip coating), a method of applying the treatment liquid composition using a roll coater or the like (roller coating), a method of spraying the treatment liquid composition using a spray device or the like (spray coating), and a method of spraying the treatment liquid composition by an inkjet method (inkjet coating), and any of these methods may be used. Coating the treatment liquid composition by inkjet coating is preferred because it makes it easier to control the uniform application of the treatment liquid composition to the fabric. Furthermore, dip coating or spray coating of the treatment liquid composition is preferred because it allows the treatment liquid composition to be applied to the fabric in a short period of time.

[0121] The amount of the treatment liquid composition applied is 50 to 200 g / m per unit area of ​​the fabric. 2 It is preferable that the density is 70 to 170 g / m 2 More preferably, it is 90 to 140 g / m 2 More preferably, it is 100 to 120 g / m 2 When the coating amount of the treatment liquid composition is within the above range, the effects of the present invention may be more easily achieved.

[0122] 3.2 Heating process The treatment method according to this embodiment includes a heating step, which follows the application step, in which the fabric to which the treatment liquid composition has been applied is heated. The heating method is not particularly limited, but examples thereof include convection heat drying, radiant heat drying, and conductive heat drying. The heat source used for heating can be heat generated by a combustible gas combustion burner, a carbon heater, a ceramic heater, a halogen lamp, or an infrared lamp.

[0123] The lower limit of the surface temperature of the fabric in the heating step is preferably 40°C or higher, more preferably 80°C or higher, and even more preferably 100°C or higher. The upper limit of the surface temperature of the fabric in the heating step is preferably 180°C or lower. Setting the heating temperature to 180°C or lower can suppress damage to the fabric due to heat stress during heat drying. Setting the heating temperature to the lower limit or higher can efficiently evaporate moisture and solvents contained in the treatment liquid composition, thereby facilitating drying of the treated fabric. Furthermore, when the fabric contains cotton as a material, setting the heating temperature to 100°C or higher can promote the crosslinking reaction of the polyamide epihalohydrin polymer contained in the treatment liquid composition with the cellulose fibers in the cotton fabric.

[0124] 4. Working Example The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "%" below is based on mass.

[0125] 4.1 Preparation of processing liquid composition Each treatment liquid composition was obtained by mixing the components in the amounts shown in Tables 1 and 2 below, stirring at room temperature for 2 hours, and then filtering through a membrane filter with a pore size of 5 μm. Note that the units of the contents of the components shown in Tables 1 and 2 below are % by mass, and are indicated in the tables as "wt%."

[0126] 4.2 Preparation of Inkjet Ink Composition The components were mixed in the amounts shown in the following black ink composition examples, stirred at room temperature for 2 hours, and then filtered using a membrane filter with a pore size of 5 μm to obtain an inkjet ink composition (black ink). In the following black ink composition examples, the pigment content is the pigment solids content, and the resin emulsion content is the resin solids content. The carbon black pigment used in preparing the inkjet ink composition was previously mixed with a water-soluble styrene-acrylic resin pigment dispersant (not shown in the following composition examples) in a mass ratio of 1:1 (pigment:pigment dispersant) in water, and the mixture was thoroughly stirred to form a black pigment dispersion.

[0127] [Example of black ink composition] Black pigment dispersion: Carbon black pigment 5% by mass Resin emulsion: WS6021 6% by mass Glycerin 6% by mass Trimethylolpropane 8% by mass Triethylene glycol 5% by mass EDTA 0.1% by mass Inorganic alkali: KOH 0.1% by mass Surfactant: Olfine E1010 1% by mass Surfactant: Surfynol 104 0.5% by mass Pure water 68.3% by mass

[0128] A supplementary explanation will be given regarding the black ink. Carbon black pigment: CI Pigment Black 7 WS6021: Takelac WS-6021, Mitsui Chemicals product name, solid content 30% by mass, urethane resin EDTA: Ethylenediaminetetraacetic acid, a metal chelating agent Olfine E1010: Product name of Nissin Chemical Industry Co., Ltd., acetylene glycol surfactant, HLB=14 Surfynol 104: Trade name of Nissin Chemical Industry Co., Ltd., acetylene glycol surfactant, HLB=4

[0129] The pH of the black ink was greater than 8. The pH was measured using a desktop pH meter F-72 (manufactured by Horiba, Ltd.) by immersing the electrode portion in the inkjet ink composition.

[0130] 4.3 Recording Media The following fabric was used as the recording medium. [Cotton fabric] Fiber:Cotton Type: Taffeta Composition: 100% cotton Weight:8.04~8.55(g / m 2 ) Standard size: 145~150(cm) Manufacturer: A.FERRARIO Whiteness L * Value: 91.5

[0131] In addition, the fabric L * The values ​​were measured using a colorimeter "Gretag Macbeth Spectrolino" (product name, manufactured by X-Rite).

[0132] [Table 1]

[0133] [Table 2]

[0134] The following is a supplementary explanation of the descriptions in Tables 1 and 2 above.

[0135] <Composition> Further explanations of the polyamide epihalohydrin polymer, quaternary ammonium salt polymer, resin particles, surfactant and preservative are as follows. [Polyamide epihalohydrin polymer] Polyamide-epichlorohydrin polymer A: Product name "WS4020", manufactured by Seiko PMC Corporation Polyamide polyamine-epichlorohydrin polymer: Product name "AF-255", manufactured by Arakawa Chemical Industries, Ltd. Polyamide-epichlorohydrin polymer B: Product name "WS4030", manufactured by Seiko PMC Corporation Dimethylamine-ethylenediamine-epichlorohydrin polycondensate: trade name "PE-30", manufactured by Yokkaichi Synthetic Co., Ltd. [Quaternary ammonium salt polymer] Quaternary ammonium salt polymer A: Trade name "PAS-J-41", manufactured by Nittobo Medical Co., Ltd., diallyldimethylammonium chloride-acrylamide copolymer, average molecular weight 10,000 Quaternary ammonium salt polymer B: Product name "PAS-J-81", manufactured by Nittobo Medical Co., Ltd., diallyldimethylammonium chloride-acrylamide copolymer, average molecular weight 180,000 Quaternary ammonium salt polymer C: Product name "EP1137", manufactured by Takamatsu Oil & Fat Co., Ltd. [Resin particles] Urethane resin: Product name "SF-620", manufactured by Daiichi Pharmaceutical Co., Ltd. [Surfactant] Acetylene glycol: Trade name "Surfynol 485", manufactured by Nissin Chemical Industry Co., Ltd., HLB=17 [Preservatives] Proxel XL2: Trade name manufactured by Lonza

[0136] <Processing conditions> The drying temperature after application of the pretreatment liquid composition (treatment liquid composition) and the drying temperature after printing of the ink are shown in the table as the surface temperature of the fabric when subjected to a heat drying treatment using a conveyor drying oven "Economax D" (product name of M&R).

[0137] <Evaluation items> The spray application stability evaluation test was performed using the "1008" spraying system manufactured by Spraying Systems. + The spray controller was combined with a two-fluid nozzle that produced a flat spray pattern. The pH was measured using a desktop pH meter F-72 model (manufactured by Horiba Ltd.) by immersing the electrode portion in the treatment liquid composition.

[0138] 4.4 Evaluation method The evaluation tests were carried out on spray coating stability, color development, rub fastness, texture and light resistance, using the following evaluation methods.

[0139] 4.4.1 Spray application stability (two-fluid nozzle) Spraying Systems' 1008 + Each of the treatment liquid compositions obtained above was sprayed at a rate of 110 g / m per unit area using a combination of a spray controller and a two-fluid nozzle that generates a flat spray pattern. 2 The coating amount was adjusted to 100g and uniformly applied to the surface of the fabric described in "4.3 Recording Medium" above. The change in coating weight consumed during the coating treatment time of the treatment liquid composition was monitored, and whether the specified amount was applied without nozzle clogging was evaluated as spray coating stability. The spray coating stability was judged as follows: (Judgment criteria) A: The rate of change in coating weight at the end of coating is less than ±10% of the initial setting value. B: The rate of change in coating weight at the end of coating is ±10% or more and less than 20% of the initial setting value. C: The rate of change in coating weight at the end of coating is ±20% or more compared to the initial setting value.

[0140] 4.4.2 Color development (black ink 100% duty) The fabric to which the treatment liquid composition had been applied by the above method was subjected to a heat drying treatment for 7 minutes at the drying temperature shown in the table using a conveyor drying oven "Economax D" (manufactured by M&R), completing the fabric treatment. The inkjet ink composition prepared as described above was applied to the fabric by an inkjet method using an inkjet printer (product name "PX-G930", manufactured by Seiko Epson Corporation), and an image was printed. The print pattern (image) was a solid image printed at a resolution of 1440 x 720 dpi, with a printing area of ​​210 mm x 297 mm. Here, "solid image" means an image in which dots are recorded for all pixels, which are the minimum recording unit area defined by the recording resolution. The fabric to which the inkjet ink composition was attached was subjected to a heat drying treatment at 160°C for 5 minutes using a conveyor drying oven "Economax D" (manufactured by M&R), and then returned to 25°C to obtain a printed item. The optical density (hereinafter also referred to as "OD value") of the image on the printed fabric was measured using a fluorescent spectrodensitometer (FD-7, manufactured by Konica Minolta) and the color development was evaluated. The evaluation was made as follows: (Judgment criteria) S:OD value is 1.5 or more (particularly good) A: OD value is 1.4 or more but less than 1.5 (good). B: OD value is 1.25 or more and less than 1.4. C:OD value less than 1.25.

[0141] 4.4.3 Rubbing resistance (discoloration) The fabrics printed at 100% duty using the above method were tested for dry and wet abrasion resistance using a test method in accordance with ISO105-X12 and judged according to the following criteria: The wet and dry abrasion resistance was judged as the difference in OD value due to discoloration before and after the abrasion resistance test, according to the following criteria. (Dry friction strength evaluation criteria) S: The difference in OD value before and after the abrasion resistance test is less than 0.15 (very good). A: The difference in OD value before and after the abrasion resistance test is 0.15 or more and less than 0.20 (good). B: The difference in OD value before and after the abrasion resistance test is 0.20 or more and less than 0.25. C: The difference in OD value before and after the abrasion resistance test is 0.25 or more. (Wet friction strength evaluation criteria) S: The difference in OD value before and after the abrasion resistance test is less than 0.20 (very good). A: The difference in OD value before and after the abrasion resistance test is 0.20 or more and less than 0.25 (good). B: The difference in OD value before and after the abrasion resistance test is 0.25 or more and less than 0.30. C: The difference in OD value before and after the abrasion resistance test is 0.30 or more.

[0142] 4.4.4 Texture (shear stiffness) The shear stiffness of the fabric printed at a duty of 100% by the above method was evaluated using a tensile shear tester KES-FB1-A manufactured by Kato Tech Co., Ltd. The feel was evaluated using the shear stiffness value according to the following criteria. (Judgment criteria) S: Shear stiffness is less than 6.0 gf / cm·deg. A: The shear stiffness is 6.0 gf / cm·deg or more and less than 8.0 gf / cm·deg. B: Shear stiffness is 8.0 gf / cm·deg or more and less than 10.0 gf / cm·deg. C: Shear stiffness is 10.0 gf / cm·deg or more.

[0143] 4.4.5 Lightfastness (yellowing) The treatment liquid composition was applied to a fabric that had been dried under the conditions described in "4.4.2 Color development (black ink 100% duty)" and the fabric was subjected to a test at 20 MJ / m using a Suga Test Instruments xenon weather meter: XL75s. 2 The pretreated fabric was irradiated with xenon light having a cumulative irradiance of 10 ... * The value of the color difference was 91.5. The lightfastness was evaluated using the color difference value according to the following criteria. (Judgment criteria) A: The color difference is less than 2.0. B: The color difference is 2.0 or more and less than 4.0. C: The color difference is 4.0 or more.

[0144] 4.5 Evaluation results The evaluation results are shown in Tables 1 and 2 above.

[0145] A comparison of the examples and comparative examples shows that the treatment liquid composition, the set of inkjet ink composition and treatment liquid composition, and the recording method according to this embodiment can achieve both excellent color development and excellent wet rub fastness.

[0146] A comparison between Example 2 and Comparative Example 1 shows that by using a specific quaternary ammonium salt polymer instead of a polyvalent metal salt, it is possible to achieve excellent color development and wet rub fastness at the same time. Furthermore, a comparison between Example 2 and Comparative Examples 1 and 2 reveals that the treatment liquid composition according to this embodiment is less likely to turn yellow.

[0147] A comparison of Example 2 with Comparative Examples 3 and 4 shows that by containing a polyamide epihalohydrin polymer and a specific quaternary ammonium salt polymer, it is possible to achieve both excellent color development and excellent wet rubbing fastness.

[0148] The results of Examples 1 to 3 show that various polyamide epihalohydrin polymers can achieve both excellent color development and excellent wet rub fastness. Furthermore, the results of Examples 2, 4 and 5 show that various specific quaternary ammonium salt polymers can achieve excellent color development and wet rub fastness at the same time.

[0149] The results of Examples 2 and 6 to 9 show that excellent color development and wet rubbing fastness can both be achieved with a polyamide epihalohydrin polymer content within a predetermined wide range. Furthermore, the results of Examples 2 and 10 to 13 show that excellent color development and wet rub fastness can both be achieved at a specific quaternary ammonium salt polymer content within a predetermined wide range. Furthermore, the results of Examples 2, 14 and 15 show that excellent color development and wet rubbing fastness can be achieved simultaneously over a wide range of contents of both the polyamide epihalohydrin polymer and the specific quaternary ammonium salt polymer.

[0150] The results of Examples 2, 16 and 17 show that good spray application stability can be maintained even when a predetermined amount of water-insoluble components is contained.

[0151] The results of Examples 4 and 18 show that when the pH of the treatment liquid composition is lower, the color development is good.

[0152] The results of Examples 2, 19 and 20 show that the rubbing fastness can be improved by drying the fabric after application of the treatment liquid composition at a predetermined temperature or higher.

[0153] The following can be derived from the above-described embodiment.

[0154] One embodiment of the treatment liquid composition is a polyamide epihalohydrin polymer; and a quaternary ammonium salt polymer other than the polyamide epihalohydrin polymer.

[0155] In one embodiment of the treatment liquid composition, It may be used by applying it to fabric.

[0156] In any one of the above-mentioned embodiments of the treatment liquid composition, The L of the fabric * The value may be 90 or greater.

[0157] In any one of the above-mentioned embodiments of the treatment liquid composition, The pH of the treatment composition may be less than 7.

[0158] In any one of the above-mentioned embodiments of the treatment liquid composition, The treatment liquid composition may contain no more than 1.0% by mass of water-insoluble components relative to the total mass of the treatment liquid composition.

[0159] One embodiment of the set of the inkjet ink composition and the treatment liquid composition is A set of an inkjet ink composition and a treatment liquid composition of any one of the above aspects, The inkjet ink composition is a water-based pigment inkjet ink containing pigment particles and resin particles, and has a pH of more than 8 and contains particle components with a volume average particle diameter of 20 to 500 nm.

[0160] In one embodiment of the set of the inkjet ink composition and the treatment liquid composition, The particle component may be anionic.

[0161] One aspect of the processing method is an application step of applying the treatment liquid composition of any of the above embodiments to a fabric; 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.

[0162] The present invention is not limited to the above-described embodiments, and various modifications are possible. For example, the present invention includes configurations that are substantially the same as the configurations described in the embodiments, such as configurations with the same functions, methods, and results, or configurations with the same purpose and effects. The present invention also includes configurations in which non-essential parts of the configurations described in the embodiments are replaced. The present invention also includes configurations that achieve the same effects or purposes as the configurations described in the embodiments. The present invention also includes configurations in which publicly known technology is added to the configurations described in the embodiments.

Claims

1. a polyamide epihalohydrin polymer; a quaternary ammonium salt polymer other than the polyamide epihalohydrin polymer; Contains The quaternary ammonium salt polymer is diallyldimethylammonium chloride acrylate. containing an amide copolymer, The content of the polyamide epihalohydrin polymer is 0.01 to 0.01% by weight based on the total amount of the treatment liquid composition. 10% by mass or more and 5.0% by mass or less, The content of the quaternary ammonium salt polymer is 0.50 with respect to the total amount of the processing liquid composition. % by mass or more and 1.2% by mass or less, A fabric treatment liquid composition that is applied to fabric to which ink is to be attached.

2. 2. The treatment liquid composition according to claim 1, wherein the pH of the treatment liquid composition is less than 7.

3. The treatment liquid composition contains no more than 1.0% by mass of water-insoluble components relative to the total mass of the treatment liquid composition. The treatment liquid composition according to claim 1 or 2.

4. An inkjet ink composition and the process of any one of claims 1 to 3 A set of liquid compositions, The inkjet ink composition is a water-based pigment inkjet ink composition containing pigment particles and resin particles. the ink-jet ink composition has a pH greater than 8, and the pigment particles and The resin particles contain particle components having a volume average particle diameter of 20 to 500 nm. A set of an inkjet ink composition and a treatment liquid composition.

5. The ink-jet ink composition of claim 4, wherein the particulate component has anionic properties. A set of processing liquid compositions.

6. A method for applying the treatment liquid composition according to any one of claims 1 to 3 to a fabric. The process and a heating step of heating the fabric to which the treatment liquid composition is attached, The treatment method, wherein the surface temperature of the fabric in the heating step is 100°C or higher.

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