Ink set, printing method, and printed material

Abstract

To provide an ink set capable of suppressing degradation of fabric texture even in the case of printing onto fabric.SOLUTION: An ink set comprises: a pretreatment liquid containing a polyether-modified silicone compound having a hydroxyl value of 50 mgKOH / g or more, and a flocculant; and an aqueous pigment ink containing a urethane resin and a pigment. The content of the polyether-modified silicone compound is 3 mass% or more and 15 mass% or less relative to the total amount of the pretreatment liquid.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an ink set, a printing method, and a printed matter.

Background Art

[0002] In recent years, due to the ease of recording color images and low running costs, the inkjet printing method has been rapidly spreading. Even in the field of textile printing that has been carried out by an analog method centered on dyes, by using an aqueous pigment ink containing a pigment as a coloring material, industrial wastewater generated by printing can be significantly reduced, and it is adopted as an environmentally friendly printing method.

[0003] As the aqueous pigment ink used for printing, an ink containing a polycarbonate-based urethane resin as a binder resin and a styrene acrylic resin having an alkyl group with 10 to 24 carbon atoms as a pigment dispersion resin has been proposed for the purpose of improving storage stability, color development property, and rubbing fastness (see, for example, Patent Document 1). In addition, for the purpose of forming an image having a sufficient density without impairing the texture of the fabric, a printing ink containing a pigment, polymer particles having a glass transition temperature of 50°C or higher, and water, and defining the content ratio of the pigment and the polymer particles has been proposed (see, for example, Patent Document 2).

Summary of the Invention

Problems to be Solved by the Invention

[0004] An object of the present invention is to provide an ink set that can suppress deterioration of the texture even when printing on a fabric.

Means for Solving the Problems

[0005] The ink set of the present invention as a means for solving the above problems is A pretreatment liquid containing a polyether-modified silicone compound having a hydroxyl value of 50 mgKOH / g or more and a flocculant, and An aqueous pigment ink containing a urethane resin and a pigment, and An ink set containing The content of the polyether-modified silicone compound is 3% by mass or more and 15% by mass or less based on the total amount of the pretreatment liquid.

Advantages of the Invention

[0006] According to the present invention, it is possible to provide an ink set capable of suppressing deterioration in texture even when printing on a fabric.

Brief Description of the Drawings

[0007]

Figure 1

Figure 2

Embodiments for Carrying Out the Invention

[0008] Conventionally, in printing on fabrics, pigment inks containing pigments as colorants have a problem of inferior texture compared to the case of using dye inks. This is due to the resin as a binder contained in the pigment ink filling between the fibers of the fabric and forming a film.

[0009] The ink set of the present invention can sufficiently solve various concerns in the prior art. More specifically, it is possible to realize an ink set capable of suppressing deterioration in texture even when printing on a fabric.

[0010] The details of the present invention will be described below.

[0011] (Ink Set) The ink set of the present invention contains a pretreatment liquid and an aqueous pigment ink, and may contain a post-treatment liquid and other members as required. In this specification, "aqueous pigment ink" may be simply referred to as "ink". The "texture" in this specification refers to the feel and touch of the surface obtained by processing a substrate (fabric).

[0012] <Pretreatment liquid> The pretreatment liquid in the present invention contains a polyether-modified silicone compound having a hydroxyl value of 50 mgKOH / g or more and a flocculant, and may contain other components (A) as required. In this specification, "polyether-modified silicone compound having a hydroxyl value of 50 mgKOH / g or more" may be referred to as "polyether-modified silicone compound" or "silicone compound".

[0013] <<Polyether-modified silicone compound>> The polyether-modified silicone compound is a silicone compound having a polyether group in the molecule and a hydroxyl value of 50 mgKOH / g or more.

[0014] The polyether-modified silicone compound in the pretreatment liquid can copolymerize with the urethane resin contained in the aqueous pigment ink described later to modify the properties of the resin. The modification of the resin properties means introducing a silicone structure into the resin, and accordingly, the flexibility of the resin is improved, so that a printed matter with excellent texture can be obtained. This is particularly effective when the printing target is a fabric. In addition, when the hydroxyl value of the polyether-modified silicone compound is 50 mgKOH / g or more, it has excellent reactivity with the resin and a high modification effect can be obtained, so that a printed matter with excellent texture can be obtained.

[0015] In the present invention, the content of the polyether-modified silicone compound is 3% by mass or more and 15% by mass or less based on the total amount of the pretreatment liquid. When the content of the polyether-modified silicone compound is 3% by mass or more and 15% by mass or less based on the total amount of the pretreatment liquid, a sufficient resin modification effect can be obtained, and accordingly, the flexibility of the resin is improved, so that a printed matter with excellent texture can be obtained. In addition, the upper limit of the hydroxyl value of the polyether-modified silicone compound is 100 mgKOH / g.

[0016] There is no particular limitation on the method for measuring the hydroxyl value in the polyether-modified silicone compound, and it can be appropriately selected according to the purpose. For example, it can be measured by titrating with 0.5 M potassium hydroxide using tetrahydrofuran as a solvent.

[0017] The polyether-modified silicone compound may be a both-end functional group type polyether-modified silicone compound having functional groups at both ends of the silicone molecular chain, a single-end functional group type polyether-modified silicone compound having a functional group at one end of the silicone molecular chain, or a side-chain type polyether-modified silicone compound. Among these, from the viewpoint of obtaining a printed matter with excellent texture, it is preferably a both-end functional group type polyether-modified silicone compound. When the both-end functional group type polyether-modified silicone compound is contained in the pretreatment liquid, it undergoes block copolymerization with the resin, and the flexibility of the resin (copolymer) is further improved.

[0018] As the both-end functional group type polyether-modified silicone compound, those synthesized appropriately may be used, or commercially available products may be used. Examples of commercially available products of the both-end functional group type polyether-modified silicone compound include, for example, X-22-4952, X-22-4272, KF-6123 (all manufactured by Shin-Etsu Chemical Co., Ltd.) under the trade name.

[0019] As the polyether-modified silicone compound, those synthesized as appropriate may be used, or commercially available products may be used. Examples of commercially available products of the polyether-modified silicone compound include, for example, X-22-4741, KE-1002, X-22-4952 (all manufactured by Shin-Etsu Chemical Co., Ltd.) under their trade names.

[0020] <<Flocculant>> The flocculant is not particularly limited and can be appropriately selected according to the purpose. Examples include water-soluble cationic polymers, acids, polyvalent metal compounds, and the like.

[0021] The polyvalent metal compound is not particularly limited and can be appropriately selected according to the purpose. Examples include titanium compounds, chromium compounds, copper compounds, cobalt compounds, strontium compounds, barium compounds, iron compounds, aluminum compounds, calcium compounds, magnesium compounds, nickel compounds, and salts (polyvalent metal salts) thereof.

[0022] Specific examples of the polyvalent metal salts include calcium carbonate, calcium nitrate, calcium chloride, calcium acetate, calcium sulfate, magnesium chloride, magnesium acetate, magnesium sulfate, barium sulfate, zinc sulfide, zinc carbonate, aluminum silicate, calcium silicate, magnesium silicate, aluminum hydroxide, potassium nitrate, and the like. Among these, nitrates are preferred from the viewpoint of high solubility in the solvent and good discharge stability due to the difficulty of precipitation after solvent evaporation.

[0023] The content of the flocculant in the pretreatment liquid is not particularly limited and can be appropriately selected according to the purpose. However, from the viewpoint of flocculating the ink to improve the texture, it is preferably 5% by mass or more and 25% by mass or less.

[0024] As the flocculant, those synthesized as appropriate may be used, or commercially available products may be used. Examples of commercially available products of the flocculant include, for example, by trade name, calcium nitrate tetrahydrate, sodium chloride, potassium nitrate, calcium chloride, aluminum chloride (all manufactured by Fujifilm Wako Pure Chemical Corporation), and the like.

[0025] <<Other Component (A)>> There are no particular restrictions on the other component (A), and it can be appropriately selected according to the purpose. Examples include organic solvents, surfactants, defoamers, antiseptic and antifungal agents, rust inhibitors, pH adjusters, water, and the like.

[0026] -Organic Solvent- There are no particular restrictions on the organic solvent, and it can be appropriately selected according to the purpose. For example, water-soluble organic solvents can be used. Examples of the water-soluble organic solvents include polyhydric alcohols, ethers such as polyhydric alcohol alkyl ethers and polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, sulfur-containing compounds, and the like.

[0027] Specific examples of the water-soluble organic solvent include polyhydric alcohols such as ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,3-butanediol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,3-hexanediol, 2,5-hexanediol, 1,5-hexanediol, glycerin, 1,2,6-hexanetriol, 2-ethyl-1,3-hexanediol, ethyl-1,2,4-butanetriol, 1,2,3-butanetriol, 2,2,4-trimethyl-1,3-pentanediol, petriol; polyhydric alcohol alkyl ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl ether; polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether; nitrogen-containing heterocyclic compounds such as 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, γ-butyrolactone; amides such as formamide, N-methylformamide, N,N-dimethylformamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide; amines such as monoethanolamine, diethanolamine, triethylamine; sulfur-containing compounds such as dimethyl sulfoxide, sulfolane, thiodiethanol; and propylene carbonate, ethylene carbonate, etc. Among these, it is preferable to use an organic solvent having a boiling point of 250°C or lower because it not only functions as a wetting agent but also provides good drying properties.

[0028] The content of the organic solvent is not particularly limited and can be appropriately selected according to the purpose. However, from the viewpoints of the drying property and ejection reliability of the pretreatment liquid, it is preferably 10% by mass or more and 60% by mass or less, more preferably 20% by mass or more and 60% by mass or less, based on the total amount of the pretreatment liquid.

[0029] -Surfactant- The surfactant is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include silicone surfactants, fluorine surfactants, amphoteric surfactants, nonionic surfactants, anionic surfactants, etc. These may be used alone or in combination of two or more. As these surfactants, those synthesized as appropriate may be used, or commercially available products may be used. Examples of such commercially available products include those available from BYK-Chemie GmbH, Shin-Etsu Chemical Co., Ltd., Toray Dow Corning Silicone Co., Ltd., Nippon Emulsion Co., Ltd., Kyoeisha Chemical Co., etc.

[0030] The silicone surfactant is not particularly limited and can be appropriately selected according to the purpose. However, those that do not decompose even at high pH (pH 11 to 14) are preferred. Examples of the silicone surfactant that does not decompose even at high pH (pH 11 to 14) include side-chain modified polydimethylsiloxane, both-terminal modified polydimethylsiloxane, one-terminal modified polydimethylsiloxane, side-chain and both-terminal modified polydimethylsiloxane, etc. Among these, those having a polyoxyethylene group or a polyoxyethylene polyoxypropylene group as a modifying group are preferred from the viewpoints of improving hydrophilicity and increasing solubility in water.

[0031] A polyether-modified silicone surfactant can also be used as the silicone surfactant. The polyether-modified silicone surfactant is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include those in which a polyalkylene oxide structure represented by the following general formula (S-1) is introduced into the Si part side chain of dimethylpolysiloxane.

[0032] [Chemical formula] (However, in the general formula (S-1), m, n, a, and b each independently represent an integer. R represents an alkylene group, and R' represents an alkyl group.)

[0033] As the above polyether-modified silicone surfactant, commercially available products can be used. For example, under the trade names, KF-618, KF-642, KF-643 (all manufactured by Shin-Etsu Chemical Co., Ltd.), EMALEX-SS-5602, EMALEX-SS-1906EX (all manufactured by Nippon Emulsion Co., Ltd.), FZ-2105, FZ-2118, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ-2164 (all manufactured by Toray Dow Corning Silicone Co., Ltd.), BYK-33, BYK-387 (all manufactured by BYK-Chemie GmbH), TSF4440, TSF4452, TSF4453 (all manufactured by Toshiba Silicone Co., Ltd.), SAG503A (manufactured by Nissin Chemical Industry Co., Ltd.), etc. can be mentioned.

[0034] The fluorosurfactant is not particularly limited and can be appropriately selected according to the purpose. However, from the viewpoint of low foaming property, perfluoroalkyl sulfonic acid compounds, perfluoroalkyl carboxylic acid compounds, perfluoroalkyl phosphate ester compounds, perfluoroalkyl ethylene oxide adducts, and polyoxyalkylene ether polymer compounds having a perfluoroalkyl ether group in the side chain are preferred. Examples of the perfluoroalkyl sulfonic acid compound include perfluoroalkyl sulfonic acid, perfluoroalkyl sulfonate, etc. Examples of the perfluoroalkyl carboxylic acid compound include perfluoroalkyl carboxylic acid, perfluoroalkyl carboxylate, etc. Examples of the polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain include a sulfate ester salt of a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in the side chain, a salt of a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in the side chain, and the like.

[0035] Examples of the counter ion of the salt in these fluorosurfactants include, for example, Li, Na, K, NH 4 , NH 3 CH 2 CH 2 OH, NH 2 (CH 2 CH 2 OH) 2 , NH(CH 2 CH 2 OH) 3 and the like.

[0036] Among these, fluorosurfactants represented by the following general formulas (F-1) and (F-2) are preferable.

[0037]

Chemical formula

[0038]

Chemical formula

[0039] As the fluorosurfactant, a compound having 2 to 16 carbon atoms with fluorine substitution is preferable, and a compound having 4 to 16 carbon atoms with fluorine substitution is more preferable.

[0040] As the fluorosurfactant, those synthesized as appropriate may be used, or commercially available products may be used. Examples of commercially available products of the fluorosurfactant include, for example, under the trade names Surfron S-111, Surfron S-112, Surfron S-113, Surfron S-121, Surfron S-131, Surfron S-132, Surfron S-141, Surfron S-145 (all manufactured by AGC, Inc.); Fluorad FC-93, Fluorad FC-95, Fluorad FC-98, Fluorad FC-129, Fluorad FC-135, Fluorad FC-170C, Fluorad FC-430, Fluorad FC-431 (all manufactured by 3M Japan Ltd.); Megafac F-470, Megafac F-1405, Megafac F-474 (all manufactured by DIC Corporation); Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, UR (all manufactured by DuPont); FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW (all manufactured by Neos Co., Ltd.); Polyfox PF-136A, Polyfox PF-156A, Polyfox PF-151N, Polyfox PF-154, Polyfox PF-159 (manufactured by Omnova), Unidine DSN-403N (manufactured by Daikin Industries, Ltd.), and the like. Among these, FS-300 manufactured by DuPont, FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW manufactured by Neos Co., Ltd., Polyfox PF-151N manufactured by Omnova, and Unidine DSN-403N manufactured by Daikin Industries, Ltd. are particularly preferable because of the significantly improved printing quality, especially color development, penetrability, wettability, and leveling property with respect to paper.

[0041] The amphoteric surfactant is not particularly limited and can be appropriately selected according to the purpose. For example, lauryl aminopropionate, lauryl dimethyl betaine, stearyl dimethyl betaine, lauryl dihydroxyethyl betaine, etc. can be mentioned.

[0042] The nonionic surfactant is not particularly limited and can be appropriately selected according to the purpose. For example, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkyl amine, polyoxyethylene alkyl amide, polyoxyethylene propylene block polymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, ethylene oxide adduct of acetylene alcohol, etc. can be mentioned.

[0043] The anionic surfactant is not particularly limited and can be appropriately selected according to the purpose. For example, polyoxyethylene alkyl ether acetate, dodecyl benzene sulfonate, laurate, salt of polyoxyethylene alkyl ether sulfate, etc. can be mentioned.

[0044] The content of the surfactant is not particularly limited and can be appropriately selected according to the purpose. However, from the viewpoints of excellent wettability and discharge stability and improved image quality, it is preferably 0.001% by mass or more and 5% by mass or less, more preferably 0.05% by mass or more and 5% by mass or less, based on the total amount of the pretreatment liquid.

[0045] - Defoaming agent - The surfactant used as the other component (A) can be used as a defoaming agent. The defoaming agent is not particularly limited and can be appropriately selected according to the purpose. For example, silicone-based defoaming agents, polyether-based defoaming agents, fatty acid ester-based defoaming agents, etc. can be mentioned. Among these, silicone-based defoaming agents are preferred from the viewpoint of excellent defoaming effect. These may be used alone or in combination of two or more.

[0046] -Antiseptic and mildew-proof agent- The antiseptic and mildew-proof agent is not particularly limited and can be appropriately selected according to the purpose. For example, 1,2-benzisothiazolin-3-one and the like can be mentioned.

[0047] -Rust inhibitor- The rust inhibitor is not particularly limited and can be appropriately selected according to the purpose. For example, acid sulfite, sodium thiosulfate and the like can be mentioned. As the rust inhibitor, those synthesized appropriately may be used, or commercially available products may be used. Examples of commercially available products of the rust inhibitor include, for example, Proxel LV (manufactured by Avecia) under the trade name.

[0048] -pH adjuster- The pH adjuster is not particularly limited as long as it can adjust the pH to 7 or more, and can be appropriately selected according to the purpose. For example, amines such as diethanolamine and triethanolamine can be mentioned.

[0049] -Water- The water is not particularly limited and can be appropriately selected according to the purpose. The content of the water is not particularly limited and can be appropriately selected according to the purpose. However, from the viewpoints of the drying property and ejection reliability of the pretreatment liquid, it is preferably 10% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 60% by mass or less, based on the total amount of the pretreatment liquid.

[0050] Examples of the qualitative and quantitative methods for various components contained in the pretreatment liquid and other components (A) and the like include gas chromatography-mass spectrometry (GC-MS). Examples of the measuring apparatus by gas chromatography-mass spectrometry (GC-MS) include, for example, GCMS-QP2020NX (manufactured by Shimadzu Corporation). In addition, the water contained in the pretreatment liquid can be measured by general methods, such as quantification of volatile components by gas chromatography-mass spectrometry (GC-MS) and mass variation by thermogravimetry-differential thermal simultaneous measurement method (TG-DTA).

[0051] There are no particular restrictions on the physical properties of the pretreatment liquid, and it can be appropriately selected according to the purpose. For example, it is preferable that the viscosity, surface tension, pH, etc. are within the following ranges. From the viewpoint of improving the printing density and the quality of characters and obtaining good dischargeability, the viscosity of the pretreatment liquid at 25°C is preferably 5 mPa·s or more and 30 mPa·s or less, and more preferably 5 mPa·s or more and 25 mPa·s or less. Here, the viscosity can be measured, for example, using a rotational viscometer (RE85L manufactured by Toki Sangyo Co., Ltd.). As the measurement conditions, it can be measured at 25°C, with a standard cone rotor (1°34’×R24), a sample liquid volume of 1.2 mL, a rotation speed of 50 rpm, and for 3 minutes. From the viewpoint of the pretreatment liquid being preferably leveled on the fabric and shortening the drying time of the pretreatment liquid, the surface tension of the pretreatment liquid at 25°C is preferably 35 mN / m or less, and more preferably 32 mN / m or less. From the viewpoint of preventing corrosion of the metal members in contact with the liquid, the pH of the pretreatment liquid is preferably 7 to 12, and more preferably 8 to 11.

[0052] <Water-based pigment ink> The water-based pigment ink contains a urethane resin and a pigment, and may contain other components (B) as necessary.

[0053] <<Urethane resin>> There are no particular restrictions on the urethane resin as long as it is a resin having a urethane skeleton, and it can be appropriately selected according to the purpose.

[0054] There are no particular restrictions on the shape of the urethane resin, and it can be appropriately selected according to the purpose. It may be regular or irregular. Among these, it is preferably regular. When the urethane resin is regular, it is preferably spherical. When the urethane resin is spherical, it is preferably particulate. The particles of the urethane resin can be mixed with materials such as pigments and organic solvents described later in the state of a resin emulsion in which water is used as a dispersion medium to obtain an ink.

[0055] The volume average particle diameter of the urethane resin is not particularly limited and can be appropriately selected according to the purpose. However, from the viewpoints of obtaining good fixing property and high image hardness, it is preferably 10 nm or more and 1,000 nm or less, more preferably 10 nm or more and 200 nm or less, and still more preferably 10 nm or more and 100 nm or less. The volume average particle diameter can be measured, for example, using a particle size analyzer (NanoTrack Wave-UT151, manufactured by Microtrac Bell Corporation).

[0056] The content (solid content concentration) of the urethane resin is not particularly limited and can be appropriately selected according to the purpose. However, from the viewpoint of obtaining an image with good texture, it is preferably 8% by mass or more and 15% by mass or less, more preferably 8% by mass or more and 12% by mass or less, based on the total amount of the ink.

[0057] The urethane resin may be a reactive urethane resin having a reactive group or a non-reactive urethane resin having no reactive group. Among these, from the viewpoint of obtaining an image with good texture, a reactive urethane resin having a reactive group is preferable. In addition, the "reactive group" in this specification includes, for example, an isocyanate group.

[0058] As the urethane resin, those synthesized appropriately may be used, or commercially available products may be used. Examples of commercially available products of the urethane resin include, by trade name, Takelac WS-6021, Takelac WS-5000, Takelac WS-5100, Takelac WS-4000, Takelac W-6110 (all manufactured by Mitsui Chemicals, Inc.), Elastron BAP, Elastron BM-69, Elastron BN-P18 (all manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), and the like.

[0059] <<Pigment>> There are no particular restrictions on the pigment, and it can be appropriately selected according to the purpose. For example, an inorganic pigment or an organic pigment can be used. These may be used alone or in combination of two or more. Also, mixed crystals may be used.

[0060] As the pigment, for example, a black pigment, a yellow pigment, a magenta pigment, a cyan pigment, a white pigment, a green pigment, an orange pigment, a metallic pigment such as a metallic color pigment like gold or silver, etc. can be used.

[0061] As the inorganic pigment, for example, titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow, and in addition, carbon black produced by known methods such as the contact method, the furnace method, the thermal method, etc. can be used. As the organic pigment, for example, azo pigments, polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments, etc.), dye chelates (for example, basic dye type chelates, acid dye type chelate sugars), nitro pigments, nitroso pigments, aniline black, etc. can be used. Among these pigments, those having good affinity with the solvent are preferably used. In addition, the use of resin hollow particles and inorganic hollow particles is also possible.

[0062] Specific examples of the pigment include the following. As the pigment for black, for example, carbon blacks (C.I. Pigment Black 7) such as furnace black, lamp black, acetylene black, channel black, etc., or metals such as copper, iron (C.I. Pigment Black 11), titanium oxide, and organic pigments such as aniline black (C.I. Pigment Black 1) can be mentioned. Examples of pigments for colors include, for example, C.I. Pigment Yellow 1, C.I. Pigment Yellow 3, C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, C.I. Pigment Yellow 17, C.I. Pigment Yellow 24, C.I. Pigment Yellow 34, C.I. Pigment Yellow 35, C.I. Pigment Yellow 37, C.I. Pigment Yellow 42 (Yellow Iron Oxide), C.I. Pigment Yellow 53, C.I. Pigment Yellow 55, C.I. Pigment Yellow 74, C.I. Pigment Yellow 81, C.I. Pigment Yellow 83, C.I. Pigment Yellow 95, C.I. Pigment Yellow 97, C.I. Pigment Yellow 98, C.I. Pigment Yellow 100, C.I. Pigment Yellow 101, C.I. Pigment Yellow 104, C.I. Pigment Yellow 108, C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow 117, C.I. Pigment Yellow 120, C.I. Pigment Yellow 138, C.I. Pigment Yellow 150, C.I. Pigment Yellow 153, C.I. Pigment Yellow 155, C.I. Pigment Yellow 180, C.I. Pigment Yellow 185, C.I. Pigment Yellow 213, C.I. Pigment Orange 5, C.I. Pigment Orange 13, C.I. Pigment Orange 16, C.I. Pigment Orange 17, C.I. Pigment Orange 36, C.I. Pigment Orange 43, C.I. Pigment Orange 51, C.I. Pigment Red 1, C.I. Pigment Red 2, C.I. Pigment Red 3, C.I. Pigment Red 4, C.I. Pigment Red 5, C.I. Pigment Red 17, C.I. Pigment Red 22, C.I. Pigment Red 23, C.I. Pigment Red 31, C.I. Pigment Red 38, C.I. Pigment Red 48:2, C.I. Pigment Red 48:3, C.I. Pigment Red 48:4, C.I. Pigment Red 49:1, C.I. Pigment Red 52:2, C.I. Pigment Red 53:1, C.I. Pigment Red 57:1 (Brilliant Carmine 6B), C.I. Pigment Red 60:1, C.I.Pigment Red 63:1, C.I. Pigment Red 63:2, C.I. Pigment Red 64:1, C.I. Pigment Red 81, C.I. Pigment Red 83, C.I. Pigment Red 88, C.I. Pigment Red 101 (vermilion), C.I. Pigment Red 104, C.I. Pigment Red 105, C.I. Pigment Red 106, C.I. Pigment Red 108 (cadmium red), C.I. Pigment Red 112, C.I. Pigment Red 114, C.I. Pigment Red 122 (quinacridone magenta), C.I. Pigment Red 123, C.I. Pigment Red 146, C.I. Pigment Red 149, C.I. Pigment Red 166, C.I. Pigment Red 168, C.I. Pigment Red 170, C.I. Pigment Red 172, C.I. Pigment Red 177, C.I. Pigment Red 178, C.I. Pigment Red 179, C.I. Pigment Red 184, C.I. Pigment Red 185, C.I. Pigment Red 190, C.I. Pigment Red 193, C.I. Pigment Red 202, C.I. Pigment Red 207, C.I. Pigment Red 208, C.I. Pigment Red 209, C.I. Pigment Red 213, C.I. Pigment Red 219, C.I. Pigment Red 224, C.I. Pigment Red 254, C.I. Pigment Red 264, C.I. Pigment Violet 1 (rhodamine lake), C.I. Pigment Violet 3, C.I. Pigment Violet 5:1, C.I. Pigment Violet 16, C.I. Pigment Violet 19, C.I. Pigment Violet 23, C.I. Pigment Violet 38, C.I. Pigment Blue 1, C.I. Pigment Blue 2, C.I. Pigment Blue 15 (phthalocyanine blue), C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:2, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4 (phthalocyanine blue), C.I. Pigment Blue 16, C.I. Pigment Blue 17:1, C.I. Pigment Blue 56, C.I. Pigment Blue 60, C.I. Pigment Blue 63, C.I. Pigment Green 1, C.I. Pigment Green 4, C.I.Examples include Pigment Green 7, C.I. Pigment Green 8, C.I. Pigment Green 10, C.I. Pigment Green 17, C.I. Pigment Green 18, C.I. Pigment Green 36, and the like.

[0063] From the viewpoints of improving image density, achieving good fixability and ejection stability, the content of the pigment is preferably 0.1% by mass or more and 15% by mass or less, more preferably 1% by mass or more and 10% by mass or less, based on the total amount of the ink.

[0064] In order to obtain ink by dispersing a pigment, examples include (1) a method of introducing a hydrophilic functional group into the pigment to obtain a self-dispersible pigment, (2) a method of coating the surface of the pigment with a resin for dispersion, and (3) a method of dispersing using a dispersant. As the method (1) of introducing a hydrophilic functional group into the pigment to obtain a self-dispersible pigment, for example, a method of making it dispersible in water by adding a functional group such as a sulfone group or a carboxyl group to the pigment (for example, carbon) can be mentioned. As the method (2) of coating the surface of the pigment with a resin for dispersion, a method of including the pigment in microcapsules to make it dispersible in water can be mentioned. The pigment whose surface is coated with a resin for dispersion can be rephrased as a resin-coated pigment. When coating the surface of the pigment with a resin for dispersion, not all the pigments incorporated in the ink need to be coated with the resin, and uncoated pigments or partially coated pigments may be dispersed in the ink as long as the effects of the present invention are not impaired. As the method (3) of dispersing using a dispersant, methods of dispersing using known low-molecular-type dispersants and high-molecular-type dispersants typified by surfactants can be mentioned. As the dispersant, for example, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, etc. can be used according to the pigment. Pyionin RT-100 (nonionic surfactant) manufactured by Takemoto Yushi Co., Ltd. and sodium naphthalene sulfonate formalin condensate can also be suitably used as the dispersant. The dispersant may be used alone or in combination of two or more.

[0065] - Pigment Dispersion - It is possible to obtain ink by mixing materials such as water and organic solvents with the pigment. It is also possible to manufacture ink by mixing a pigment with other materials such as water and a dispersant to form a pigment dispersion and then mixing materials such as water and organic solvents therewith. The pigment dispersion is obtained by mixing, dispersing water, a pigment, a pigment dispersant, and other components as necessary, and adjusting the particle size. A disperser may be used for the dispersion. Further, the pigment dispersion is preferably filtered to remove coarse particles and degassed using a filter, a centrifugal separator, or the like as necessary.

[0066] The particle size of the pigment in the pigment dispersion is not particularly limited, but from the viewpoint of good dispersion stability of the pigment and high image quality such as ejection stability and image density, the maximum frequency in terms of the maximum number is preferably 20 nm or more and 500 nm or less, and more preferably 20 nm or more and 150 nm or less. The particle size of the pigment can be measured using a particle size analyzer (Nanotrac WaveII-UT151, manufactured by Microtrac MRB Co., Ltd.).

[0067] The content of the pigment in the pigment dispersion is not particularly limited and can be appropriately selected according to the purpose. However, from the viewpoint of obtaining good ejection stability and increasing the image density, it is preferably 0.1% by mass or more and 50% by mass or less, and more preferably 0.1% by mass or more and 30% by mass or less, based on the total amount of the pigment dispersion.

[0068] The particle size of the solid content in the ink is not particularly limited and can be appropriately selected according to the purpose. However, from the viewpoint of improving ejection stability and image quality such as image density, the maximum frequency of the particle size of the solid content in the ink is preferably 20 nm or more and 1,000 nm or less, and more preferably 20 nm or more and 150 nm or less, in terms of the maximum number. The solid content includes the resin particles and the pigment particles. The particle size can be measured using a particle size analyzer (Nanotrac WaveII-UT151, manufactured by Microtrac MRB Co., Ltd.).

[0069] <<Other Component (B)>> The other component (B) is not particularly limited and can be appropriately selected according to the purpose. For example, additives such as surfactants, defoamers, antiseptics, rust inhibitors, and pH adjusters may be added. The surfactant, the defoamer, the antiseptic, the rust inhibitor, and the pH adjuster are not particularly limited and can be appropriately selected according to the purpose. For example, those similar to those described in the item of <pretreatment liquid> mentioned above can be used.

[0070] The content of the surfactant is not particularly limited and can be appropriately selected according to the purpose. However, from the viewpoints of excellent wettability and ejection stability and improved image quality, it is preferably 0.001% by mass or more and 5% by mass or less, more preferably 0.05% by mass or more and 5% by mass or less, based on the total amount of the ink.

[0071] The contents of the defoamer, the antiseptic, the rust inhibitor, and the pH adjuster are not particularly limited and can be appropriately set according to the contents of various materials.

[0072] Examples of the qualitative and quantitative methods for the organic solvent, resin, pigment, and other component (B) contained in the ink include gas chromatography-mass spectrometry (GC-MS). Examples of the measuring device by gas chromatography-mass spectrometry (GC-MS) include GCMS-QP2020NX (manufactured by Shimadzu Corporation). In addition, the water contained in the ink can be measured by general methods, such as quantification of volatile components by gas chromatography-mass spectrometry (GC-MS) and mass variation by thermogravimetry-differential thermal simultaneous measurement method (TG-DTA).

[0073] The physical properties of the ink are not particularly limited and can be appropriately selected according to the purpose. For example, it is preferable that the viscosity, surface tension, pH, etc. are in the following ranges. The viscosity of the ink at 25°C is preferably 5 mPa·s or more and 30 mPa·s or less, more preferably 5 mPa·s or more and 25 mPa·s or less, from the viewpoints of improving the printing density and the character quality and obtaining good ejection properties. Here, for measuring the viscosity, for example, a rotational viscometer (RE85L manufactured by Toki Sangyo Co., Ltd.) can be used. As the measurement conditions, it can be measured at 25°C, with a standard cone rotor (1°34’×R24), a sample liquid volume of 1.2 mL, a rotation speed of 50 rpm, and for 3 minutes. As for the surface tension of the ink, from the viewpoints of the ink being preferably leveled on the fabric and shortening the drying time of the ink, it is preferably 35 mN / m or less, more preferably 32 mN / m or less at 25°C. As for the pH of the ink, from the viewpoint of preventing corrosion of the metal members in contact with the liquid, 7 to 12 is preferable, and 8 to 11 is more preferable.

[0074] <Post-treatment liquid> The post-treatment liquid is not particularly limited as long as it can form a transparent layer. The post-treatment liquid is obtained by selectively choosing and mixing, as necessary, an organic solvent, water, resin, surfactant, defoaming agent, pH adjuster, antiseptic and antifungal agent, rust preventive agent, etc. In addition, since these respective components can use the same ones as those described in the above item (ink set), duplicate descriptions are omitted. The post-treatment liquid may be applied to the entire recording area formed on the recording medium, or may be applied only to the area where the ink image is formed.

[0075] The use of the ink set is not particularly limited and can be appropriately selected according to the purpose, but it is preferably for inkjet.

[0076] (Printed matter) The printed matter of the present invention is a printed matter obtained by printing an ink set on a fabric. Since the ink set is the same as the above-mentioned (ink set), duplicate descriptions are omitted.

[0077] <Fabric> The fabric is not particularly limited and can be appropriately selected according to the purpose. For example, cotton broadcloth, polyester tropical fabric, etc. can be mentioned.

[0078] (Printing method and printing apparatus) The printing method of the present invention includes a pretreatment liquid application step, an ink application step, and a drying step, and may include other steps as necessary. The printing apparatus according to the present invention has a pretreatment liquid application means, an ink application means, and a drying means, and may have other means as necessary. The pretreatment liquid application step can be preferably carried out by the pretreatment liquid application means, the ink application step can be preferably carried out by the ink application means, the drying step can be preferably carried out by the drying means, and the other steps can be preferably carried out by the other means.

[0079] <Pretreatment liquid application step and pretreatment liquid application means> The pretreatment liquid application step is a step of applying a pretreatment liquid to the fabric. The pretreatment liquid application means is a means for applying a pretreatment liquid to the fabric. Since the pretreatment liquid and the fabric are the same as those described in the above item (Inkjet), duplicate descriptions are omitted.

[0080] The pretreatment liquid application step (means) is not particularly limited and can be appropriately selected according to the purpose. For example, an inkjet method, a blade coating method, a gravure coating method, a bar coating method, a roll coating method, a dip coating method, a curtain coating method, a slide coating method, a die coating method, a spray coating method, etc. can be mentioned. Among these, the inkjet method is preferable.

[0081] <Ink application step and ink application means> The ink application step is a step of applying aqueous pigment ink to the fabric to which the pretreatment liquid has been applied. The ink application means is a means for applying aqueous pigment ink to the fabric to which the pretreatment liquid has been applied. Since the same ones as the pretreatment liquid application step and the pretreatment liquid application means can be used for the ink application step and the ink application means, duplicate descriptions are omitted.

[0082] <Drying step and drying means> The drying step is a step of drying the fabric to which the aqueous pigment ink has been applied at 120°C or higher and 160°C or lower. The drying means includes a means for drying the fabric to which the aqueous pigment ink has been applied at 120°C or higher and 160°C or lower. The drying step can be preferably carried out by the drying means. The drying step (means) can also be paraphrased as a heating step (means).

[0083] The drying (heating) step and the drying (heating) means are not particularly limited, but for example, a hot air heater, an infrared heater, etc. can be used. Heating and drying can be carried out before printing, during printing, after printing, etc.

[0084] <Other steps and other means> The other steps are not particularly limited and can be appropriately selected according to the purpose. For example, a post-treatment liquid application step can be mentioned. The other means are not particularly limited and can be appropriately selected according to the purpose. For example, a post-treatment liquid application means can be mentioned.

[0085] <<Post-treatment liquid application step and post-treatment liquid application means>> The post-treatment liquid application step is a step of applying a post-treatment liquid to the fabric to which the aqueous pigment ink has been applied. The post-treatment liquid application means is a means for applying a post-treatment liquid to the fabric to which the aqueous pigment ink has been applied. The post-treatment liquid application step can be preferably carried out by the post-treatment liquid application means.

[0086] As one aspect of the post-treatment liquid applying means, in the case of aqueous pigment inks such as black (K), cyan (C), magenta (M), and yellow (Y), a liquid storage section containing the post-treatment liquid and a liquid ejection head are added, and there is an aspect of ejecting the post-treatment liquid by an inkjet recording method, similar to the case of aqueous pigment inks. The post-treatment liquid applying means is not particularly limited and can be appropriately selected according to the purpose. For example, the same means as the above-described pre-treatment liquid applying means can be used.

[0087] The printing apparatus according to the present invention can be applied to various recording apparatuses using an inkjet recording method, such as printers, facsimile apparatuses, copying apparatuses, printer / fax / copier multifunction machines, and three-dimensional modeling apparatuses.

[0088] The printing method and printing apparatus of the present invention are not limited to those in which significant images such as characters and figures are visualized by ink. For example, those forming patterns such as geometric patterns and those forming three-dimensional images are also included. The printing apparatus includes, unless otherwise particularly limited, both a serial type apparatus that moves the ejection head and a line type apparatus that does not move the ejection head. Further, the printing apparatus includes not only desktop types but also wide-format recording apparatuses capable of printing on A0-sized fabrics, and continuous printers that can use, for example, fabrics wound in a roll shape as a recording medium.

[0089] In the terms of the present invention, image formation, recording, printing, etc. are all synonymous.

[0090] Here, an embodiment of the printing apparatus of the present invention will be described with reference to the drawings. However, the present invention is not limited to these embodiments at all. In each drawing, the same reference numerals are given to the same components, and redundant explanations may be omitted. Also, the number, position, shape, etc. of the following components are not limited to this embodiment, and can be set to preferable numbers, positions, shapes, etc. for carrying out the present invention.

[0091] FIG. 1 is a schematic diagram showing an embodiment of a printing apparatus according to the present invention. FIG. 2 is a schematic diagram showing an example of a main tank of the printing apparatus according to the present invention. An image forming apparatus 400 as an example of a recording apparatus is a serial type image forming apparatus. Inside an exterior 401 of the image forming apparatus 400, a mechanism unit 420 is provided. For example, each ink storage unit 411 of main tanks 410 (410k, 410c, 410m, 410y) for respective colors such as black (K), cyan (C), magenta (M), and yellow (Y) is formed of a packaging member such as an aluminum laminate film. The ink storage unit 411 is accommodated in an accommodation container case 414 made of plastics, for example. Thereby, the main tank 410 is used as an ink cartridge for each color. Note that the colors of the inks are not limited to black (K), cyan (C), magenta (M), and yellow (Y), and other colors such as white and metallic ink may be used. The same applies to the main tanks 410 for respective colors and the ink storage units 411. On the other hand, a cartridge holder 404 is provided on the back side of the opening when the cover 401c of the apparatus main body is opened. The main tank 410 is detachably attached to the cartridge holder 404. Thereby, each ink discharge port 413 of the main tank 410 communicates with a discharge head 434 for each color through a supply tube 436 for each color, and ink can be discharged from the discharge head 434 onto a recording medium. Further, the main tanks 410 for respective colors and the ink storage units 411 may be filled with a pretreatment liquid or a post-treatment liquid instead of the ink, and discharged from the discharge head 434 onto a recording medium (fabric).

Example

[0092] Hereinafter, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to these examples at all. In the following examples and comparative examples, unless otherwise specified, “parts” means “parts by mass” and “%” means “mass %”.

[0093] <Production Example of Black Pigment Dispersion> In a flask, 11.2 g of styrene, 2.8 g of acrylic acid, 12 g of lauryl methacrylate, 4 g of polyethylene glycol methacrylate, 4 g of styrene macromer, and 0.4 g of mercaptoethanol were mixed and heated to 65°C. Next, a mixed solution of 100.8 g of styrene, 25.2 g of acrylic acid, 108 g of lauryl methacrylate, 36 g of polyethylene glycol methacrylate, 60 g of hydroxyethyl methacrylate, 36 g of styrene macromer, 3.6 g of mercaptoethanol, 2.4 g of azobis(methylvaleronitrile), and 18 g of methyl ethyl ketone was dropped into the flask over 2.5 hours. Thereafter, a mixed solution of 0.8 g of azobis(methylvaleronitrile) and 18 g of methyl ethyl ketone was dropped into the flask over 0.5 hours. Next, after aging at 65°C for 1 hour, 0.8 g of azobis(methylvaleronitrile) was added, and the reaction was carried out by further aging for 1 hour. After completion of the reaction, 364 g of methyl ethyl ketone was added to the flask to obtain 800 g of polymer solution A having a solid content concentration of 50%. Next, 28 g of polymer solution A, 42 g of carbon black (Black Pearls 1000, manufactured by Cabot Corporation), 13.6 g of 1 mol / L potassium hydroxide aqueous solution, 20 g of methyl ethyl ketone, and 13.6 g of water were sufficiently stirred and then kneaded with a roll mill to obtain a paste. The obtained paste was put into 200 g of pure water and sufficiently stirred, then methyl ethyl ketone was removed with an evaporator, and after pressure filtration with a polyvinylidene fluoride membrane filter having an average pore diameter of 5 μm, the water content was adjusted so that the solid content concentration became 20%, and a black pigment dispersion having a solid content concentration of 20% was obtained.

[0094] <Preparation Example of Example 1> The following [ink formulation] and [pretreatment liquid formulation] were each mixed and stirred, and filtered through a filter (Mini Sartorius, manufactured by Sartorius) having an average pore diameter of 5 μm to prepare the pretreatment liquid and ink of Example 1. [Pretreatment Liquid Formulation 1] · Both - terminal functional - group - type polyether - modified silicone compound (trade name: X - 22 - 4272, manufactured by Shin - Etsu Chemical Co., Ltd.): 3 parts by mass · Calcium nitrate tetrahydrate (manufactured by Fujifilm Wako Pure Chemical Corporation): 20 parts by mass · Propylene glycol: 20 parts by mass · Ion - exchanged water: balance (total: 100 parts by mass) [Ink formulation 1] · Black pigment dispersion: 20 parts by mass · Reactive urethane resin (trade name: Takelac WS - 6021, manufactured by Dai - Ichi Kogyo Seiyaku Co., Ltd.): 10 parts by mass · Silicone surfactant (trade name: SAG503A, manufactured by Nissin Chemical Industry Co., Ltd., HLB value: 11): 0.1 part by mass · Propylene glycol: 20 parts by mass · Antiseptic and antifungal agent (trade name: Proxel LV, manufactured by Avecia): 0.1 part by mass · Ion - exchanged water: balance (total: 100 parts by mass)

[0095] <Preparation examples of Examples 2 - 10 and Comparative Examples 1 - 5> In the preparation example of Example 1, except that the ink formulations described in Tables 1 - 3 were changed, the pretreatment liquid and ink of Examples 2 - 10 and Comparative Examples 1 - 5 were prepared in the same manner as the preparation example of Example 1. The detailed contents of each component in Tables 1 - 3 are as follows. · Side - chain - type polyether - modified silicone (trade name: X - 22 - 4741, manufactured by Shin - Etsu Chemical Co., Ltd) · Polyether - modified silicone (trade name: SAG503A, manufactured by Shin - Etsu Chemical Co., Ltd) · Non - reactive urethane resin particles (trade name: W - 6110, manufactured by Mitsui Chemicals, Inc.) · Acrylic resin particles (trade name: FX - 2033, manufactured by Nippon Carbide Industries Co., Ltd.) · Polyester resin particles (trade name: KT - 8904, manufactured by Unitika Ltd.)

[0096] <Example 1> For the production of the printed matter, the Ri100 (manufactured by Ricoh Company, Ltd.), a DTG printer, was used. Each pretreatment liquid and each ink were filled into the ink tanks installed in the inkjet printer.

[0097] [Evaluation of texture] Using the inkjet printer, for the fabric (cotton), after printing with the pretreatment liquid at an adhesion amount of 10 g / m 2 immediately, black ink was printed at an adhesion amount of 20 g / m 2 and dried at 160 °C for 5 minutes to obtain a printed matter. The obtained printed matter was cut into a square of 85 mm on each side, and the stiffness was measured using a hand-held hardness meter (product name: HOM-200, manufactured by Daiei Kagaku Seiki Co., Ltd.). The results are shown in Tables 1 to 3. [Evaluation criteria] ◎: Stiffness is less than 20 g 〇: Stiffness is 20 g or more and less than 35 g △: Stiffness is 35 g or more and less than 50 g ×: Stiffness is 50 g or more

[0098] [Evaluation of image quality] Each printed matter obtained in the above [Evaluation of texture] was visually observed to evaluate the degree of bleeding of the characters. The results are shown in Tables 1 to 3. [Evaluation criteria] 〇: No bleeding of characters is observed △: Slight bleeding of characters is observed ×: Obvious bleeding of characters is observed

[0099]

Table 1

[0100]

Table 2

[0101]

Table 3

[0102] Examples of aspects of the present invention include, for example, the following. <1> A pretreatment liquid containing a polyether-modified silicone compound having a hydroxyl value of 50 mgKOH / g or more and a flocculant, and An aqueous pigment ink containing a urethane resin and a pigment, and an ink set, wherein The content of the polyether-modified silicone compound is 3% by mass or more and 15% by mass or less with respect to the total amount of the pretreatment liquid, and the ink set is characterized in that. <2> The polyether-modified silicone compound is of a both-end functional group type, and the ink set according to <1>. <3> The urethane resin is a reactive urethane resin, and the ink set according to <1> or <2>. <4> The content of the polyether-modified silicone compound is 5% by mass or more and 10% by mass or less with respect to the total amount of the pretreatment liquid, and the ink set according to any one of <1> to <3>. <5> The solid content concentration of the urethane resin in the ink is 8% by mass or more and 15% by mass or less, and the ink set according to any one of <1> to <4>. <6> The ink set according to any one of <1> to <5>, which is for inkjet. <7> A pretreatment liquid application step of applying a pretreatment liquid containing a polyether-modified silicone compound having a hydroxyl value of 50 mgKOH / g or more and a flocculant to a fabric, and An ink application step of applying an aqueous pigment ink containing a urethane resin and a pigment to the fabric to which the pretreatment liquid has been applied, and A drying step of drying the fabric to which the aqueous pigment ink has been applied at 120° C. or higher and 160° C. or lower, and a printing method including the steps. A printing method characterized in that the content of the polyether-modified silicone compound is 3% by mass or more and 15% by mass or less based on the total amount of the pretreatment liquid. <8> A printed matter obtained by printing an ink set on a fabric, wherein the ink set includes a pretreatment liquid containing a polyether-modified silicone compound having a hydroxyl value of 50 mgKOH / g or more and a flocculant, and an aqueous pigment ink containing a urethane resin and a pigment, and a printed matter characterized in that the content of the polyether-modified silicone compound is 3% by mass or more and 15% by mass or less based on the total amount of the pretreatment liquid.

[0103] The ink set according to any one of <1> to <6>, the printing method according to <7>, and the printed matter according to <8> can solve the above-mentioned various problems in the prior art and achieve the object of the present invention.

Explanation of Signs

[0104] 400 Image forming apparatus 401 Exterior 401c Cover 404 Cartridge holder 410 Main tank 411 Ink storage section 420 Mechanism section 434 Discharge head 436 Supply tube

Prior Art Documents

Patent Documents

[0105]

Patent Document 1

Patent Document 2

Claims

1. A pretreatment liquid containing a polyether-modified silicone compound having a hydroxyl value of 50 mg KOH / g or more and a flocculant, and An ink set containing an aqueous pigment ink containing a urethane resin and a pigment, wherein The content of the polyether-modified silicone compound is 3% by mass or more and 15% by mass or less based on the total amount of the pretreatment liquid. The ink set is characterized by this.

2. The ink set according to claim 1, wherein the polyether-modified silicone compound is of a both-end functional group type.

3. The ink set according to claim 1 or 2, wherein the urethane resin is a reactive urethane resin.

4. The ink set according to claim 1 or 2, wherein the content of the polyether-modified silicone compound is 5% by mass or more and 10% by mass or less based on the total amount of the pretreatment liquid.

5. The ink set according to claim 1 or 2, wherein the solid content concentration of the urethane resin in the aqueous pigment ink is 8% by mass or more and 15% by mass or less.

6. The ink set according to claim 1 or 2, which is for inkjet.

7. A pretreatment liquid application step of applying a pretreatment liquid containing a polyether-modified silicone compound having a hydroxyl value of 50 mg KOH / g or more and a flocculant to a fabric, and An ink application step of applying an aqueous pigment ink containing a urethane resin and a pigment to the fabric to which the pretreatment liquid has been applied, and A drying step of drying the fabric to which the aqueous pigment ink has been applied at 120°C or higher and 160°C or lower. A printing method characterized in that The content of the polyether-modified silicone compound is 3% by mass or more and 15% by mass or less based on the total amount of the pretreatment liquid.

8. A printed matter obtained by printing an ink set on a fabric, wherein The ink set is A pretreatment liquid containing a polyether-modified silicone compound having a hydroxyl value of 50 mg KOH / g or more and a flocculant, and An aqueous pigment ink containing a urethane resin and a pigment, and The content of the polyether-modified silicone compound is 3% by mass or more and 15% by mass or less based on the total amount of the pretreatment liquid. The printed matter is characterized by this.

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