JP2000265381A - Pre-treating agent for printing by ink jet recording and cloth for printing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a pre-treating agent for getting a sharp and high quality image without a bleeding and soiling on its white part on printing with an ink jet recording, and a cloth for printing with the ink jet recording, having a waterproof endurance and obtained by coating the above agent. SOLUTION: This pre-treating agent for an ink jet recording contains and a graft copolymer of 0.5-50 wt.% macromonomer obtained by polymerizing an olefin with 0.5-80 wt.% N-vinylacetamide and 0.5-99 wt.% at least one kind of a monomer containing an unsaturated group selected from a (meth) acrylamide, (meth)acrylic acid ester, epoxy(meth)acrylic acid, vinyl compound and urethane(meth)acrylic acid. The cloth for a printing with the ink jet recording has an ink-receiving layer prepared by coating the pre-treating agent on the printing cloth.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a printing pretreatment agent for obtaining a sharp image during printing by ink jet recording, and a printing cloth coated with the same.

[0002]

2. Description of the Related Art In textile printing, there is screen printing or the like which is performed on a large scale, since a fine image can be obtained without bleeding. On the other hand, in recent years, printing by simple inkjet recording using a color inkjet printer has also been performed.
For example, Japanese Patent Publication No. 4-35351 discloses that a cellulose fiber is treated with a pretreatment agent of an alkaline substance, urea, a nonionic or anionic water-soluble polymer substance, and then a reactive dye ink is printed by inkjet recording. A method for fixing a reactive dye by a dry heat method is disclosed. However, prevention of bleeding and white background contamination is insufficient, and a sharp image cannot be obtained. Japanese Patent Publication No. 4-33913 discloses that a cellulosic fiber is treated with a pretreatment agent of an alkaline substance and a water-soluble metal salt or a water-soluble polymer substance, and a reactive dye is printed by ink jet recording, and a wet heat method or a dry heat method is used. A method of fixing by a thermal method is disclosed. However, since no hydrotrope such as urea was contained in the pretreatment agent, the dye was not sufficiently fixed and the water fastness was low.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and has been made in order to obtain a sharp and high-quality image without bleeding or white background contamination during printing by ink jet recording. It is an object of the present invention to provide a treating agent, and a textile for inkjet recording which has waterfastness and is coated with the treating agent.

[0004]

The pretreatment agent for textile printing of ink jet recording of the present invention, which has been made in order to achieve the above object, comprises 0.5 to 10% of a macromonomer obtained by polymerizing an olefin.
50% by weight and 0.5-80% of N-vinylacetamide
% By weight of at least one kind of unsaturated group-containing monomer selected from (meth) acrylamides, (meth) acrylates, epoxy (meth) acrylic acids, vinyl compounds, and urethane (meth) acrylic acids. 0.5-99% by weight of the graft copolymer resin. The graft copolymer resin has a number average molecular weight of 5,000.
-100,000, which is a resin soluble in water, a hydrophilic solvent, and a hydrophobic solvent, that is, an amphiphilic resin.

When the olefin component of the macromonomer is alkyl (meth) acrylate, styrene, acrylonitrile, acrylamide, N-vinylpyrrolidone, dimethylsiloxane, styrene-acrylonitrile copolymer,
It is preferably at least one selected from methyl methacrylate-hydroxyethyl methacrylate copolymer and ethylhexyl methacrylate-hydroxyethyl methacrylate copolymer. The number average molecular weight of these macromonomers is preferably from 2,000 to 20,000.

The macromonomer whose one end is a methacryloyl group and whose olefin component is an alkyl (meth) acrylate is, specifically, a product of Toagosei Co., Ltd., whose trade name is a macromonomer 45 whose trade name is methyl methacrylate. % AA-6, AA-6SR, AA-
6, the same AA-10, the same butyl acrylate AB-
6, the same AW-6S which is isobutyl methacrylate. In addition, the olefin component is styrene,
S-6, AK-5 and AK which are dimethylsiloxanes
-30, AK-32, styrene-acrylonitrile copolymer AN-6S, methyl methacrylate-
A, which is a hydroxyethyl methacrylate copolymer
A-714SK, an ethylhexyl methacrylate-hydroxyethyl methacrylate copolymer AY-
707S and AY-714S.

(Meth) acrylamides include, for example,
N, N-dimethylaminopropylacrylamide, diacetone acrylamide, N-methylacrylamide,
N, N-dimethylacrylamide, N, N-dimethylaminoacrylamide, N, N-dimethylamino (meth)
Acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethylamino-2
-Hydroxypropyl (meth) acrylamide, N-methyl-N-ethylacrylamide, N-methyl-Nn
-Propylacrylamide, N-methyl-N-isopropylacrylamide, N-ethylacrylamide, N,
N-diethylacrylamide, Nn-butylacrylamide, N-sec-butylacrylamide, N-te
rt-butylacrylamide, Nn-propyl (meth) acrylamide, N, N-di-n-propylacrylamide, N-isopropyl (meth) acrylamide,
N-cyclopropyl (meth) acrylamide, N, N-
Diisopropylacrylamide, Nn-hexylacrylamide, Nn-octylacrylamide, Nt
tert-octylacrylamide, N-tetrahydrofurfuryl (meth) acrylamide, N-hydroxyethylacrylamide, N-methoxymethylacrylamide, N-methoxyethyl (meth) acrylamide, N-
Methoxypropyl (meth) acrylamide, N-ethoxymethylacrylamide, N-ethoxyethyl (meth)
Acrylamide, N-ethoxypropyl (meth) acrylamide, Nn-butoxymethylacrylamide, N
-N-butoxypropylacrylamide, N-isopropoxypropyl (meth) acrylamide, N- (2,2
-Dimethoxyethyl) -N-methylacrylamide, N
-1-methyl-2-methoxyethyl (meth) acrylamide, N-1-methoxymethylpropyl (meth) acrylamide, N- (1,3-dioxolan-2-ylmethyl) -N-methylacrylamide, N-methylolacrylamide, N-2-ethylhexyloxypropylacrylamide, N-furfurylacrylamide, N-methylthiopropylacrylamide, N-chloropropylacrylamide, N-acryloylpyrrolidine, N-acryloylpyrrolidine, N-acryloylmorpholine, N
-Acryloyl-2,6-dimethylmorpholine, and quaternary salts thereof.

(Meth) acrylates include, for example, methyl methacrylate, ethyl methacrylate, n
-Butyl methacrylate, isobutyl methacrylate,
2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate, methoxydiethylene glycol methacrylate, methoxy polyethylene glycol methacrylate, methoxy polyethylene glycol methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, benzyl methacrylate, phenoxyethyl Methacrylate, isobornyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl Methacrylate, dimethylaminoethyl methacrylate hydrochloride, methacrylic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl-2-hydroxypropyl phthalate, glycidyl methacrylate, 2- Methacryloyloxyethyl acid phosphate, tert-butyl methacrylate,
Isostearyl methacrylate, methoxytriethylene glycol methacrylate, n-butoxyethyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, trifluoroethyl methacrylate, 2,2,2
3,3-tetrafluoropropyl methacrylate, 2,
2,3,4,4,4-hexafluorobutyl methacrylate, perfluorooctylethyl methacrylate, isoamyl acrylate, lauryl acrylate, stearyl acrylate, butoxyethyl acrylate, ethoxy-diethylene glycol acrylate, methoxy-triethylene glycol acrylate, methoxy-polyethylene glycol Acrylate, methoxydipropylene glycol acrylate, phenoxyethyl acrylate, phenoxy-polyethylene glycol acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate,
2-hydroxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl-succinic acid, 2-acryloyloxyethyl-phthalic acid, 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid , Isooctyl acrylate,
Isomyristyl acrylate, isostearyl acrylate, 2-ethylhexyl-diglycol acrylate, 2-hydroxybutyl acrylate, 2-acryloyloxyethyl hexahydrophthalic acid, 2-hydroxy-3-phenoxypropyl acrylate, alkyl methacrylate (Kyoeisha Co., Ltd.) Brand name light ester L-5, L-7, L-8), nonylphenol-
Ethylene oxide adduct acrylate (trade name: Light Acrylate NP-4EA, manufactured by Kyoeisha Co., Ltd.)
8EA).

Epoxy (meth) acrylic acids include, for example, light ester 130MA, light ester 041MA and light acrylate 130A (all trade names manufactured by Kyoeisha Chemical Co., Ltd.) which are ethylene oxide-added methacrylates, and polyethylene glycol ( Blenmer PE-90, which is meth) acrylate, PE
-200 and PE-350 (both are trade names manufactured by NOF Corporation). Also, in addition to ethylene glycol and ethylene glycol alkyl ether, alkylene oxide addition (meth) acrylate of polyalcohol, melamine and hydantoin, (meth) acrylate of polyester of polyalkylene oxide, (meth) acrylate of epoxy group-containing compound of polyalkylene oxide Or an alkylaminoalkyl (meth) acrylate adduct or an amine-added (meth) acrylate of a polyalkylene oxide polyepoxide.

[0010] Vinyl compounds include, for example, styrene, N
-Vinylpyrrolidone, ethyl vinyl ether.

Urethane (meth) acrylic acids include, for example, polyalcohols, polyalkylene oxides, polyalkylene glycols, and diisocyanates such as hexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate and lysine diisocyanate. Is reacted with a compound having a terminal isocyanate group,
Examples thereof include urethane (meth) acrylate to which hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxy-3-phenoxypropyl acrylate are added. Further, an alkylene oxide-added acrylate of isocyanurate may be used.

The printing pretreatment agent for ink jet recording is preferably an aqueous solution or an aqueous emulsion of a graft copolymer resin. When obtaining a graft copolymer resin,
The method can be suitably carried out by graft copolymerization using a microsuspension method, a dispersion polymerization method in polyvinyl alcohol or poly-N-vinylacetamide, an emulsion polymerization method, or a solution polymerization method. The pretreatment agent for printing preferably contains 0.05 to 100% by weight of the graft copolymer resin. The pretreatment agent for printing can be used as a solution by dissolving the graft copolymer resin in water, a hydrophilic solvent, or a hydrophobic solvent. 5-30% by weight
An aqueous solution is more preferable.

[0013] The pretreatment agent for textile printing for ink jet recording includes water-soluble or water-dispersible resin, wax emulsion,
Sizing agents, water-repellents of fluorine-containing organic compounds or organosilicon compounds, pH adjusters, surfactants, water-soluble organic solvents, cationic polymers, reduction inhibitors, urea, thiourea, organic or inorganic fine particles At least one additive may be included.

Examples of the water-soluble or water-dispersible resin include poly-N-vinylacetamide, oxidized starch, methylcellulose, hydroxycellulose, carboxymethylcellulose, trangant gum, guar gum, gum arabic, sodium alginate, sodium polyacrylate, Polyvinyl alcohol, modified polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyalkylene oxide, polyarylamine hydrochloride, polydiaryldimethylammonium chloride, casein, polystyrene sodium sulfonate, and a resin latex such as a styrene-butadiene copolymer Latex and vinyl chloride-vinyl acetate copolymer emulsion are mentioned. The printing pretreatment agent can contain at least one kind of this resin, and preferably contains 0.1 to 50% by weight.

The wax emulsion is, for example, an emulsion of an ester of a higher fatty acid and an aliphatic alcohol, and specifically includes a fatty acid such as stearic acid, behenic acid, palmitic acid, and a fatty acid ester such as dotriconsyl ligrinoselate. Carnauba wax, lanolin wax, fatty acid glyceride such as caster wax containing 12-hydroxystearic acid glyceride as a main component, Japan wax, alcohol wax such as seryl alcohol, ketone wax, fatty acid amide such as N-stearyl stearamide, N, N-ethylenebisoleic acid amide, alkyl amide of dimer acid, stearic acid ester amide, hydrocarbon such as candelilla wax, paraffin wax, microcrystalline wax Or include rosin esters as a main component Aebichin glycerides.

Examples of the sizing agent include styrene-maleic anhydride copolymer and styrene-acrylic acid copolymer.

Examples of the water repellent for a fluorine-containing organic compound include:
Perfluoroalkyl ether-acrylate copolymers, Light Guard TR-220, and water repellents for organosilicon compounds include, for example, organopolysiloxanes,
Light silicone P-290.

Examples of the pH or hydrogen ion concentration regulator include phosphoric acid, hydrochloric acid, sulfuric acid, boric acid, silicic acid, acetic acid, carbonic acid, citric acid, tartaric acid, maleic acid, phthalic acid, and alkali metal salts and ammonium salts thereof. , Triethylamine salts, triethanolamine salts, caustic soda and triethanolamine.

Surfactants include cationic surfactants such as alkyl ammonium salts, carboxylate salts of N, N-alkylethylenediamine, anionic surfactants such as alkylbenzene sulfonates, dialkyl sulfosuccinates, and nonionic surfactants. Surfactants such as polyoxyethylenacyl phenol, polyoxyethylene fatty acid esters, amphoteric surfactants such as alkyl betaine, N
-Alkyl-N, N-dimethylglycine.

Examples of the water-soluble organic solvent include methanol,
Ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, tetrahydrofuran, dioxane,
N, N-dimethylformamide, dimethylsulfoxide, ethylene glycol-n-butyl ether, diethylene glycol-n-butyl ether.

Examples of the cationic polymer include polyethyleneimine salts, dimethylamine-epihalohydrin condensates, polyvinylamine salts, polyallylamine salts, polydimethylaminoethyl methacrylate quaternary salts, polydiallyldimethylammonium salts, and diallylamine-acrylamide copolymer salts. And quaternary ammonium salts of polystyrene.

The organic fine particles include, for example, organic acrylic fine particles, and the inorganic fine particles include, for example, alumina, silicon oxide, and zeolite.

The textile for textile printing of ink-jet recording of the present invention has an ink-receiving layer in which the above-mentioned textile printing pretreatment agent for ink-jet recording is coated on the cloth to be dyed. The ink receiving layer is formed by applying, impregnating, or spraying a textile printing treatment agent on the cloth to be dyed.

The ink receiving layer preferably contains 0.05 to 50% by weight of the graft copolymer resin based on the weight of the cloth to be dyed. If the amount is less than 0.05% by weight, bleeding of the ink occurs, and if the amount is more than 50% by weight, the dyeing ratio of the ink to the fabric decreases.

The fabric to be dyed is preferably a knitted or nonwoven fabric made of at least one kind of fiber selected from silk, cotton, hemp, rayon, acetate, nylon and polyester.

The pH of the pretreatment agent for printing depends on the type of fiber.
Adjust the value appropriately. If the fiber is cotton, silk, hemp, rayon, adjust the pH of the pretreatment agent to alkaline, if it is nylon, adjust it to acidic, and if it is acetate, polyester, adjust it to near neutral Good.

Printing is performed by printing a dye or pigment ink on the above-described textile for printing by ink jet recording and depositing the dye or pigment on the ink receiving layer.
The dye ink contains a reactive dye, an acid dye, a direct dye, or a disperse dye, and the pigment ink contains a disperse pigment. This ink contains at least water or a mixed solvent of water and a water-soluble organic solvent. Examples of the water-soluble organic solvent include glycols, glycol ethers, and nitrogen-containing solvents. Further, a pH adjuster, a fungicide, a surfactant, and an additive of a water-soluble resin may be contained. As the surfactant, any of nonionic, anionic, cationic and amphoteric surfactants can be used.

Printing can be carried out by using an ink containing an appropriate dye or pigment according to the type of the fiber of the fabric, and scanning the ink jet recording head on the fabric to print the ink at a predetermined position. Thereby, a desired image is obtained on the cloth. After printing the ink, a coloring process may be performed as necessary. The coloring process is performed by heating coloring, that is, a high-temperature steam method or a thermosol method.

The image obtained by printing by ink-jet recording is sharp, sharp and dark even without bleeding or white background contamination. Furthermore, it has sufficient water fastness.

[0030]

Embodiments of the present invention will be described below in detail. The textile printing pretreatment agent of the present invention and the textile for printing coated with the same are specifically manufactured as follows.

In a solvent in the presence of a polymerization initiator 2,2'-azobis (isobutyronitrile), a macromonomer obtained by polymerizing methyl methacrylate, N-vinylacetamide,
Dialkylaminoalkyl acrylamide and hydroxyalkyl methacrylate are added dropwise at 80 ° C. and copolymerized to obtain a pre-printing agent for inkjet recording containing a graft copolymer resin. When the pretreatment agent is applied to the cloth to be dyed and dried, an ink receiving layer is formed, and a textile for printing is obtained.

Next, a method of performing printing by performing ink jet recording on the printing cloth will be described. An image of an aqueous or water-dispersed ink containing a dye and a pigment is printed on a printing fabric by inkjet recording. Since the graft copolymer resin in the ink receiving layer formed on the textile for printing is a resin that is soluble in water, a hydrophilic solvent, and a hydrophobic solvent, the ink is absorbed by the ink receiving layer and the ink is diffused. Is suppressed, the occurrence of bleeding is suppressed. Further, since the dye of the ink is deposited in the graft copolymer resin of the ink receiving layer, the dyeing ratio of the dye and the like is improved, and sufficient color density and clearness can be obtained without bleeding.

An example in which the present invention is implemented according to the above embodiment will be described below. Examples 1 to 4 are examples of trial production of a graft copolymer resin in a pretreatment agent for textile printing of ink jet recording to which the present invention is applied. Example 1 is a microsuspension method, Example 2 is a dispersion polymerization method, and Example 3 Is an emulsion polymerization method, and Example 4 is a solution polymerization method, each of which is obtained by graft copolymerization. Comparative Examples 1 and 2 are examples of trial production of a copolymer resin to which the present invention is not applied.

Example 1 Macromonomer AA-6 (macromonomer of methyl methacrylate: Toa Gosei Co., Ltd.)
10 parts by weight, N-vinylacetamide 30 parts by weight, light ester 130MA (methanol-ethylene oxide 9 mol addition methacrylate: manufactured by Kyoeisha Chemical Co., Ltd.) 20 parts by weight, N, N-dimethylaminopropylacrylamide 30 Parts by weight, 10 parts by weight of 2-hydroxypropyl methacrylate, 1 part by weight of 2,2′-azobis (isobutyronitrile), C ₁₂ H ₂₃ SH 0.1 part by weight.
1 part by weight, 3 parts by weight of a higher alkyltrimethylammonium chloride of a cationic surfactant as an emulsifier, 1 part by weight of a polyoxyethylene nonylphenyl ether of a nonionic surfactant, and 36 parts by weight of water were mixed with a homomixer or a homogenizer. After adjusting to a submicron oil droplet of 1 μm or less to form a pre-emulsion, water 1
The mixture was gradually added to 18 g, and a copolymerization reaction was performed by a microsuspension method at 80 ° C. for 6 hours in a nitrogen gas atmosphere to obtain a graft copolymer resin as an aqueous suspension polymer.
The number average molecular weight of the graft copolymer resin was measured by gel permeation chromatography,
30,000.

(Example 2) Polyvinyl alcohol PV
A-124 (manufactured by Kuraray Co., Ltd.) 0.5 part by weight, PVA
0.5 parts by weight of -217 (manufactured by Kuraray Co., Ltd.) is dissolved in 50 parts by weight of water to prepare an aqueous polyvinyl alcohol solution. N, N-dimethylaminopropylacrylamide 3
In a mixture of 0 parts by weight, 30 parts by weight of N-vinylacetamide, 10 parts by weight of 2-hydroxypropyl methacrylate, 20 parts by weight of light ester 130MA, and 1 part by weight of 2,2′-azobis (isobutyronitrile), Dissolve 10 parts by weight of monomer AA-6, add thereto the previously prepared aqueous solution of polyvinyl alcohol and 254 parts by weight of water, and carry out a copolymerization reaction by a dispersion polymerization method at 75 ° C. for 6 hours under a nitrogen gas atmosphere, A graft copolymer resin as a water-dispersed polymer was obtained. The number average molecular weight of this graft copolymer resin was 40,000 as measured by gel permeation chromatography.

Example 3 N-vinylacetamide 30
Parts by weight, 30 parts by weight of N, N-dimethylaminopropylacrylamide, 20 parts by weight of light ester 130MA, and 2-hydroxypropyl methacrylate 1
10 parts by weight of the macromonomer AA-6 was dissolved in 0 parts by weight of a mixture, and 3 parts by weight of a polymer surfactant Pluronic P-84 (manufactured by Asahi Denka Kogyo KK), which is an emulsifier, and a nonionic compound 7 parts by weight of surfactant Newcol 2614 (manufactured by Nippon Emulsifier Co., Ltd.) and 56 parts by weight of water are added and emulsified by a homomixer. 80 ° C in a nitrogen gas atmosphere
Then, the mixture was dropped into 226 parts by weight of water over 3 hours, and at the same time, 10 parts by weight of 3% ammonium persulfate as a polymerization initiator was dropped over 4 hours, and a copolymerization reaction was carried out by an emulsion polymerization method.
A graft copolymer resin as an emulsion polymer was obtained. The number average molecular weight of this graft copolymer resin was measured by gel permeation chromatography and found to be 50,0.
00.

Example 4 N-vinylacetamide 30
Parts by weight, 20 parts by weight of light ester 130MA, N,
30 parts by weight of N-dimethylaminopropylacrylamide, 10 parts by weight of 2-hydroxypropyl methacrylate, and 2,2′-azobis (isobutyronitrile)
10 parts by weight of the macromonomer AA-6 is dissolved in 1 part by weight of the mixture, and the resulting mixture is dissolved in 100 parts by weight of a 1: 1 mixed solution of water and isopropyl alcohol to prepare a monomer solution. A reaction vessel was charged with 200 parts by weight of a 1: 1 mixture of water and isopropyl alcohol, and a monomer solution was added dropwise at 75 ° C. over 5 hours under a nitrogen gas atmosphere to carry out a copolymerization reaction by a solution polymerization method to obtain a solution polymer. A graft copolymer resin was obtained. The number average molecular weight of this graft copolymer resin was 40,000 as measured by gel permeation chromatography.

Comparative Example 1 Methyl methacrylate 10
Parts by weight, 20 parts by weight of light ester 130MA, N,
30 parts by weight of N-dimethylaminopropyl acrylamide, 10 parts by weight of 2-hydroxypropyl methacrylate, 30 parts by weight of diacetone acrylamide, 2,2 ′
1 part by weight of azobis (isobutyronitrile) and Newcol 2614-5 which is a surfactant as an emulsifier
A monomer solution is prepared by dissolving parts by weight in 100 parts by weight of a 1: 1 mixed solvent of water and isopropyl alcohol. A reaction vessel was charged with 200 parts by weight of a 1: 1 mixed solvent of water and isopropanol, and a monomer solution was added dropwise at 75 ° C. over 2 hours in a nitrogen gas atmosphere to carry out a copolymerization reaction by an emulsion polymerization method and aged for 2 hours. Thus, a copolymer resin of an emulsion polymer was obtained.

Comparative Example 2 20 parts by weight of light ester 130MA, 30 parts by weight of N, N-dimethylaminopropylacrylamide, 10 parts by weight of 2-hydroxypropyl methacrylate, 30 parts by weight of diacetone acrylamide, 2,2'- In a mixture of 1 part by weight of azobis (isobutyronitrile) and 5 parts by weight of Newcol 2614, 10 parts by weight of the macromonomer AA-6 is dissolved,
This is dissolved in 100 parts by weight of isopropyl alcohol to prepare a monomer solution. A reaction vessel was charged with 200 parts by weight of a water-isopropyl alcohol 1: 1 mixed solution,
The monomer solution was added dropwise at 75 ° C. over 3 hours in a nitrogen gas atmosphere, copolymerized by an emulsion polymerization method, and aged for 2 hours to obtain a copolymer resin of an emulsion polymer.

The copolymer resins obtained in Examples and Comparative Examples were diluted with water to prepare a pretreatment agent having a solid content of 20%.
100 g of a polyester fabric is immersed in the pretreatment liquid and squeezed using a mangle, and the cloth is impregnated with 50 g of the pretreatment liquid, that is, has a solid content of 10 g, forms a 50 μm receiving layer, and is heated with hot air at 70 ° C. After drying for 10 minutes, a textile for ink jet recording was obtained.

Next, a commercially available ink jet color printer (manufactured by Canon Inc .: BJC-44) was added to this cloth.
0), a character of 1 to 15 mm square and a pattern of 150 mm square are printed using an acid dye ink, and then printed according to JIS.
Washing and drying were performed according to L-0217 No.103.

The image on the cloth is visually observed,
Evaluation was made on white background contamination, image density, and glossiness. Table 1 shows the results of each of the evaluation items. In the table, the evaluation items are indicated by three grades, in which a good evaluation item is indicated by ○, a slightly defective item is indicated by Δ, and a defective item is indicated by x.

[0043]

[Table 1]

As is clear from Table 1, images printed by ink jet recording on textiles for textiles treated with the textile printing pretreatment agent containing the graft copolymer resin obtained in the examples are not bleeding or white background contamination. No image density and good gloss were obtained.

[0045]

As described above in detail, according to the printing method for ink jet recording of the present invention, a sharp, clear and deep surface can be formed on a fabric treated with a pretreatment agent without causing bleeding or white background contamination. A certain high-quality image can be formed. This has excellent water fastness and is equivalent to an image obtained by screen printing. For inkjet recording, a commercially available inkjet printer can be used, and textiles of various fibers can be printed.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C09D 11/00 B41J 3/04 101Z D06M 101: 34 (72) Inventor Toshifumi Okudo Nishi, Nara Prefecture 5-2-5 Kujo-cho Kyoeisha Chemical Co., Ltd. Nara Research Laboratory F-term (reference) 2C056 EA05 FB03 FC06 2H086 BA15 BA22 BA31 4H057 AA01 BA81 CA23 CA38 CB08 CC01 DA01 DA17 DA20 DA21 DA24 GA06 4J039 BC09 BC13 BC32 BE01 BE02 BE03 BE04 BE08 BE12 BE19 BE22 BE30 CA03 CA06 GA24 4L033 AA02 AA03 AA07 AA08 AB04 AC15 CA18 CA50

Claims (6)

[Claims] (1) 0.5 to 50% by weight of an olefin polymerized macromonomer, 0.5 to 80% by weight of N-vinylacetamide, and (meth) acrylamides;
Grafting with 0.5 to 99% by weight of at least one unsaturated group-containing monomer selected from (meth) acrylic esters, epoxy (meth) acrylic acids, vinyl compounds, and urethane (meth) acrylic acids A pretreatment agent for textile printing of ink-jet recording, comprising a polymer resin. 2. The olefin component of the macromonomer is an alkyl (meth) acrylate, styrene, acrylonitrile, acrylamide, N-vinylpyrrolidone,
2. The method according to claim 1, wherein the copolymer is at least one selected from dimethylsiloxane, styrene-acrylonitrile copolymer, methyl methacrylate-hydroxyethyl methacrylate copolymer, and ethylhexyl methacrylate-hydroxyethyl methacrylate copolymer.
3. The pretreatment agent for textile printing of inkjet recording according to item 1. 3. The pretreatment agent according to claim 1, wherein the pretreatment agent is an aqueous solution or an aqueous emulsion of the graft copolymer resin. 4. A textile printing fabric for inkjet recording, characterized in that the textile printing pretreatment agent according to any one of claims 1 to 3 has an ink-receiving layer coated on a fabric to be dyed. . 5. The ink jet recording according to claim 4, wherein the graft copolymer resin is contained in the ink receiving layer in an amount of 0.05 to 50% by weight based on the weight of the cloth to be dyed. Textile for printing. 6. The fabric to be dyed is a knitted or non-woven fabric made of at least one kind of fiber selected from silk, cotton, hemp, rayon, acetate, nylon, and polyester. 5. The textile for textile printing of inkjet recording according to 4.