JP2015132027A - Resin composition for fiber processing, pigment printing agent and fabric using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for fiber processing which can be used for a pigment printing agent without generating harmful formaldehyde, can impart excellent texture to a fabric printed with the pigment printing agent, can impart high washing resistance and abrasion resistance to a printed part and further can impart high water resistance to a dye multicolored part printed by overlapping the pigment printing agent and a dye printing agent, and to provide a pigment printing agent and a fabric using the same.SOLUTION: There is provided a resin composition for fiber processing which comprises a polymer (A) obtained by polymerizing a polymerizable monomer containing a polymerizable monomer having a carboxyl group (a1), 0.1 to 5 mass% of a polymerizable monomer having an epoxy group (a2) and 0.1 to 3.5 mass% of a polymerizable monomer having a hydrolyzable silyl group (a3), where the mass ratio [(a2)/(a3)] between the polymerizable monomer (a2) and the polymerizable monomer (a3) is in the range of 10/90 to 90/10.

Description

  The present invention can be used in a pigment printing agent without generating harmful formaldehyde, can impart an excellent texture to a fabric printed with the pigment printing agent, and has high washing resistance and friction resistance on the printed portion. Resin for fiber processing that can impart high water resistance to the heavy-colored portion of the dye that is printed by overlapping the pigment printing agent and the dye printing agent on the fabric, and pigment printing using the same The present invention relates to an agent and a fabric.

  Conventionally, a binder resin of a pigment printing agent is a heavy resin using a polymerizable monomer having a reactive functional group such as N-methylol (meth) acrylamide in order to impart washing resistance, friction resistance, and the like. Coalescence was used. Since this polymer has a reactive functional group, high crosslinking resistance and friction resistance can be imparted by the crosslinking reaction of the functional group, but there is a problem that harmful formaldehyde is generated during the crosslinking reaction. there were.

  As a method for solving the above-mentioned problem of formaldehyde, it has been proposed to perform a cross-linking reaction with something other than N-methylol (meth) acrylamide. For example, a cross-linking agent such as an oxazoline compound or a blocked isocyanate compound may be used. Attempts have been made (for example, see Patent Document 1). However, even when a pigment printing agent containing these cross-linking agents is used, it has not been possible to sufficiently impart excellent texture and high washing resistance, friction resistance, etc. to the printed part. .

  Further, in the case of a conventional pigment printing agent, after printing on a fabric and further printing a dye printing agent thereon, or after printing a dye printing agent and further printing a pigment printing agent thereon. In the case of printing, there is also a problem that the water resistance (washing resistance) of a printing portion where the pigment and the dye overlap (hereinafter abbreviated as “dye heavy color portion”) is lowered.

  Therefore, it can be used in a pigment printing agent without generating harmful formaldehyde, can give an excellent texture to a fabric printed with the pigment printing agent, and has high washing resistance and friction resistance on the printed portion. There has been a demand for a fiber processing resin composition that can be imparted, and can also impart high water resistance to a dyed heavy color portion printed by overlapping the pigment printing agent and dye printing agent on a fabric.

JP 2009-15010 A

  The problem to be solved by the present invention is that it can be used in a pigment printing agent without generating harmful formaldehyde, can give an excellent texture to a fabric printed with the pigment printing agent, and is high in the printed part. Resin composition for fiber processing that can impart washing resistance and friction resistance, and can also impart high water resistance to dyed heavy-colored parts printed by overlapping the pigment printing agent and dye printing agent on the fabric Product, pigment printing agent and fabric using the same.

  As a result of intensive studies to solve the above problems, the present inventors have found that a polymerizable monomer having a carboxyl group and a polymerizable monomer having an epoxy group and a hydrolyzable silyl group. The inventors have found that the above problems can be solved by using a polymer obtained by polymerizing a polymerizable monomer containing a specific amount of a monomer, and have completed the present invention.

  That is, the present invention is a polymerization comprising a polymerizable monomer (a1) having a carboxyl group, a polymerizable monomer (a2) having an epoxy group, and a polymerizable monomer (a3) having a hydrolyzable silyl group. A fiber processing resin composition containing a polymer (A) obtained by polymerizing a polymerizable monomer, wherein the polymerizability in the total amount of the polymerizable monomer as a raw material of the polymer (A) The ratio of the monomer (a2) is in the range of 0.1 to 5% by mass, the ratio of the polymerizable monomer (a3) is in the range of 0.1 to 3.5% by mass, and the polymerizable Resin for fiber processing, wherein the mass ratio [(a2) / (a3)] of the monomer (a2) and the polymerizable monomer (a3) is in the range of 10/90 to 90/10 The present invention provides a composition, a pigment printing agent and a fabric using the composition.

  The pigment printing agent using the fiber processing resin composition of the present invention is excellent in washing resistance, friction resistance, etc. of the printed part without damaging the original texture of the fabric even when printed on the fabric, and on the fabric. After printing, even if a dye printing agent is further printed thereon, or even after a dye printing agent is printed, and a pigment printing agent is further printed thereon, the water resistance of the dye heavy color portion is improved. Since it is excellent, it is possible to obtain a printed fabric with a natural texture and suppressed color fading during washing or the like. In addition, the pigment printing agent using the fiber processing resin composition of the present invention can be used in combination with a dye printing agent to give various prints to the fabric without any restrictions on the design.

  The resin composition for fiber processing of the present invention comprises a polymerizable monomer (a1) having a carboxyl group, a polymerizable monomer (a2) having an epoxy group, and a polymerizable monomer having a hydrolyzable silyl group ( A fiber processing resin composition containing a polymer (A) obtained by polymerizing a polymerizable monomer containing a3), the total amount of the polymerizable monomer as a raw material of the polymer (A) The ratio of the polymerizable monomer (a2) in the range is 0.1 to 5% by mass, and the ratio of the polymerizable monomer (a3) is in the range of 0.1 to 3.5% by mass. Yes, the mass ratio [(a2) / (a3)] of the polymerizable monomer (a2) and the polymerizable monomer (a3) is in the range of 10/90 to 90/10.

  The polymerizable monomer (a1) is a polymerizable monomer having a carboxyl group, and for example, (meth) acrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic anhydride, citraconic acid and the like are used. be able to.

  Although the polymerizable monomer (a2) is a polymerizable monomer having an epoxy group, for example, glycidyl (meth) acrylate, glycidyl allyl ether, or the like can be used.

  The polymerizable monomer (a3) is a polymerizable monomer having a hydrolyzable silyl group, and examples thereof include vinylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris (2-methoxyethoxy). ) Vinylsilane compounds such as silane; 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxy (Meth) acryloyloxyalkylsilane compounds such as propylmethyldiethoxysilane can be used. These polymerizable monomers (a3) can be used alone or in combination of two or more.

  In the present invention, “(meth) acrylic acid” refers to one or both of methacrylic acid and acrylic acid, “(meth) acrylate” refers to one or both of methacrylate and acrylate, and “(meta) “) Acryloyl” refers to one or both of methacryloyl and acryloyl.

  Polymers other than the above polymerizable monomer (a1) having a carboxyl group, polymerizable monomer (a2) having an epoxy group, and polymerizable monomer (a3) having a hydrolyzable silyl group (A As a polymerizable monomer (a4) that can be used as a raw material of methyl), methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl Alkyl (meth) acrylates such as (meth) acrylate, isopropyl (meth) acrylate, and isobutyl (meth) acrylate; aromatic (meth) acrylates such as benzyl (meth) acrylate; silanes such as trimethylsiloxyethyl (meth) acrylate ( Meth) acrylate; methoxypolyethylene glycol mono (meth) acrylate Alkyl polyalkylene glycol mono (meth) acrylates such as methoxypolypropylene glycol mono (meth) acrylate; Fluorine-based (meth) acrylates such as perfluoroalkylethyl (meth) acrylate; Styrene, styrene derivatives (p-dimethylsilylstyrene, (p -Vinylphenyl) methyl sulfide, p-hexynylstyrene, p-methoxystyrene, p-tert-butyldimethylsiloxystyrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, α-methylstyrene, etc.) , Vinyl naphthalene, vinyl anthracene, aromatic vinyl compounds such as 1,1-diphenylethylene; glycidyl (meth) acrylate, epoxy (meth) acrylate, ethylene glycol di (meth) acrylate Diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylene glycol tetra (meth) acrylate, 2-hydroxy-1,3-diaacryloxypropane, 2,2-bis [4- (acrylic) Roxymethoxy) phenyl] propane, 2,2-bis [4- (acryloxyethoxy) phenyl] propane, dicyclopentenyl (meth) acrylate tricyclodecanyl (meth) acrylate, tris (acryloxyethyl) isocyanurate, urethane (Meth) acrylate compounds such as (meth) acrylate; dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate and other alkylamino groups (meth) Acrylate; acrylamide compounds such as (meth) acrylamide, N, N-dimethylacrylamide, isopropylacrylamide, diacetone acrylamide; vinylpyridine compounds such as 2-vinylpyridine, 4-vinylpyridine, naphthylvinylpyridine; 1,3-butadiene, Examples thereof include conjugated dienes such as 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene and 1,3-cyclohexadiene. These polymerizable monomers (a4) can be used alone or in combination of two or more.

  The ratio of the polymerizable monomer (a2) in the total amount of the polymerizable monomers (a1) to (a4) that is a raw material of the polymer (A) is in the range of 0.1 to 5% by mass. However, the fabric printed with the pigment printing agent using the resin composition for fiber processing of the present invention can give an excellent texture, and can give high washing resistance and friction resistance to the printed portion. The range of 2 to 3.5 is preferable, and the range of 0.3 to 3% by mass is more preferable.

  The ratio of the polymerizable monomer (a3) in the total amount of the polymerizable monomers (a1) to (a4) serving as the raw material of the polymer (A) is 0.1 to 3.5% by mass. Although it is within the range, it is possible to impart excellent texture to the fabric printed with the pigment printing agent using the fiber processing resin composition of the present invention, and further to impart high washing resistance and friction resistance to the printed portion. The range of 0.2 to 2.5% by mass is preferable, and the range of 0.3 to 2% by mass is more preferable.

  In addition, the ratio of the polymerizable monomer (a1) in the total amount of the polymerizable monomers (a1) to (a4) that are the raw materials of the polymer (A) is the resin composition for fiber processing of the present invention. Since it is possible to impart better dispersibility to water in the product, and further impart high washing resistance and friction resistance to the printed part, the range of 0.5 to 5% by mass is preferable, and 1 to 4% by mass The range is more preferable, and the range of 1.5 to 3% by mass is further preferable.

  Furthermore, the mass ratio [(a2) / (a3)] of the polymerizable monomer (a2) and the polymerizable monomer (a3) is in the range of 10/90 to 90/10. The fabric printed with the pigment printing agent using the above fiber processing resin composition can be provided with an excellent texture, and the printed part can be provided with high washing resistance and friction resistance. A range of 15 is preferred.

  As a manufacturing method of the resin composition for fiber processing of this invention, a well-known emulsion polymerization method can be used, for example.

  The pigment printing agent of the present invention comprises the fiber processing resin composition of the present invention and the pigment (B). There is no restriction | limiting in particular as said pigment (B), An organic pigment and an inorganic pigment can be used. Examples of the organic pigment include lake red, permanent red, brilliant carmine, calcium lake, naphthol AS red, benzimidazolone yellow, disazo yellow HR, virazolone red, condensed azo yellow, condensed azo red, condensed azo brown, nickel azo. Azo pigments such as yellow; phthalocyanine pigments such as phthalocyanine blue, chlorinated phthalocyanine green, brominated phthalocyanine green; anthraquinone yellow, dianthraquinolyl red, indanthrene blue, thioindigo Bordeaux, perinone orange, perylene scarlet, perylene Red, Perylene Maroon, Quinacridone Red, Quinacridone Magenta, Quinacridone Scarlet, Dioxazine Violet, Isoindolinone Ye Chromatography, quinophthalone yellow, isoindoline yellow, etc. condensed polycyclic pigments such as diketopyrrolopyrrole red and the like.

  Examples of the inorganic pigment include metal oxide pigments such as zinc white, titanium oxide, dial, iron black and chromium oxide; titanium yellow, zinc-iron brown, titanium cobalt green, cobalt green, cobalt blue, copper -Metal complex oxide pigments such as chromium black and copper-iron black; Chromic acid pigments such as chrome lead and molybdate orange; Ferrocyan pigments such as bitumen; Sulfides such as cadmium yellow, cadmium red, zinc sulfide and barium sulfide Pigment; ultramarine, calcium carbonate, cobalt violet, yellow iron oxide, carbon black and the like. These organic pigments and inorganic pigments can be used alone or in combination of two or more.

  The blending amount of the pigment (B) in the pigment printing agent of the present invention varies depending on the desired hue, but usually it is preferably in the range of 0.05 to 5% by mass in the pigment printing agent. In addition, when blending the pigment (B) in the pigment printing agent of the present invention, it is preferable to blend in advance using a pigment dispersant or the like in water to obtain a pigment dispersion.

  In the pigment printing agent of the present invention, a printing paste or the like can be blended in order to impart suitability such as viscosity according to the printing method. Printing paste is a material that thickens pigment printing agents and imparts printability to screen printing, such as sodium carboxymethylcellulose, hydroxyethylcellulose, propioxycellulose, sodium alginate, alginate, polycarboxylate, etc. The thing melt | dissolved or disperse | distributed to water is mentioned.

  In addition to the above, the pigment printing agent of the present invention includes a pH adjuster such as ammonia water, petroleum solvents such as mineral spirits, thickeners, crosslinking agents, antioxidants, ultraviolet absorbers, pigment dispersants, repellents. Additives such as a liquid agent, a leveling agent, and an antifoaming agent can be blended.

  Examples of the method for printing the pigment printing agent of the present invention on a fabric include a screen printing method using a roller printing machine, a flat screen, a rotary screen printing machine or the like with a squeegee such as rubber or urethane resin. Moreover, the screen used for screen printing normally uses a 60-300 mesh thing. After printing, a drying and heat treatment step is performed at 100 to 150 ° C. for 1 to 5 minutes to fix the pigment printing agent to the fabric.

  In addition, when printing a dye printing agent after printing the pigment printing agent of the present invention on a fabric, the pigment printing agent of the present invention is printed on the fabric and then dried once to print the dye printing agent. The method (wet-on-dry method) or the method of printing the pigment printing agent of the present invention on a fabric and then printing the dye-printing agent without drying may be used.

  In addition to the above screen printing, various printing methods such as gravure coating, roll coating, comma coating, air knife coating, kiss coating, wire bar coating, and flow coating can also be used as a method for printing the pigment printing agent of the present invention on a fabric. Can do. Furthermore, the pigment printing agent of this invention can also be apply | coated to a cloth by immersion (padding method), a spray system, and an inkjet system.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.

(Synthesis Example 1: Synthesis of polymer (A-1))
652 parts by mass of n-butyl acrylate (hereinafter abbreviated as “BA”), 92 parts by mass of methyl methacrylate (hereinafter abbreviated as “MMA”), styrene (hereinafter abbreviated as “St”) 140 parts by mass, acrylic acid (hereinafter abbreviated as “AA”) 20 parts by mass, 2-hydroxyethyl methacrylate (hereinafter abbreviated as “HEMA”) 12 parts by mass, glycidyl methacrylate (hereinafter, “GMA”) Abbreviated.) 12 parts by mass, 4 parts by mass of vinyltriethoxysilane (hereinafter abbreviated as “VSi”), 400 parts by mass of water, and nonionic emulsifier (Daiichi Kogyo Seiyaku Co., Ltd. “Neugen EA-207D” ", Polyoxyethylene distyrenated phenyl ether) after mixing 10 parts by mass, homogenizer (" TK Homo Disper "manufactured by Tokushu Kika Kogyo Co., Ltd.) Was emulsified with a monomer emulsion was prepared using.

  Next, after adding 500 parts by mass of water to a flask equipped with a stirrer, a nitrogen inlet tube and a reflux condenser, the temperature was raised to 50 ° C. while stirring and mixing in a nitrogen gas atmosphere, and then ammonium persulfate (hereinafter referred to as “APS”). (Abbreviated) 2 parts by mass and 2 parts by mass of sodium metabisulfite (hereinafter abbreviated as “SMS”) were added to the flask and dissolved. Then, 40 mass parts of 5 mass% APS aqueous solution and 40 mass parts of 5 mass% SMS aqueous solution prepared above were dripped in the flask over 3 hours. The temperature in the flask during the dropping was controlled to 50 to 60 ° C. After completion of dropping, the mixture was further reacted at 60 ° C. for 1 hour to obtain a polymer (A-1). Thereafter, after cooling to room temperature, the mixture was neutralized by adding 7 parts by mass of 25% by mass aqueous ammonia, and water was added and mixed uniformly so that the resin content would be 45% by mass. An aqueous resin emulsion was obtained.

(Synthesis Examples 2 to 8: Synthesis of Polymers (A-2) to (A-8))
Except having used the raw material shown in the following Table 1, it carried out similarly to the synthesis example 1, and obtained the aqueous resin emulsion of polymer (A-2)-(A-8).

  The aqueous resin emulsions of the polymers (A-1) to (A-8) obtained in Synthesis Examples 1 to 8 can be used as they are as the fiber processing resin composition of the present invention.

(Comparative Synthesis Examples 1 to 8: Synthesis of Polymers (RA-1) to (RA-8))
Except having used the raw material shown in the following Table 2, it carried out similarly to the synthesis example 1, and obtained the aqueous resin emulsion of the polymer (RA-1)-(RA-8) for a comparison.

(Preparation Example 1: Preparation of terpene emulsion)
60 parts by mass of mineral spirit (“Exor D40” manufactured by ExxonMobil), 5 parts by mass of an emulsifying thickener (“RYUDYE-W REDUCER CONC 720ENF” manufactured by DIC Corporation), and 35 parts by mass of water are mixed together, and a homogenizer (special A terpene emulsion was obtained by emulsification using “TK Homomixer” manufactured by Meika Kogyo Co., Ltd.

(Example 1: Preparation of pigment printing agent (1))
30 parts by mass (13.5 parts by mass as a resin) of an aqueous resin emulsion (resin content 45% by mass) of the polymer (A-1) obtained in Synthesis Example 1, 5 parts by mass of ethylene glycol, obtained in Preparation Example 1 60 parts by weight of a terpene emulsion, 2 parts by weight of a thickener (“RYUDYE-W NT CONC 117” manufactured by DIC Corporation), and 0.5 parts by weight of 25% by weight ammonia water were uniformly mixed using a dispersion stirrer. Furthermore, 5 parts by mass of a black pigment dispersion (“DEXCEL BLACK NT-900” manufactured by DIC Corporation, pigment content: 30% by mass) is uniformly mixed using a dispersion stirrer to obtain a pigment printing agent (1). It was.

(Examples 2 to 8: Preparation of pigment printing agents (2) to (8))
Instead of the aqueous resin emulsion (resin content 45 mass%) of the polymer (A-1) used in Example 1, the polymers (A-2) to (A-8) obtained in Synthesis Examples 2 to 8 were used. The pigment printing agents (2) to (8) were obtained in the same manner as in Example 1 except that each was used.

(Comparative Examples 1 to 8: Preparation of pigment printing agents (R1) to (R8))
Instead of the aqueous resin emulsion (resin content 45 mass%) of the polymer (A-1) used in Example 1, the polymers (RA-1) to (RA-8) obtained in Comparative Synthesis Examples 1-8 ) Was used in the same manner as in Example 1 except that pigment printing agents (R1) to (R8) for comparison were obtained.

(Production of evaluation fabric)
The pigment printing agents (1) to (8) and (R1) to (R8) obtained in the above Examples 1 to 8 and Comparative Examples 1 to 9 were respectively used as autoscreen printing machines (manufactured by Sakurai Dyeing Machine Co., Ltd.). ) On a B4 size cotton broad on a 135 mesh rectangular pattern screen. Next, the printed cotton broad was dried at 100 ° C. for 1 minute with a pad dryer (manufactured by Sakurai Dyeing Machine Co., Ltd.) and then heat-treated at 150 ° C. for 2 minutes to obtain an evaluation fabric.

(Evaluation of texture)
The evaluation fabric obtained above was evaluated by the tentacles according to the following criteria.
○: A soft tactile sensation where the boundary between the printed surface and the fabric is not felt.
(Triangle | delta): It is the touch feeling of the grade which can feel the boundary of a printed surface and cloth | dough slightly.
X: A firm tactile sensation in which the boundary between the printed surface and the fabric is felt.

(Evaluation of washing resistance)
For the evaluation fabric obtained above, the test was repeated 30 times in accordance with JIS L 0844: 2005 A-4 method, and then the visual sensation using the gray scale for fading color of JIS L 0801: 2004 The grades were judged from 1st grade to 5th grade according to the judgment criteria of the law. In addition, as for the grade, 1st grade has the largest fading, and the closer to 5th grade, the less fading.

(Evaluation of friction resistance)
The evaluation fabric obtained above was subjected to dry and wet tests using a Gakushin type friction fastness tester in accordance with JIS L 0849: 2004, and then changed to JIS L 0801: 2004. The grades were judged from 1st to 5th grades according to the judgment criteria of the visual method using the gray scale for fading. In addition, as for the grade, 1st grade has the largest fading, and the closer to 5th grade, the less fading.

(Preparation Example 2: Preparation of dye printing agent)
10 parts by weight of water, 20 parts by weight of a 4% by weight sodium alginate aqueous solution, 20 parts by weight of a 6% by weight carboxymethylcellulose aqueous solution, 40 parts by weight of the terpene emulsion obtained in Preparation Example 1, 2 parts by weight of sodium bicarbonate, 10 parts by weight of urea, And 5 parts by mass of a dye (“Kayacion Red P-BN Liquid 33” or “Kayacion Blue P-NFB Liquid 50” manufactured by Nippon Kayaku Co., Ltd.) are uniformly mixed using a dispersion stirrer and used for dye combination processing A printing agent was obtained.

(Preparation of fabric for evaluation processed with dye)
The pigment printing agents (1) to (8) and (R1) to (R8) obtained in Examples 1 to 8 and Comparative Examples 1 to 8 were used as an auto screen printing machine (manufactured by Sakurai Dyeing Machine Co., Ltd.). After printing on a B4 size cotton broad on a 135 mesh rectangular pattern screen, the dye printing agent obtained in Preparation Example 2 was continuously applied twice in the same manner as the pigment printing agent. I printed it. Next, after drying at 100 ° C. for 1 minute with a pad dryer (manufactured by Sakurai Dyeing Machine Co., Ltd.), a steaming process was performed at 100 ° C. for 8 minutes to develop the dye. Then, after washing with warm water at 80 ° C. for 10 minutes to wash away the undyed dye, the fabric for evaluation was obtained by drying naturally and dye-dyeing.

(Evaluation of dyed heavy-colored fabric)
The above-described evaluation fabric subjected to dye heavy color processing was tested in the same manner as the above-described evaluation of washing resistance, and the water resistance of the dye heavy color portion was evaluated.

  The evaluation results using the pigment printing agents (1) to (8) and (R1) to (R8) obtained in Examples 1 to 8 and Comparative Examples 1 to 9 are shown in Tables 3 and 4.

  From the evaluation results shown in Table 1, the fabric printed with the pigment printing agent using the fiber processing resin composition of the present invention is excellent in washing resistance and friction resistance without impairing the original texture of the fabric, It was also confirmed that there was no problem in water resistance of the portion (dye heavy color portion) printed with the dye printing agent.

  On the other hand, Comparative Example 1 is an example of a pigment printing agent containing a polymer that does not use the polymerizable monomer (a2) having an epoxy group, but compared with the pigment printing agent of the present invention, It was confirmed that the property was poor in water resistance, friction resistance, and water resistance of the dye heavy color part.

  Comparative Example 2 is an example of a pigment printing agent containing a polymer that does not use the polymerizable monomer (a3) having a hydrolyzable silyl group, but compared with the pigment printing agent of the present invention. It was confirmed that the washability, abrasion resistance, and water resistance of the heavy-colored dye portion were inferior.

  In Comparative Example 3, the ratio of the polymerizable monomer (a2) having an epoxy group exceeds the upper limit of 5% by mass, and the polymerizable monomer (a2) having an epoxy group and a hydrolyzable silyl group are included. Although it is an example of the pigment printing agent containing the polymer whose mass ratio with the polymerizable monomer (a3) is also outside the specified range, the original texture of the fabric is impaired as compared with the pigment printing agent of the present invention. In addition, it was confirmed that the washing resistance, the friction resistance and the water resistance of the dye heavy color portion were inferior.

  In Comparative Example 4, the ratio of the polymerizable monomer (a3) having a hydrolyzable silyl group exceeds the upper limit of 3.5% by mass, and the polymerizable monomer (a2) having an epoxy group is hydrolyzed. This is an example of a pigment printing agent containing a polymer whose mass ratio to the polymerizable monomer (a3) having a functional silyl group is also outside the specified range, but compared with the pigment printing agent of the present invention, It was confirmed that the original texture was impaired and the washing resistance, friction resistance, and water resistance of the dye heavy color portion were inferior.

  Comparative Example 5 has an epoxy group although the mass ratio of the polymerizable monomer (a2) having an epoxy group and the polymerizable monomer (a3) having a hydrolyzable silyl group is within a specified range. Although it is an example of the pigment printing agent containing the polymer in which the ratio of the polymerizable monomer (a2) exceeds the upper limit of 5% by mass, compared to the pigment printing agent of the present invention, the original texture of the fabric is improved. It was confirmed that it was inferior in water resistance, washing resistance, friction resistance, and water resistance of the heavy-colored portion of the dye.

  In Comparative Example 6, the mass ratio of the polymerizable monomer (a2) having an epoxy group and the polymerizable monomer (a3) having a hydrolyzable silyl group is within a specified range, but the hydrolyzable silyl This is an example of a pigment printing agent containing a polymer in which the ratio of the polymerizable monomer having a group (a3) exceeds the upper limit of 3.5% by mass, but compared with the pigment printing agent of the present invention, It was confirmed that the original texture of the fabric was impaired and the washing resistance, friction resistance, and water resistance of the dye heavy color portion were inferior.

  In Comparative Examples 7 and 8, the ratio of the polymerizable monomer (a2) having an epoxy group and the polymerizable monomer (a3) having a hydrolyzable silyl group is within a specified range, but has an epoxy group. This is an example of a pigment printing agent containing a polymer in which the mass ratio of the polymerizable monomer (a2) and the polymerizable monomer (a3) having a hydrolyzable silyl group is outside the specified range. Compared with the pigment printing agent of the invention, it was confirmed that the original texture of the fabric was impaired and the washing resistance, friction resistance and water resistance of the dye-colored portion were inferior.

Claims (4)

  Polymerizing a polymerizable monomer including a polymerizable monomer (a1) having a carboxyl group, a polymerizable monomer (a2) having an epoxy group, and a polymerizable monomer (a3) having a hydrolyzable silyl group It is the resin composition for fiber processing containing the polymer (A) obtained by this, Comprising: The said polymerizable monomer (a2) in the polymerizable monomer whole quantity used as the raw material of the said polymer (A) The ratio of the polymerizable monomer (a3) is in the range of 0.1 to 3.5% by mass, and the polymerizable monomer (a2) is in the range of 0.1 to 3.5% by mass. And a mass ratio [(a2) / (a3)] of the polymerizable monomer (a3) in the range of 10/90 to 90/10.   A pigment printing agent comprising the resin composition for fiber processing according to claim 1 and a pigment (B).   A fabric printed with the pigment printing agent according to claim 2.   A fabric obtained by further printing a dye printing agent on the fabric according to claim 3.