JPWO2016190208A1 - Pigment printing agent and fabric using the same - Google Patents

Abstract

The present invention relates to a polymer obtained by polymerizing a polymerizable monomer containing a polymerizable monomer (a1) having a carboxyl group and a polymerizable monomer (a2) having a hydrolyzable silyl group (A ) And titanium oxide (B), wherein the elongation percentage of the polymer (A) alone film is in the range of 1,200 to 5,000%, and the 1,000% modulus is 0. A pigment printing agent having a pressure of 1 MPa or more is provided. This pigment printing agent can impart excellent texture to the printed fabric without generating harmful formaldehyde, can impart high washing resistance and friction resistance to the printed portion, and also to the dye-colored portion. High washability can be imparted.

Description

  The present invention can impart an excellent texture to a printed fabric without generating harmful formaldehyde, can impart high washing resistance and friction resistance to the printed portion, and further overlays a dye printing agent on the fabric. The present invention relates to a pigment printing agent capable of imparting high washing resistance to a printed part and a fabric using the same.

  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, pigment printing agents containing these cross-linking agents can sufficiently impart excellent texture to the fabric and high washing resistance, friction resistance, etc. to the printed part when titanium oxide is used as the pigment. There wasn't.

  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 washing resistance of a printing portion where the pigment and the dye overlap (hereinafter abbreviated as “dye heavy color portion”) is lowered.

  Therefore, an excellent texture can be imparted to the printed fabric without generating harmful formaldehyde, high washing resistance and friction resistance can be imparted to the printed portion, and high water resistance can be imparted to the dye-heavy color portion. There has been a need for pigment printing agents that can be applied.

JP 2009-15010 A

  The problem to be solved by the present invention is that a printed fabric can be given an excellent texture without generating harmful formaldehyde, high washing resistance and friction resistance can be given to the printed portion, and further, It is an object to provide a pigment printing agent that can impart high washability to the color portion, and a fabric using the pigment printing agent.

  As a result of intensive studies to solve the above problems, the present inventors polymerized a polymerizable monomer including a polymerizable monomer having a carboxyl group and a polymerizable monomer having a hydrolyzable silyl group. It was found that the above-mentioned problems can be solved by using the polymer obtained in the above-mentioned manner and setting the film elongation rate and 1,000% modulus of the polymer alone within a specific range, thereby completing the present invention.

  That is, the present invention relates to a polymer obtained by polymerizing a polymerizable monomer containing a polymerizable monomer (a1) having a carboxyl group and a polymerizable monomer (a2) having a hydrolyzable silyl group. A pigment printing agent comprising (A) and titanium oxide (B), wherein the elongation percentage of the polymer (A) alone is in the range of 1,200 to 5,000%, and 1,000% modulus. The present invention provides a pigment printing agent characterized in that is 0.1 MPa or more and a fabric using the same.

  The pigment printing agent 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 if it contains titanium oxide as a pigment or is printed on the fabric. Since it is excellent in the washing resistance of the dye heavy color portion, 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 of the present invention can be used in combination with a dye printing agent to print various designs on a fabric without being restricted by the design.

  The pigment printing agent of the present invention was obtained by polymerizing a polymerizable monomer containing a polymerizable monomer (a1) having a carboxyl group and a polymerizable monomer (a2) having a hydrolyzable silyl group. A pigment printing agent containing a polymer (A) and titanium oxide (B), wherein the elongation percentage of the polymer (A) alone film is in the range of 1,200 to 5,000%, 1,000 % Modulus is 0.1 MPa or more.

  The polymerizable monomer (a1) is a polymerizable monomer having a carboxyl group, and examples thereof include (meth) acrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic anhydride, and citraconic acid. It is done.

  The polymerizable monomer (a2) is a polymerizable monomer having a hydrolyzable silyl group. For example, vinylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) ) Vinylsilane compounds such as silane; 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxy Examples include (meth) acryloyloxyalkylsilane compounds such as propylmethyldiethoxysilane.

  The polymerizable monomers (a1) and (a2) 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.

  Other polymerizable monomers that can be used as raw materials for the polymer (A) other than the polymerizable monomer (a1) having a carboxyl group and the polymerizable monomer (a2) having a hydrolyzable silyl group. Examples of the monomer (a3) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, and isopropyl (meth). Alkyl (meth) acrylates such as acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate; aromatic (meth) acrylates such as benzyl (meth) acrylate; silanes such as trimethylsiloxyethyl (meth) acrylate (meta ) Acrylate; methoxypolyethylene glycol mono (me ) Acrylate, alkyl polyalkylene glycol mono (meth) acrylate such as methoxypolypropylene glycol mono (meth) acrylate; fluorine-based (meth) acrylate such as perfluoroalkylethyl (meth) acrylate; styrene, styrene derivative (p-dimethylsilylstyrene) , (P-vinylphenyl) methyl sulfide, p-hexynylstyrene, p-methoxystyrene, p-tert-butyldimethylsiloxystyrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, α-methyl Styrene, 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- (Acryloxymethoxy) phenyl] propane, 2,2-bis [4- (acryloxyethoxy) phenyl] propane, dicyclopentenyl (meth) acrylate tricyclodecanyl (meth) acrylate, tris (acryloxyethyl) isocyanurate , (Meth) acrylate compounds such as urethane (meth) acrylate; alkylamino groups such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and dimethylaminopropyl (meth) acrylate (Meth) acrylate having; acrylamide compounds such as (meth) acrylamide, N, N-dimethylacrylamide, isopropylacrylamide and diacetone acrylamide; acrylonitrile; vinylpyridine compounds such as 2-vinylpyridine, 4-vinylpyridine and naphthylvinylpyridine; Conjugated dienes such as 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-cyclohexadiene Etc. These polymerizable monomers (a3) can be used alone or in combination of two or more.

  Further, among the polymerizable monomers (a3), the elongation percentage of the polymer (A) alone film is in the range of 1,200 to 5,000%, and the 1,000% modulus is 0.1 MPa or more. Therefore, it is preferable to use a polymerizable monomer having a glass transition temperature (Tg) of a homopolymer such as 2-ethylhexyl acrylate, n-butyl acrylate, and ethyl acrylate of −20 ° C. or lower.

  The ratio of the polymerizable monomer (a1) in the total amount of the polymerizable monomers (a1) to (a3), which is a raw material of the polymer (A), is determined by adding the pigment printing agent of the present invention to water. A range of 0.1 to 10% by mass is preferable, and a range of 0.5 to 8% by mass is more preferable because it can impart better dispersibility and can further impart high washing resistance and friction resistance to the printed part. The range of 1 to 6% by mass is more preferable.

  In addition, the ratio of the polymerizable monomer (a2) in the total amount of the polymerizable monomers (a1) to (a3) as the raw material of the polymer (A) is marked with the pigment printing agent of the present invention. A range of 0.1 to 5% by mass is preferable, because an excellent texture can be imparted to the printed fabric, and high washing resistance and friction resistance can be imparted to the printed part. Is more preferable, and the range of 0.5 to 2.5% by mass is more preferable.

  As a manufacturing method of the polymer (A), for example, a known emulsion polymerization method can be used.

  The elongation percentage of the polymer (A) alone is in the range of 1,200 to 5,000%, but since it can impart high washing resistance and friction resistance to the printed part, 1,500 to A range of 4,000% is preferred. Further, the 1,000% modulus of the film is 0.1 MPa or more, and the upper limit is preferably 3 MPa because the printing part can impart high washing resistance and friction resistance with a soft texture. Is more preferable.

  In addition, the elongation percentage and 1,000% modulus of the polymer (A) alone are values obtained by preparing a film with the polymer (A) alone and measuring with a tensile tester. As the tensile tester, for example, “Tensilon” manufactured by Orientec Co., Ltd., “Autograph” manufactured by Shimadzu Corporation, etc. can be used. Moreover, as a manufacturing method of the said polymer (A) single film, the said polymer (A) of the quantity used as the film thickness of about 0.5 mm is poured into a glass-made type | mold, and it heat-drys, for example. For example, a method of peeling after peeling.

  The pigment printing agent of the present invention contains titanium oxide (B). The titanium oxide (B) is used for coloring the pigment printing agent of the present invention in white, and there are anatase type (tetragonal), rutile type (tetragonal) and brookite type (orthorhombic). In addition to the rutile type having low activity and excellent thermal stability, an anatase type can also be used.

  The titanium oxide (B) may be added directly to the polymer (A) and mixed uniformly. However, the titanium oxide (B) is previously dispersed in water together with a surfactant and a pigment dispersant. After preparing the liquid, it is preferable to use a method in which the dispersion is added to the polymer (A) and mixed uniformly to improve concealability and miscibility.

  Further, in the pigment printing agent of the present invention, in addition to the titanium oxide (B), an extender pigment (C) such as silica, alumina silicate, calcium carbonate, precipitated barium sulfate is blended for the purpose of enhancing the hiding property. Also good.

  The extender pigment (C) may be added directly to the polymer (A) and mixed uniformly. However, the extender pigment (C) is dispersed in water together with a surfactant and a pigment dispersant in advance. After preparing the liquid, it is preferable to use a method in which the dispersion is added to the polymer (A) and mixed uniformly to improve concealability and miscibility.

  In order to obtain a desired hue, the pigment printing agent of the present invention may be blended with other pigments (D) other than the titanium oxide (B). There is no restriction | limiting in particular as said other pigment (D), 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, pyrazolone red, condensed azo yellow, condensed azo red, condensed azo brown, nickel azo yellow. Phthalocyanine pigments such as phthalocyanine blue, chlorinated phthalocyanine green, brominated phthalocyanine green; anthraquinone yellow, dianthraquinonyl red, indanthrene blue, thioindigo Bordeaux, perinone orange, perylene scarlet, perylene orange Perylene red, perylene maroon, quinacridone red, quinacridone magenta, quinacridone scarlet, dioxazine violet, Isoindolinone yellow, 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, petal, iron black, and chromium oxide; titanium yellow, zinc-iron brown, titanium cobalt green, cobalt green, cobalt blue, and copper-chrome black. Metal complex oxide pigments such as copper-iron black; Chromic acid pigments such as yellow lead and molybdate orange; Ferrocyanide pigments such as bitumen; Sulfide pigments such as cadmium yellow, cadmium red, zinc sulfide, and barium sulfide; Examples include ultramarine blue, calcium carbonate, cobalt violet, yellow iron oxide, and carbon black. These organic pigments and inorganic pigments can be used alone or in combination of two or more.

  Similar to the titanium oxide (B), the other pigment (D) may be directly added to the polymer (A) and mixed uniformly. However, the pigment (D) may be added in advance to a surfactant or a pigment. It is preferable to use a method of preparing a dispersion dispersed in water together with a dispersant, and then adding the dispersion to the polymer (A) and mixing them uniformly, because the saturation and miscibility are improved. Moreover, when preparing a dispersion liquid, you may prepare the dispersion liquid of each pigment separately, or may disperse | distribute it in water with the said titanium oxide (B) and the said extender pigment (C).

  The blending amount of the titanium oxide (B), the extender pigment (C) and the other pigment (D) in the pigment printing agent of the present invention varies depending on the desired hue, but usually the pigment printing agent of the present invention. The total of the titanium oxide (B), the extender pigment (C) and the other pigment (D) is preferably in the range of 5 to 40% by mass.

  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, emulsifiers, thickeners, crosslinking agents, antioxidants, ultraviolet absorbers, dispersants, Additives such as water repellents, leveling agents, antifoaming agents, bactericides, and preservatives 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))
8 parts by mass of acrylic acid (hereinafter abbreviated as “AA”), 12 parts by mass of maleic anhydride (hereinafter abbreviated as “MAH”), vinyltriethoxysilane (hereinafter abbreviated as “VSi”) 2 parts by mass, 2-ethylhexyl acrylate (hereinafter abbreviated as “2EHA”) 277 parts by mass, styrene (hereinafter abbreviated as “St”) 100 parts by mass, water 200 parts by mass and a nonionic emulsifier (No. After mixing 10 parts by weight of “Neugen EA-207D” manufactured by Ichi Kogyo Seiyaku Co., Ltd. and polyoxyethylene distyrenated phenyl ether), the mixture was emulsified using a homogenizer (“TK Homo Disper” manufactured by Tokushu Kika Kogyo Co., Ltd.). A monomer emulsion was prepared.

  Next, after adding 300 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 “APS”) was used. (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 at 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). Then, after cooling to room temperature, 9 mass parts of 25 mass% ammonia water was added and neutralized, water was added and mixed uniformly so that a non-volatile content might be 36 mass%, and polymer (A-1) An aqueous resin emulsion was obtained.

(Synthesis Examples 2 to 4: Synthesis of Polymers (A-2) to (A-4))
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-4).

(Comparative Synthesis Example 1 and: Synthesis of Polymers (RA-1) and (RA-2))
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 polymer emulsion of the polymer (RA-1) and (RA-2) for a comparison.

[Measurement of film properties]
About the polymers (A-1) to (A-4), (RA-1) and (RA-2) obtained in Synthesis Examples 1 to 4 and Synthesis Comparative Examples 1 and 2, respectively, A film having a thickness of 0.5 mm was produced by pouring into a mold and drying by heating. Subsequently, about the obtained film, the elongation rate and 1000% modulus were measured using the tensile testing machine ("Tensilon RTC-1310A" by Orientec Co., Ltd.).

  The raw material compositions and film properties of the polymers (A-1) to (A-4), (RA-1) and (RA-2) obtained in Synthesis Examples 1 to 3 and Synthesis Comparative Examples 1 and 2 are as follows. Table 1 shows.

The abbreviations in Table 1 represent the following.
IA: itaconic acid EA: ethyl acrylate AN: acrylonitrile BA: n-butyl acrylate GMA: glycidyl methacrylate

(Example 1: Preparation of pigment printing agent (1))
30 parts by mass of an aqueous acrylic resin emulsion of the polymer (A-1) obtained in Synthesis Example 1, 3 parts by mass of ethylene glycol, 4.5 parts by mass of water, and a white pigment dispersion (“WHITE 70 BASE” manufactured by DIC Corporation) , 60 mass parts of pigment content) was uniformly mixed using a dispersion stirrer. Next, 1.5 parts by weight of a thickener (“RYUDYE-W NT CONC 117” manufactured by DIC Corporation) and 1 part by weight of 25% by weight ammonia water are added, and mixed uniformly using a dispersion stirrer to produce a pigment printing agent. (1) was obtained.

(Examples 2 to 4: Preparation of pigment printing agents (2) to (4))
Instead of the aqueous resin emulsion of the polymer (A-1) used in Example 1, the aqueous resin emulsions of the polymers (A-2) to (A-4) obtained in Synthesis Examples 2 to 4 were used respectively. Except that, pigment printing agents (2) to (4) were obtained in the same manner as in Example 1.

(Comparative Examples 1 and 2: Preparation of pigment printing agents (R1) and (R2))
Instead of the aqueous resin emulsion of the polymer (A-1) used in Example 1, the aqueous resin emulsions of the polymers (RA-1) and (RA-2) obtained in Comparative Synthesis Examples 1 and 2 were respectively used. Except having used, it carried out similarly to Example 1 and obtained the pigment printing agents (R1) and (R2) for a comparison.

[Production of evaluation fabric]
The pigment printing agents (1) to (4), (R1) and (R2) obtained in Examples 1 to 3 and Comparative Examples 1 and 2 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 Machinery Co., Ltd.), and then heat treated at 140 ° C. for 2 minutes to obtain a fabric for evaluation.

[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 Washing resistance was evaluated by judging grades from grades 1 to 5 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. In accordance with the criteria for the visual method using the gray scale for fading, the grades were judged from grades 1 to 5 to evaluate the friction resistance. The grade 1 has the lowest wear resistance (large fading), and the grade 5 has higher wear resistance (less fading).

(Preparation Example 1: Preparation of emulsion paste)
50 parts by mass of mineral spirit (“Exol D40” manufactured by ExxonMobil), 5 parts by mass of an emulsifying thickener (“RYUDYE-W REDUCER CONC 720ENF” manufactured by DIC Corporation), and 45 parts by mass of water are mixed together, and a homogenizer (special Emulsion paste was obtained by emulsification using “TK Homomixer” manufactured by Meika Kogyo Co., Ltd.

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

[Preparation of fabric for evaluation processed with dye]
The pigment printing agents (1) to (3), (R1) and (R2) obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were respectively used as autoscreen printing machines (manufactured by Sakurai Dyeing Machine Co., Ltd.). ) Using a 135 mesh rectangular pattern screen on a B4 size cotton broad, and then the dye printing agent obtained in Preparation Example 2 was continuously applied twice in the same manner as the pigment printing agent. And 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 Dye Heavy Color Fabric]
About the fabric for evaluation which carried out dye heavy color processing obtained above, it tested similarly to evaluation of said wash resistance, and evaluated the wash resistance of the dye heavy color part.

  Table 2 shows the evaluation results using the pigment printing agents (1) to (4), (R1) and (R2) obtained in Examples 1 to 4 and Comparative Examples 1 and 2.

  From the evaluation results shown in Table 1, the fabric printed with the pigment printing agent of the present invention (Examples 1 to 4) is excellent in washing resistance and friction resistance without impairing the original texture of the fabric. It was confirmed that there was no problem with the water resistance of the portion (dye heavy color portion) printed with the printing agent.

  On the other hand, Comparative Example 1 is an example in which a polymer that did not use the polymerizable monomer (a2) having a hydrolyzable silyl group was used, and the 1,000% modulus of the polymer film was less than 0.1 MPa. However, as compared with the pigment printing agent of the present invention, it was confirmed that it was inferior in washing resistance, wet friction resistance and washing resistance of the dye-heavy color part.

  Comparative Example 2 is an example in which the elongation percentage of the polymer alone used in the pigment printing agent is less than 1,200%. However, compared with the pigment printing agent of the present invention, the original texture of the fabric is impaired, and It was confirmed that the washability, the wet rub resistance, and the washability of the dye heavy color portion were inferior.

Claims (5)

  Polymer (A) and titanium oxide obtained by polymerizing polymerizable monomer containing polymerizable monomer (a1) having carboxyl group and polymerizable monomer (a2) having hydrolyzable silyl group A pigment printing agent containing (B), wherein the polymer (A) alone has a film elongation of 1,200 to 5,000%, and a 1,000% modulus of 0.1 MPa or more. A pigment printing agent characterized by   The ratio of the polymerizable monomer (a1) in the total amount of the polymerizable monomer as a raw material of the polymer (A) is in the range of 0.1 to 10% by mass, and the polymerizable monomer (a2 The pigment printing agent according to claim 1, wherein the ratio of   The pigment printing agent according to claim 1 or 2, further comprising an extender pigment (C) and / or a pigment (D) other than the titanium oxide (B).   A fabric printed with the pigment printing agent according to any one of claims 1 to 3.   The fabric according to claim 4, which has a portion in which the pigment printing agent according to any one of claims 1 to 3 and the dye printing agent are overprinted.