JP2007046176A - Color-deepening agent, method for processing textile product using the color-deepening agent and textile product using the color-deepening agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a color-deepening agent for providing a textile product especially using a polyester fiber with excellent color deepening effect, antistatic properties and stability of mixed liquid, to provide a method for processing a textile product using the color-deepening agent and to obtain a textile product by using the color-deepening agent. <P>SOLUTION: The color-deepening agent is attached to a textile and heat-treated in use. The color-deepening agent is obtained by mixing a water dispersion (A-1) of an acrylic resin that has ≤1.50 refractive index, 100-150°C glass transition temperature and is internally crosslinked, with a water dispersion (A-3) of an acrylic resin that has ≤1.50 refractive index, -20 to 20°C glass transition temperature and is internally crosslinked, a betaine type compound (B) and an acidic phosphoric acid alkyl ester salt (C). The method for processing a textile product comprises attaching the color-deepening agent to a textile, pre-drying it and further heat-treating the textile at a higher temperature condition. The textile product is obtained by attaching the color-deepening agent to a textile and heat-treating the textile. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a darkening agent used for darkening polyester fiber products and the like, and also relates to a method of processing a fiber product using the darkening agent, and a fiber product using the darkening agent. .
More specifically, it is used for the purpose of improving characteristics such as color depth, depth, and sharpness of dyed polyester fiber products, etc., and imparting antistatic properties (that is, antistatic effect). The present invention relates to a thickening agent having excellent liquid stability, a method for processing a fiber product using the darkening agent, and a fiber product using the same.

In general, synthetic fibers, especially polyester fibers, are widely used in various textile products, but they have characteristics such as color depth, depth, and sharpness in dyed goods compared to natural fibers such as wool and silk. The product value in the market tended to be evaluated low.
Synthetic fibers have a problem that they are easily charged with static electricity and easily cause dust adsorption and uncomfortable clinging to the body.

  As countermeasures against such problems, various proposals for improving characteristics such as color depth, depth, and sharpness of dyed products obtained from synthetic fibers such as polyester fibers and imparting antistatic properties. Has been made. For example, it comprises an aqueous dispersion of a polymer obtained by polymerizing an ethylenically unsaturated monomer in the presence of a cationic surfactant, and has a refractive index of 1.50 or less and a glass transition point exceeding 110 ° C. A darkening agent comprising a polymer and a polymer having a refractive index of 1.50 or less and a glass transition point of less than 20 ° C. has been proposed (for example, see Patent Document 1). Is said to give a good darkening effect and scratch resistance to textiles.

  And an antistatic agent for a fiber structure in which at least one alkyl group bonded to a nitrogen atom has 1 to 4 carbon atoms, and the remainder is hydrogen and / or an alkyl group having 1 to 4 carbon atoms, and a low refractive index. The darkening agent was treated alone by using in combination with a darkening agent that essentially required at least one resin selected from the group consisting of urethane resin, fluorine resin, silicone, vinyl resin, and acrylic resin. It has been proposed that the darkening effect is improved as compared with the case, and that a treatment agent in which a darkening agent and an antistatic agent are mixed is stabilized (for example, see Patent Document 2).

  However, normally, in the darkening process of synthetic fibers, the darkening process and the antistatic process are simultaneously performed using a darkening agent and an antistatic agent in combination, and the method proposed in Patent Document 1 is , A processing method using a darkening agent in combination with a cationic emulsion and a nonionic antistatic agent such as a higher alcohol polyoxyethylene ether or a cationic antistatic agent such as a quaternary ammonium salt. Therefore, there is a problem that the darkening effect is remarkably lowered.

  Furthermore, the processing method using an anionic antistatic agent such as acidic phosphate ester salt does not reduce the darkening effect so much, but the cationic emulsion aggregates in a short time after blending, and the stability of the blended solution And had serious problems in practical use.

  Further, the method proposed in Patent Document 2 has a problem that the surface tension of the treatment agent is too large, and the amount of the treatment agent attached to the synthetic fiber is reduced, resulting in poor antistatic properties. .

As described above, a darkening agent capable of simultaneously imparting an excellent darkening effect and an antistatic effect to fiber products using synthetic fibers, in particular, fiber products using polyester fibers, is not yet known. Was the current situation.
Japanese Patent Laid-Open No. 9-3774 JP-A-11-172576

  Therefore, the object of the present invention is to impart an excellent darkening effect to fiber products, particularly fiber products using polyester fibers, and improve properties such as color depth, depth, and sharpness, At the same time, it is used for the purpose of imparting antistatic properties (that is, an antistatic effect), a thickening agent having excellent stability of the blended liquid, a method for processing a textile product using the thickening agent, and the darkening The object is to provide a textile product using a coloring agent.

  As a result of intensive studies to solve the above problems, the present inventors have found that an aqueous dispersion of an internally crosslinked acrylic resin having a glass transition temperature of 100 to 150 ° C or a glass transition temperature of 100 to 150 ° C. An aqueous dispersion of an acrylic resin that is not internally crosslinked within a range, an aqueous dispersion of an acrylic resin that is internally crosslinked within a range of a glass transition temperature of -20 to 20 ° C, and a betaine type represented by the following general formula (I) It has been found that the above-mentioned problems can be solved by using a darkening agent comprising a compound and an acidic phosphoric acid alkyl ester salt, and the present invention has been completed.

  That is, the present invention relates to a thickening agent used by adhering to a fiber and heat-treating, wherein the thickening agent is t-butyl methacrylate, an alkylene di (meta) which may contain a nitrogen atom in the main chain. ) Using acrylate (a-2) and N-methylolacrylamide as essential components, emulsion polymerization in the presence of a cationic surfactant, having a refractive index of 1.50 or less and a glass transition temperature of 100 to 150 ° C. A range of internally crosslinked acrylic resin aqueous dispersion (A-1), alkyl mono (meth) acrylate (a-1) in which the hydrogen atom of the alkyl group may be substituted with a halogen atom, nitrogen in the main chain An alkylene di (meth) acrylate (a-2) which may contain atoms, an alkyl monomethacrylate (a-3) having a hydroxyl group, and N-methylolacrylamide are essential components. Used as an aqueous dispersion of an internally crosslinked acrylic resin having a refractive index of 1.50 or less and a glass transition temperature in the range of -20 to 20 ° C. (A-3) obtained by emulsion polymerization in the presence of a cationic surfactant. And the following general formula (I)

[However, in the general formula (I), n represents an integer of 8 to 18, and C _n H _{2n + 1} which is an alkyl group bonded to a nitrogen atom may be a linear structure or a branched structure. ] A darkening agent characterized by comprising a betaine-type compound (B) represented by formula (B) and an acidic phosphoric acid alkyl ester salt (C).

  The present invention also relates to a darkening agent used by adhering to a fiber and heat-treating, the darkening agent using t-butyl methacrylate and N-methylolacrylamide as essential components, and the presence of a cationic surfactant. An aqueous dispersion (A-2) of an acrylic resin which is not cross-linked by emulsion polymerization under the conditions of a refractive index of 1.50 or less and a glass transition temperature of 100 to 150 ° C., and hydrogen of an alkyl group Alkyl mono (meth) acrylate (a-1) optionally substituted with halogen atom, alkylene di (meth) acrylate (a-2) optionally containing nitrogen atom in main chain, hydroxyl group An alkyl monomethacrylate (a-3) and N-methylolacrylamide are used as essential components, and emulsion polymerization is carried out in the presence of a cationic surfactant. Aqueous dispersion of an acrylic resin having a glass transition temperature has an internal cross-linking in the range of -20 to 20 ° C. at 50 or less and (A-3), the following general formula (I)

[However, in the general formula (I), n represents an integer of 8 to 18, and C _n H _{2n + 1} which is an alkyl group bonded to a nitrogen atom may be a linear structure or a branched structure. ] A darkening agent characterized by comprising a betaine-type compound (B) represented by formula (B) and an acidic phosphoric acid alkyl ester salt (C).

  In addition, the present invention provides a method for processing a fiber product, characterized in that the darkening agent is adhered to a fiber, and after the preliminary drying, heat treatment is performed under a temperature condition higher than the preliminary drying temperature. .

  In addition, the present invention provides a fiber product obtained by attaching the darkening agent to a fiber and heat-treating it.

  In the present invention, “(meth) acrylate” means “acrylate and / or methacrylate”.

  The glass transition temperature (Tg) in the present invention is measured by differential scanning calorimetry (DSC method) in a nitrogen atmosphere using a solid content obtained by drying an acrylic resin aqueous dispersion at 60 ° C. under reduced pressure. It is the value.

  Moreover, the refractive index as used in the field of this invention is the value which measured the film which dried the acrylic resin aqueous dispersion at 140 degreeC with the Abbe refractometer.

  The darkening agent of the present invention imparts an excellent darkening effect to fiber products, particularly fiber products using polyester fibers, and improves properties such as color depth, depth, and sharpness. At the same time, an antistatic effect (that is, an antistatic effect) can be imparted, and the stability of the blended liquid is excellent, and no aggregates are generated during storage.

  Further, the processing method using the darkening agent of the present invention is characterized in that the darkening agent is adhered to the fiber, and after the preliminary drying, heat treatment is further performed under a temperature condition higher than the preliminary drying temperature. The product processing method, the fiber product obtained by processing using the darkening agent of the present invention is imparted with a darkening effect, and the properties such as color depth, depth, and sharpness are improved, It is extremely effective in improving the texture and has excellent antistatic properties (that is, an antistatic effect).

The matters necessary for carrying out the present invention are described below.
The internally-crosslinked acrylic resin aqueous dispersion (A-1) is t-butyl methacrylate, alkylene di (meth) acrylate (a-2) which may contain a nitrogen atom in the main chain, and N-methylolacrylamide. As an essential component, preferably 90 to 100% by mass of these in total, and if necessary, emulsion polymerization in the presence of a cationic surfactant together with other monomers copolymerizable with these, refraction An aqueous dispersion of an internally cross-linked acrylic resin having a rate of 1.50 or less and a glass transition temperature in the range of 100 to 150 ° C. may be used, and in particular, a thickening agent having excellent darkening effect and scratch resistance is obtained. Therefore, an aqueous dispersion of an internally crosslinked acrylic resin having a refractive index of 1.40 to 1.45 and a glass transition temperature of 100 to 130 ° C. is preferable.

  Examples of the alkylene di (meth) acrylate (a-2) that may contain a nitrogen atom in the main chain used herein include ethylene glycol dimethacrylate, butylene glycol dimethacrylate, N, N′-methylenebisacrylamide, and the like. These may be used alone or in combination of two or more.

  As the aqueous dispersion (A-1) of the internally cross-linked acrylic resin, in particular, it promotes irregular reflection of visible light on the fiber surface by maintaining the particle shape in the heat treatment step, and exhibits a high darkening effect, and is also scratch resistant. Since a thickening agent having excellent properties can be obtained, t-butyl methacrylate, alkylene di (meth) acrylate (a-2) which may contain a nitrogen atom in the main chain, and N-methylol acrylamide, T-butyl methacrylate is 87 to 95% by mass with respect to the total of 100% by mass, alkylene di (meth) acrylate (a-2) which may contain a nitrogen atom in the main chain is 3 to 7% by mass, and An aqueous dispersion of an acrylic resin formed by using N-methylolacrylamide in a proportion of 2 to 10% by mass is preferable, and t-butyl methacrylate is preferably 90 to 9 % By mass, alkylene di (meth) acrylate (a-2), which may contain a nitrogen atom in the main chain, 4-6% by mass, and N-methylolacrylamide 2-6% by mass. An acrylic resin aqueous dispersion is more preferred.

  Further, the aqueous dispersion (A-3) of the internally crosslinked acrylic resin has an alkyl mono (meth) acrylate (a-1) in which a hydrogen atom of an alkyl group may be substituted with a halogen atom, in the main chain. An alkylene di (meth) acrylate (a-2) which may contain a nitrogen atom, an alkyl monomethacrylate (a-3) having a hydroxyl group, and N-methylolacrylamide are essential components, preferably 90 to 90 in total. 100% by mass, and if necessary, emulsion polymerization in the presence of a cationic surfactant together with other monomers copolymerizable with these, having a refractive index of 1.50 or less and a glass transition temperature of −20 A water dispersion of an internally crosslinked acrylic resin in the range of -20 ° C. may be used, and among them, a thickening agent having excellent darkening effect and scratch resistance can be obtained. It preferably has a glass transition temperature of aqueous dispersion of internally crosslinked acrylic resin in the range of 0 to 20 ° C. at 0 to 1.45.

  As the alkyl mono (meth) acrylate (a-1) in which the hydrogen atom of the alkyl group used here may be substituted with a halogen atom, the alkyl mono (meth) having 1 to 4 carbon atoms in the alkyl group. Acrylates are preferred, and examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, heptafluorobutyl methacrylate and the like. [However, alkyl mono (meth) acrylate having a hydroxyl group is excluded. These can be used alone or in combination of two or more.

  If the number of carbon atoms of the alkyl group of the alkyl mono (meth) acrylate (a-1) in which the hydrogen atom may be substituted with a halogen atom is in the range of 1 to 4, the fiber product has an excellent darkening effect. Can be obtained.

  Moreover, as alkylene di (meth) acrylate (a-2) which may contain a nitrogen atom in the main chain, nitrogen in the main chain used in the preparation of the aqueous dispersion (A-1) of the acrylic resin is used. Any of the same as alkylene di (meth) acrylate (a-2) which may contain an atom may be mentioned, and one or more selected from the group can be used.

  The alkyl monomethacrylate (a-3) having a hydroxyl group is preferably an alkyl monomethacrylate having 1 to 4 carbon atoms in the alkyl group, such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate. It is done. These can be used alone or in combination of two or more.

  Furthermore, N-methylol acrylamide is essential for the preparation of the aqueous dispersion (A-3) of the acrylic resin.

  As the water dispersion (A-3) of the internally cross-linked acrylic resin, in particular, it promotes irregular reflection of visible light on the fiber surface by maintaining the shape of the particles in the heat treatment step, exhibits a high darkening effect, and is resistant to resistance. Alkyl mono (meth) acrylates in which hydrogen atoms may be substituted with halogen atoms, because a thickening agent is obtained that has excellent scratching properties and also provides excellent adhesion and flexibility to the fiber surface. 100 masses in total of (a-1), alkylene di (meth) acrylate (a-2) which may contain a nitrogen atom in the main chain, alkyl monomethacrylate (a-3) having a hydroxyl group and N-methylolacrylamide %, The alkyl mono (meth) acrylate (a-1) in which hydrogen atoms may be substituted with halogen atoms is 80 to 91% by mass, and nitrogen atoms are contained in the main chain. 3-7% by mass of alkylene di (meth) acrylate (a-2), which may be 3-3% by mass, 3-7% by mass of alkyl monomethacrylate (a-3) having a hydroxyl group, and 3-7% by mass of N-methylolacrylamide %, Preferably an acrylic resin aqueous dispersion used in a proportion of 82% by weight, and the alkyl mono (meth) acrylate (a-1) in which hydrogen atoms may be substituted with halogen atoms is 82 to 88% by mass, 4-6 mass% of alkylene di (meth) acrylate (a-2) which may contain a nitrogen atom in the chain, 4-6 mass% of alkyl monomethacrylate (a-3) having a hydroxyl group, and N- An aqueous dispersion of an acrylic resin that is used in a proportion of 4 to 6% by mass of methylolacrylamide is more preferable.

  The acrylic resin aqueous dispersion (A-2) not internally cross-linked has t-butyl methacrylate and N-methylolacrylamide as essential components, preferably 90 to 100% by mass in total, and as required. In addition to other monomers copolymerizable with these, emulsion-polymerization is carried out in the presence of a cationic surfactant, and an internal crosslinking having a refractive index of 1.50 or less and a glass transition temperature of 100 to 150 ° C. An aqueous dispersion of an acrylic resin that has not been used, and in particular, a thickening agent that is excellent in darkening effect and scratch resistance is obtained, so that the refractive index is 1.40 to 1.45 and the glass transition temperature is high. It is preferable that it is the aqueous dispersion of the acrylic resin which is not the internal crosslinking of the range of 100-130 degreeC.

  Furthermore, as the aqueous dispersion (A-2) of the acrylic resin not internally cross-linked, in particular, it promotes irregular reflection of visible light on the fiber surface by maintaining the shape of the particles in the heat treatment step, and exhibits a high darkening effect. In addition, since a darkening agent having excellent scratch resistance is obtained, t-butyl methacrylate and N-methylol acrylamide are 90 to 95% by mass of t-butyl methacrylate with respect to 100% by mass in total. And an aqueous dispersion of an acrylic resin used in a proportion of 5 to 10% by mass of N-methylolacrylamide, 93 to 95% by mass of t-butyl methacrylate, and 5 to 7% by mass of N-methylolacrylamide. An aqueous dispersion of an acrylic resin used at a ratio of% is more preferable.

  In the darkening agent of the present invention, the ratio of the amount of the acrylic resin aqueous dispersion (A-1) and (A-3) used, and the acrylic resin aqueous dispersion (A-2) and (A The ratio of the amount used of -3) is usually in the range of (A-1) / (A-3) = 5/95 to 30/70, and (A-2) / (A-3) in terms of solid content mass ratio. ) = 5 / 95-30 / 70, in particular, (A-1) / (A-3) = 5 / 95-15 / 85, and (A-2) / (A-3) ) = 5/95 to 15/85 is preferable. If the solid content mass ratio between the aqueous dispersion (A-1) and (A-3) and the solid content mass ratio between the aqueous dispersion (A-2) and (A-3) are within the ranges, A thickening agent having an excellent darkening effect and scratch resistance can be obtained.

  Since the acrylic resin particles in the acrylic resin aqueous dispersion (A-1) or (A-2) used in the darkening agent of the present invention have a high glass transition temperature (Tg) of 100 to 150 ° C., a textile product. Even during heat treatment during processing (for example, at 130 to 180 ° C. for 30 seconds to 1 minute), it is difficult to melt regardless of the presence or absence of internal crosslinking, and the particle state can be maintained on the fiber surface.

  On the other hand, since the acrylic resin particles in the acrylic resin aqueous dispersion (A-3) have a low glass transition temperature (Tg) of -20 to 20 ° C., they are relatively melted in the heat treatment during the processing of the textile product. Although it is easy, since it is internally cross-linked by the combined use of acrylic monomers having a plurality of double bonds, it is the non-cross-linked part that melts, and the cross-linked part forms a film with fine irregularities on the fiber surface.

  The thickening agent of the present invention using a combination of such an acrylic resin aqueous dispersion (A-1) and (A-3) or (A-2) and (A-3) is used for textile processing. During the heat treatment, the cross-linking reaction between the melted non-crosslinked parts of the particles of (A-3) by N-methylolacrylamide and the non-crosslinked part of the particle surface of (A-1) or (A-2) (A The cross-linked portion of the melted non-crosslinked portion of the particles of -3) is integrated by N-methylol acrylamide, and the particles of (A-2) may be internally cross-linked by N-methylol acrylamide. ] In order to form a coating film by forming irregularities in which fine particles of (A-1) or (A-2) are integrated in a dispersed state in a coating film having fine irregularities made of (A-3) on the fiber surface. In addition, irregular reflection of visible light is improved, and a superior color depth and higher sharpness can be imparted to the textile product, and an excellent darkening effect can be exhibited.

  For such a darkening agent of the present invention, for example, an aqueous dispersion (A-3 ′) of an acrylic resin having a glass transition temperature (Tg) of −20 to 20 ° C. and not internally crosslinked is used as the glass transition temperature. In the darkening agent used in combination with an aqueous dispersion (A-2) of an acrylic resin that has not been internally crosslinked (Tg) of 100 to 150 ° C., there is no crosslinked structure inside by heat treatment at the time of textile processing ( Since the particles of A-3 ′) are dissolved, a film in which the fine particles of (A-2) are integrated in a dispersed state in an uneven film made of a dissolved product of the particles of (A-3 ′). The unevenness of the film is only unevenness due to the fine particles of (A-2), and there are few fine unevennesses compared to the darkening agent of the present invention, and only a darkening effect inferior to that of the darkening agent of the present invention is exhibited. Can not.

  The average particle diameter in water of the aqueous dispersions (A-1), (A-2) and (A-3) of the acrylic resin used in the present invention is usually in the range of 100 to 300 nm, among which the acrylic resin The average particle diameter in water of the aqueous dispersions (A-1) and (A-2) is preferably in the range of 150 to 250 nm, and the average particle in water of the aqueous dispersion (A-3) of the acrylic resin The diameter is preferably in the range of 100 to 200 nm. If the average particle diameter is within such a range, the color density becomes sufficient and the hue hardly changes.

  In order to prepare the aqueous dispersions (A-1), (A-2) and (A-3) of the acrylic resin, for example, each monomer composition containing the above-described monomer as an essential component. May be emulsion polymerized in the presence of a cationic surfactant. In the case of preparing the aqueous dispersions (A-1) and (A-3), an aqueous dispersion (emulsion) of an internally crosslinked acrylic resin is obtained. In general, such a polymer is called “microgel”.

  Although it does not specifically limit as a cationic surfactant used in the case of the said emulsion polymerization, Especially the compound represented by the following general formula (II) or (III) is preferable. These cationic surfactants may be used alone or in combination of two or more.

[However, in the general formula (II), ^{R 1} _represents C _{n H 2n + 1, n} is an integer of 12 to 18. ]

  Examples of the compound represented by the general formula (II) or (III) include stearyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, cetyltrimethylammonium chloride, lauryltrimethylammonium chloride, alkylbenzylammonium chloride, N, N, N-trimethyl-N- (2-hydroxy-3-methacryloyloxypropyl) ammonium chloride and the like, and among these compounds, since it is particularly effective in improving the dispersibility of the acrylic resin, hexadecyltrimethylammonium chloride, More preferred are stearyltrimethylammonium chloride and N, N, N-trimethyl-N- (2-hydroxy-3-methacryloyloxypropyl) ammonium chloride, which may be used alone or in combination of two or more. It may be used in combination.

  In the emulsion polymerization, the ratio of the usage amount of the cationic surfactant to the aqueous dispersion of the acrylic resin [ie, cationic surfactant / aqueous dispersion (A-1), cationic surfactant / aqueous dispersion (A- 2) and the cationic surfactant / water dispersion (A-3)] are usually in the range of 0.1 / 99.9 to 2.0 / 98.0 in terms of solid content mass ratio, in particular 0.2 /99.8 to 1.0 / 99.0 is preferred. When the ratio of the usage amount of the cationic surfactant to the aqueous dispersion of the acrylic resin is within such a range, a darkening agent having an excellent darkening effect can be obtained.

  Furthermore, in the emulsion polymerization, a small amount of a nonionic surfactant such as polyoxyethylene nonylphenyl ether may be used in combination with the cationic surfactant.

  Further, for the purpose of improving the stability of the acrylic resin aqueous dispersions (A-1), (A-2) and (A-3) within a range that does not hinder the purpose of the present invention after the emulsion polymerization, A nonionic surfactant can be used in combination with a cationic surfactant.

  Examples of such nonionic surfactants include polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene polyoxypropylene block polymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, Examples include polyoxyethylene alkylamine ether, fatty acid diethanolamide, sucrose ester, polyoxyethylene lanolin alcohol ether, polyoxyethylene lanolin fatty acid ester, etc., and these may be used alone with a cationic surfactant. It may be used in combination with a cationic surfactant.

  When a cationic surfactant and a nonionic surfactant are used in combination in the emulsion polymerization, the amount of the nonionic surfactant used is within the same range as that of the cationic surfactant. The ratio of the amount of resin used relative to the aqueous dispersion is preferably in the range of 0.01 / 99.99 to 1.0 / 99.0 in terms of the mass ratio of the solid content.

  The acrylic resin aqueous dispersions (A-1), (A-2), and (A-3) used in the darkening agent of the present invention may be produced by using t-butyl methacrylate, where the hydrogen atom is a halogen atom. Alkyl mono (meth) acrylate (a-1) which may be substituted, alkylene di (meth) acrylate (a-2) which may contain a nitrogen atom in the main chain, alkyl monomethacrylate having a hydroxyl group (a -3) and a monomer mixture each containing a monomer selected from N-methylolacrylamide as an essential component may be emulsion-polymerized in the presence of a cationic surfactant. An emulsion dispersed in a surfactant-containing aqueous solution (which may further contain a nonionic surfactant) is dropped into water containing a polymerization initiator. A method of emulsion polymerization, or the above-mentioned monomer or mixture thereof is emulsified by dropping it into an aqueous solution containing a polymerization initiator and a cationic surfactant (which may further contain a nonionic surfactant). Examples of the polymerization method are not particularly limited.

  The polymerization initiator is not particularly limited. For example, various polymerization initiators such as azo compounds, peroxides, and persulfates can be used, but there is no agglomerate or precipitate and stable water dispersion. Water-soluble such as 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride It is preferable to use the azo compound.

  Next, the betaine compound (B) represented by the following general formula (I), which is an essential component constituting the thickening agent of the present invention, will be described.

[However, in General Formula (I), n represents an integer of 8 to 18, and C _n H _{2n + 1} which is an alkyl group bonded to a nitrogen atom may be a linear structure or a branched structure. ]

  In the darkening agent of the present invention, by using the betaine type compound (B) represented by the general formula (I), the acrylic resin aqueous dispersions (A-1) and (A-3), or The effect of suppressing the aggregation of the mixture of the acrylic resin aqueous dispersions (A-2) and (A-3) and the acidic phosphoric acid alkyl ester salt (C) described later and improving the dispersion stability of the blended liquid Excellent.

  The betaine type compound (B) may be a compound represented by the general formula (I), for example, lauryl dimethylaminoacetic acid betaine, decyldimethylaminoacetic acid betaine, stearyldimethylacetic acid betaine, tridecyldimethylaminoacetic acid betaine. And myristyldimethylaminoacetic acid betaine. Among them, lauryldimethylaminoacetic acid betaine and decyldimethylaminoacetic acid betaine are preferable because a thickening agent having excellent soft texture can be obtained.

  The amount of the betaine compound (B) used is the acrylic resin aqueous dispersions (A-1) and (A-3), or the acrylic resin aqueous dispersions (A-2) and (A-3). It is the range of 1-30 mass parts with respect to the total solid content of 100 mass parts, Preferably it is the range of 5-20 mass parts, More preferably, it is the range of 5-15 mass parts. If the amount of the betaine-type compound (B) used is within such a range, even when blended with the acidic phosphoric acid alkyl ester salt (C), aggregation does not occur in the blended solution, excellent stability, and processing suitability is remarkably high. And an excellent darkening effect can be obtained.

  Furthermore, in the darkening agent of this invention, acidic phosphoric acid alkylester salt (C) is mix | blended as an essential component. By blending the acidic phosphoric acid alkyl ester salt (C) as an essential component, an excellent antistatic effect can be imparted without impairing the darkening effect of the thickening agent.

  In addition, in the dark color processing method, the combined use of the antistatic agent is effective and preferable for preventing static electricity disasters in the processing process and preventing the electrostatic charge of the textile product, but the higher alcohol polyoxyethylene ether which has been used conventionally is preferable. The combined use of a representative nonionic antistatic agent or a cationic antistatic agent typified by a quaternary ammonium salt tends to reduce the darkening effect.

  In the present invention, the acidic phosphoric acid alkyl ester salt (C) is used in combination with the aqueous dispersions (A-1) and (A-3) of the cationic acrylic resin, or the water of the cationic acrylic resin. When used in combination with the dispersions (A-2) and (A-3), it acts as an antistatic agent without inhibiting the darkening effect, but the (A-1), (A-3) and (A-3) In the blending of only the three components of C) or the blending of only the three components (A-2), (A-3) and (C), agglomeration occurred, causing a problem in practical use.

  In the present invention, as a solution to this problem, acidic phosphoric acid alkyl ester salt (C) is added to aqueous dispersions (A-1) and (A-3) or (A-2) and (A-2) of the cationic acrylic resin. A-3) is used in combination with the betaine-type compound (B) represented by the general formula (I), so that the stability of the blended liquid can be maintained without causing aggregation, and an excellent dark color. It has been found that it is possible to develop a color-improving effect, improve characteristics such as color depth, depth, and sharpness, and at the same time impart an antistatic effect (that is, an antistatic effect).

Examples of the acidic phosphoric acid alkyl ester salt (C) include compounds represented by the following general formulas (IV) and (V):
O = P (OR ² ) ₂ OX (IV)
And O = P (OX) ₂ OR ² (V)
[In General Formulas (IV) and (V), R ² may be the same or different and is an alkyl group having 1 to 8 carbon atoms, and X represents Li, Na, K, or the like. ].

  Examples of the compounds represented by the general formulas (IV) and (V) include acidic phosphoric acid methyl ester, acidic phosphoric acid ethyl ester, acidic phosphoric acid propyl ester, acidic phosphoric acid butyl ester, and acidic 2-ethylhexyl phosphate. Examples include esters such as alkali metal salts and ammonium salts such as lithium salts, sodium salts, potassium salts, etc. Among them, acidic phosphoric acid methyl ester, acidic phosphoric acid ethyl ester, acidic Sodium salts such as propyl phosphate and acidic butyl ester are preferred. These salts may be used in combination.

  The amount of the acidic phosphoric acid alkyl ester salt (C) used is the acrylic resin aqueous dispersions (A-1) and (A-3), or the acrylic resin aqueous dispersions (A-2) and (A). 3) to 100 parts by mass of the total solid content, 1 to 100 parts by mass, preferably 10 to 50 parts by mass, and more preferably 20 to 40 parts by mass. As long as the ratio to the amount of the acidic alkyl phosphate ester salt (C) used is within this range, an excellent darkening effect, scratch resistance, and a soft texture can be obtained, and textile products are cut and processed. It also has an excellent effect of suppressing static electricity generated during work operations such as transfer, transportation.

  The thickening agent of the present invention obtained in this way is the acrylic resin aqueous dispersions (A-1) and (A-3), or the acrylic resin aqueous dispersions (A-2) and (A -3), a betaine-type compound (B) represented by the general formula (I), and the acidic phosphoric acid alkyl ester salt (C) as essential components. If a coloring agent is used, for example, a fiber product using synthetic fibers, particularly polyester fibers, can be imparted with an excellent darkening effect that has never been achieved, such as color depth, depth, and sharpness. The characteristics can be improved, and at the same time, an antistatic property (that is, an antistatic effect) can be imparted, and furthermore, the stability of the blended liquid is also excellent.

  In addition, the thickening agent of the present invention may be further used in combination with an emulsified dispersion such as polydimethylsiloxane or amino-modified polydimethylsiloxane in order to impart scratch resistance.

Next, the fiber product processing method of the present invention will be described below.
The fiber product processing method of the present invention is such that the darkening agent of the present invention is adhered to the fiber, and after preliminary drying, further dried at a temperature condition higher than the preliminary drying temperature, preferably 80 to 120 ° C. as the preliminary drying temperature. Thereafter, heat treatment is performed under a temperature condition of 130 to 180 ° C.

  In the processing method of the textile product of the present invention, the method of attaching the darkening agent of the present invention to the fiber is based on the fiber product as the object to be processed or the type or form of the fiber using the thickening agent. The fiber surface of the object to be treated can be applied to the object to be treated by an arbitrary method, and is not particularly limited. For example, the fiber surface of the object to be treated by a known and usual method such as a coating process such as immersion impregnation / drawing, coating, or spraying. The method of making it adhere to is mentioned.

  In the textile product processing method of the present invention, the conditions for preliminary drying and heat treatment are not particularly limited as long as they do not adversely affect the quality of the intended textile product. Conditions such as curing at ˜120 ° C. for 30 seconds to 3 minutes and then curing at 130 ° C. to 180 ° C. for 30 seconds to 1 minute are preferable, and predrying conditions or heat treatment conditions can be set according to the situation.

Next, the fiber product of the present invention will be described below.
The fiber product of the present invention is characterized in that the darkening agent of the present invention is adhered to fibers and heat-treated. The heat treatment method may be any heat treatment method in which the darkening agent is fixed to the fiber, and is not particularly limited. Among them, the conditions used in the above-described fiber product processing method of the present invention, that is, after preliminary drying, further preliminary treatment is performed. What is formed by heat treatment under a temperature condition higher than the drying temperature, preferably a temperature of 130-180 ° C. after drying at 80-120 ° C. as a pre-drying temperature is preferable.

  Examples of the fiber products used in the present invention include yarns using synthetic fibers such as polyester, polyamide, and acrylic, regenerated fibers such as regenerated cellulose, semisynthetic fibers such as acetate, or natural fibers such as silk, cotton, and wool. Alternatively, woven fabrics, knitted fabrics, non-woven fabrics and the like using the same can be mentioned, and the dyed products can be processed as described above with the darkening agent of the present invention to obtain the textile product of the present invention. it can.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention more concretely, this invention is not limited only to these Examples.
In the text, “part” and “%” are based on mass unless otherwise specified.
Various physical properties were evaluated by the methods described below.

[Measurement method of glass transition temperature (Tg)]
The acrylic resin aqueous dispersions (A-1) to (A-3) and (A-3 ′) obtained in Synthesis Examples 1 to 4 described below were each dried under reduced pressure at 60 ° C., and the resulting solid content was obtained. The glass transition temperature (Tg) was measured using a differential scanning calorimetry method (DSC method) [measuring device; manufactured by Seiko Instruments Inc., DSC6200, analysis software; EXTER 6000] in a nitrogen atmosphere.

[Measurement method of refractive index]
Acrylic resin aqueous dispersions (A-1) to (A-3) and (A-3 ′) obtained in Synthesis Examples 1 to 4 described later were horizontally set to a polyethylene terephthalate film having a smooth surface (Toray Industries, Inc.). (Refer to Lumirror Co., Ltd.) After coating, the thickness after drying is about 0.2 mm, dried at room temperature for 24 hours, and then dried in a hot air dryer at 140 ° C. for 5 minutes for refractive index measurement. A test piece was prepared, and the refractive index of the obtained test piece was measured in accordance with JIS K7105 using an Abbe refractometer (KPR-30A, manufactured by Kalnew Optical Industry Co., Ltd.).

[Evaluation method of darkening effect]
Acrylic resin aqueous dispersion (A-1) or (A-2) having a Tg of 120 ° C. obtained in Synthesis Example 1 or 2 described later and Tg obtained in Synthesis Example 3 or 4 described later is 0 ° C. The acrylic resin aqueous dispersion (A-3) or (A-3 ′) was blended at a solid content blending ratio shown in Tables 1 and 2, diluted with water, and the total solid content was 100 parts. 12,500 parts of the mixed liquid (A) containing was obtained, and the black polyester raw cloth was immersed once in this mixed liquid and then impregnated by drawing once (hereinafter referred to as “1 dip · 1 nip”), and the resulting impregnated cloth Was pre-dried at 100 ° C. for 3 minutes, and further heat-treated at 160 ° C. for 30 seconds. The lightness (hereinafter referred to as L value) of the obtained processed cloth and the black polyester raw cloth was measured with a spectroscopic color difference meter (Nippon Denshoku Industries Co., Ltd.). Each was measured by SE2000), and pass / fail was evaluated according to the following evaluation criteria. Note that the smaller the L value, the darker the color.
Evaluation criteria;
○ (Pass): Difference in L value between raw cloth and processed cloth is 2 or more.
X (failure): The difference in L value between the raw cloth and the processed cloth is less than 2.

[Evaluation method of scratch resistance]
Using a Gakushin type friction fastness tester (manufactured by Suga Test Instruments Co., Ltd.), the work cloth and the black polyester base cloth obtained in the same manner as in the method for evaluating the darkening effect were each loaded with 100 N at a load of 2N. After rubbing, the L values were measured using the spectral color difference meter SE2000, and pass / fail was evaluated according to the following evaluation criteria. In addition, it means that it is excellent in abrasion resistance, so that the difference of L value before and behind abrasion is small.
Evaluation criteria;
○ (Pass): Difference in L value before and after rubbing is less than 2.
X (failure): The difference in L value before and after rubbing is 2 or more.

[Static evaluation method]
The work cloth obtained in the same manner as the method for evaluating the darkening effect was conditioned for 48 hours in a constant temperature and humidity chamber set at 20 ° C. and a relative humidity of 60%, and then the frictional voltage (KV) was changed to K Each was measured with a Daikaken rotary static tester (manufactured by Koa Shokai Co., Ltd., RST301), and pass / fail was evaluated according to the following evaluation criteria. In addition, it means that there are few injuries by static electricity and it is better, so that a frictional voltage is low.
Evaluation criteria;
○ (Pass): Frictional voltage is 1 KV or less.
X (failure): Frictional voltage exceeds 1 KV.

[Method for evaluating stability of compounded liquid]
The stability of the blended liquid was evaluated by the aggregate formation rate (% by mass) of the emulsion measured by the following method. That is, 1 liter is taken out from 12,500 parts of the blended liquid (A) obtained in the same manner as the method for evaluating the darkening effect, and placed in a transparent container having a diameter of 12 cm and a height of 20 cm. 4 cm in diameter and 7 mm in width) After stirring for 5 minutes at 800 rpm (manufactured by Special Machine Chemical Co., Ltd., TK homodisper DHL type), the mixture was filtered through a 320 mesh net, and the aggregates that could not be filtered were each dried at 60 ° C. under reduced pressure. The mass (S) of the dried aggregate obtained in this manner was weighed, and the aggregate production rate (mass%) was calculated by the following formula and evaluated according to the following evaluation criteria.
Aggregate production rate (mass%) = (S / S _X ) × 100
However, S in the formula is the mass number of copies of the dry agglomerates, S _X means mass parts of the vinyl polymer contained in the fiber treatment agent.
Evaluation criteria;
○: Aggregate formation rate is less than 1% by mass.
Δ: Aggregate production rate of 1% by mass or more and less than 30% by mass.
X: Aggregate production rate of 30% by mass or more.

[Synthesis Example 1]
In a 500 ml flask, 105 parts of ion-exchanged water, 1 part of Emalmine 50 (manufactured by Sanyo Chemical Industries, Ltd., polyoxyethylene cetyl ether, HLB = 9), 1 part of Cotamine 80W (manufactured by Kao Corporation, stearyltrimethylammonium chloride), t- 184 parts of butyl methacrylate, 10 parts of N-methylol acrylamide, and 6 parts of neopentyl glycol diacrylate were mixed to prepare 307 parts of a monomer emulsion (a1).

  Next, 450 parts of deionized water and 45 parts of the monomer emulsion (a1) were added to a 1000 ml polymerization vessel equipped with a nitrogen introduction tube, a dropping funnel, a reflux condenser, and a stirring device, and the system was replaced with nitrogen while stirring. The temperature was raised to 75 ° C., and 0.2 part of 2,2-azobis (2-amidinopropane) dihydrochloride was added to initiate polymerization. Furthermore, 262 parts of the remaining monomer emulsion (a1) was added dropwise over a required time of 120 minutes while maintaining the temperature at 75 to 78 ° C. Upon completion of dropping of the monomer emulsion, 0.2 part of 2,2-azobis (2-aminodipropane) dihydrochloride was added and stirred for 2 hours, deionized water was added, and the glass transition temperature (Tg) was 120 ° C. 1,000 parts of an internally crosslinked acrylic resin aqueous dispersion (A-1) containing 20% of the solid content of The refractive index of the acrylic resin in the obtained aqueous dispersion (A-1) of the acrylic resin was 1.42.

[Synthesis Example 2]
In a 500 ml flask, 105 parts of ion-exchanged water, 1 part of Emalmine 50 (manufactured by Sanyo Chemical Industries, Ltd., polyoxyethylene cetyl ether, HLB = 9), 1 part of Cotamin 80W, 184 parts of t-butyl methacrylate, and 16 parts of N-methylolacrylamide Were mixed to prepare 307 parts of a monomer emulsion (a2), and the solid content with a glass transition temperature (Tg) of 120 ° C. was 20% in the same manner as in Synthesis Example 1 except that this monomer emulsion (a2) was used. 1,000 parts of an aqueous dispersion (A-2) of an acrylic resin containing no internal crosslinking was obtained. The refractive index of the acrylic resin in the obtained acrylic resin aqueous dispersion (A-2) was 1.42.

[Synthesis Example 3]
In a 500 ml flask, 105 parts of ion-exchanged water, 1 part of Noniolite AL-6 (manufactured by Kyoeisha Chemical Co., Ltd., polyoxyethylene lauryl ether, HLB = 11.7), 1 part of Cotamine 60W (manufactured by Kao Corporation, cetyltrimethylammonium chloride) , 10 parts of neopentyl diacrylate, 10 parts of 2-hydroxyethyl methacrylate, 10 parts of isobutyl methacrylate, 160 parts of isobutyl acrylate, and 10 parts of N-methylol acrylamide to prepare 307 parts of monomer emulsion (a3), Aqueous dispersion (A-3) 1 of an internally crosslinked acrylic resin containing 20% solids having a glass transition temperature (Tg) of 0 ° C. in the same manner as in Synthesis Example 1 except that the monomer emulsion (a3) was used. 1,000 parts were obtained. The refractive index of the acrylic resin in the obtained acrylic resin aqueous dispersion (A-3) was 1.43.

[Synthesis Example 4]
In a 500 ml flask, 105 parts of ion-exchanged water, 1 part of Emulgen 120 (manufactured by Kao Corporation, polyoxyethylene lauryl ether, HLB = 15.3), 1 part of Arcard 12-50 (manufactured by Lion Corporation, lauryltrimethylammonium chloride), Synthesis Example except that 10 parts of 2-hydroxyethyl methacrylate, 20 parts of isobutyl methacrylate and 170 parts of isobutyl acrylate were mixed to prepare 307 parts of monomer emulsion (a3 ′), and this monomer emulsion (a3 ′) was used. In the same manner as in Example 1, 1,000 parts of an aqueous dispersion (A-3 ′) of an acrylic resin not internally cross-linked containing 20% of a solid content having a glass transition temperature (Tg) of 0 ° C. was obtained. The refractive index of the acrylic resin in the obtained aqueous dispersion (A-3 ′) of the acrylic resin was 1.42.

[Examples 1 to 5]
The acrylic resin aqueous dispersions (A-1) to (A-3) obtained in Synthesis Examples 1 to 3 were respectively blended at the solid content blending ratios described in Tables 1 and 2, and diluted with water. In addition, 12,500 parts of a mixed liquid (A) containing 100 parts in total of the solid content was obtained, and the above-mentioned general formula (I) as a betaine type compound (B) with respect to 12,500 parts of the obtained mixed liquid (A) N = 12 and permastat WF-18 (manufactured by Dainippon Ink & Chemicals, Inc., sodium acid butyl ester sodium) as the acidic phosphoric acid alkyl ester salt (C) in the blending amounts shown in Table 1, respectively. The thickening agent of the present invention was obtained by blending.

A polyester satin black dyed cloth (length 80 cm, width 50 cm) is immersed in each of the darkening agents of the present invention, and then mangle (manufactured by Kyoto Machine Seisakusho, CP75 type, gauge pressure; 3.8 kg / cm ² , roll pressure). 3.5 tons), the wet pick-up value (mass increase rate with respect to the base fabric immediately after drawing) is reduced to 60%, pre-dried at 100 ° C. for 3 minutes, and further heat treated at 160 ° C. for 30 seconds (curing) After that, the obtained work cloths were evaluated by the above methods, and the results are summarized in Tables 1 and 2.

[Comparative Examples 1-4]
In Comparative Example 1, the aqueous dispersion (A-3) of the acrylic resin obtained in Synthesis Example 3 was diluted with water to obtain 12,500 parts of a blended liquid containing 100 parts of solid content. In Comparative Example 2, Synthesis Example 4 The aqueous dispersion (A-3 ′) of the acrylic resin obtained in 1 was diluted with water to obtain 12,500 parts of a blended liquid containing 100 parts of solids. Further, in Comparative Examples 3 and 4, Synthesis Examples 1 and 3 Each of the acrylic resin aqueous dispersions (A-1) and (A-3) obtained in 1 was blended at the solid content blending ratios listed in Table 2, diluted with water, and a total of 100 parts of the solid content was contained. In the comparative examples 1 and 2, the compound of n = 12 or n = 1 in the general formula (I) and acidic with respect to each of the obtained compounded liquids of 12,500 parts were obtained. In Comparative Example 3, phosphoric acid butyl ester (Permast WF-18) was blended in the blending amounts shown in Table 2. Without blending betaine compound (B), further, in Comparative Example 4, it was not added acidic alkyl phosphate ester salt (C), to obtain a darkening agent for comparison. Working cloths were obtained in the same manner as in Examples 1 to 5 except that the obtained comparative darkening agents were used, and the obtained working cloths were evaluated by the above-described methods. The results are shown in Table 2. Summarized.

  From the above results, in Comparative Example 3 in which the betaine compound (B) was not used, the stability of the blended solution was inferior, and in Comparative Example 4 in which the acidic phosphoric acid alkyl ester salt (C) was not used, the antistatic property was inferior. Was confirmed. Further, even when both the betaine type compound (B) and the acidic phosphoric acid alkyl ester salt (C) are used, only the aqueous dispersion (A-3) obtained in Synthesis Example 3 is used as the aqueous dispersion of the acrylic resin. In Comparative Example 1, the scratch resistance was inferior, and in Comparative Example 2 using only the aqueous dispersion (A-3 ′) obtained in Synthesis Example 4, it was confirmed that the darkening effect was inferior.

  Therefore, the darkening agent of the present invention, a method for processing a fiber product using the darkening agent, and a fiber product using the darkening agent have a darkening effect, antistatic properties, and a blended liquid. It was confirmed that the stability was excellent.

  The darkening agent of the present invention imparts an excellent darkening effect to fiber products, particularly fiber products using polyester fibers, and improves properties such as color depth, depth, and sharpness. At the same time, an antistatic effect (that is, an antistatic effect) can be imparted, which is extremely effective in improving the texture of the textile product, and the emulsion does not aggregate even after blending, and the stability of the blended liquid is excellent.

Furthermore, the fiber product processing method using the darkening agent of the present invention is characterized in that the darkening agent is adhered to the fiber, and after pre-drying, heat treatment is performed under a temperature condition higher than the pre-drying temperature. The textile product obtained by attaching the darkening agent of the present invention to the fiber and processing it exhibits an excellent darkening effect, such as color depth, depth, and sharpness. It is extremely effective for improving the characteristics and improving the texture, and has an excellent effect for imparting antistatic properties (that is, an antistatic effect).

Claims (9)

A darkening agent that is attached to the fiber and heat treated,
The thickening agent is t-butyl methacrylate, alkylene di (meth) acrylate (a-2) which may contain a nitrogen atom in the main chain, and N-methylol acrylamide as essential components, and cationic surface activity An aqueous dispersion (A-1) of an internally crosslinked acrylic resin having a refractive index of 1.50 or less and a glass transition temperature in the range of 100 to 150 ° C., which is obtained by emulsion polymerization in the presence of an agent;
Alkyl mono (meth) acrylate (a-1) in which hydrogen atom of alkyl group may be substituted with halogen atom, alkylene di (meth) acrylate (a-2) in which main chain may contain nitrogen atom , Alkyl monomethacrylate having a hydroxyl group (a-3), and N-methylolacrylamide as essential components and emulsion polymerization in the presence of a cationic surfactant, having a refractive index of 1.50 or less and a glass transition temperature. An internally dispersed acrylic resin aqueous dispersion (A-3) in the range of -20 to 20 ° C;
The following general formula (I)

[However, in the general formula (I), n represents an integer of 8 to 18, and C _n H _{2n + 1} which is an alkyl group bonded to a nitrogen atom may be a linear structure or a branched structure. ]
A betaine-type compound (B) represented by:
Acid phosphoric acid alkyl ester salt (C)
A thickening agent characterized by comprising A darkening agent that is attached to the fiber and heat treated,
The thickening agent is obtained by emulsion polymerization using t-butyl methacrylate and N-methylolacrylamide as essential components and in the presence of a cationic surfactant, and has a refractive index of 1.50 or less and a glass transition temperature of 100 to 100. An aqueous dispersion (A-2) of an acrylic resin that is not internally crosslinked in the range of 150 ° C .;
Alkyl mono (meth) acrylate (a-1) in which hydrogen atom of alkyl group may be substituted with halogen atom, alkylene di (meth) acrylate (a-2) in which main chain may contain nitrogen atom , Alkyl monomethacrylate having a hydroxyl group (a-3), and N-methylolacrylamide as essential components and emulsion polymerization in the presence of a cationic surfactant, having a refractive index of 1.50 or less and a glass transition temperature. An internally dispersed acrylic resin aqueous dispersion (A-3) in the range of -20 to 20 ° C;
The following general formula (I)

[However, in the general formula (I), n represents an integer of 8 to 18, and C _n H _{2n + 1} which is an alkyl group bonded to a nitrogen atom may be a linear structure or a branched structure. ]
A betaine-type compound (B) represented by:
Acid phosphoric acid alkyl ester salt (C)
A thickening agent characterized by comprising   The internally crosslinked acrylic resin aqueous dispersion (A-1) is t-butyl methacrylate, alkylene di (meth) acrylate (a-2) which may contain nitrogen atoms in the main chain, and N-methylol acrylamide. , With respect to 100% by mass in total, t-butyl methacrylate is 87 to 95% by mass, and alkylene di (meth) acrylate (a-2) which may contain a nitrogen atom in the main chain is 3 to 7 An aqueous dispersion of an acrylic resin that is used in a proportion of 2 to 10% by mass and N-methylolacrylamide, and the aqueous dispersion (A-3) of the internally crosslinked acrylic resin is an alkyl group Of the alkyl mono (meth) acrylate (a-1) which may be substituted with a halogen atom and alkylene di (meta) which may contain a nitrogen atom in the main chain In the acrylate (a-2), alkyl monomethacrylate (a-3) having a hydroxyl group and N-methylolacrylamide, the hydrogen atom of the alkyl group may be substituted with a halogen atom with respect to 100% by mass in total. The alkyl mono (meth) acrylate (a-1) is 80 to 91% by mass, the alkylene di (meth) acrylate (a-2) which may contain a nitrogen atom in the main chain is 3 to 7% by mass, and the hydroxyl group. 2. The dark color according to claim 1, which is an aqueous dispersion of an acrylic resin that is used at a ratio of 3 to 7% by mass of alkyl monomethacrylate (a-3) and 3 to 7% by mass of N-methylolacrylamide. Agent.   The aqueous dispersion (A-2) of the acrylic resin that has not been internally crosslinked contains t-butyl methacrylate and N-methylolacrylamide in a total amount of 100% by mass, and t-butyl methacrylate is 90 to 95% by mass. %, And N-methylolacrylamide is an aqueous dispersion of an acrylic resin used at a ratio of 5 to 10% by mass, and the aqueous dispersion (A-3) of the internally crosslinked acrylic resin is an alkyl group. An alkyl mono (meth) acrylate (a-1) optionally substituted with a halogen atom, an alkylene di (meth) acrylate (a-2) optionally containing a nitrogen atom in the main chain, and a hydroxyl group; Alkyl monomethacrylate (a-3) and N-methylolacrylamide having an alkyl group hydrogen source with respect to 100% by mass in total. Is an alkyl di (meth) acrylate (a-2) in which 80 to 91% by mass of the alkyl mono (meth) acrylate (a-1) which may be substituted with a halogen atom may contain a nitrogen atom in the main chain ) Is 3 to 7% by mass, alkyl monomethacrylate (a-3) having a hydroxyl group is 3 to 7% by mass, and N-methylolacrylamide is used in a proportion of 3 to 7% by mass. The darkening agent according to claim 2, wherein   The water dispersion (A-1) of the internally crosslinked acrylic resin and the water dispersion (A-3) of the internally crosslinked acrylic resin are (A-1) / (A-3) = in solid content mass ratio. The betaine type | formula mix | blended in the range of 5 / 95-15 / 85, and is represented with the said general formula (I) with respect to 100 mass parts of total solid content of the said (A-1) and (A-3). The thickening agent according to claim 1 or 3, wherein the compound (B) is blended in the range of 1 to 30 parts by mass and the acidic phosphoric acid alkyl ester salt (C) is blended in the range of 1 to 100 parts by mass.   The aqueous dispersion (A-2) of the acrylic resin that is not internally crosslinked and the aqueous dispersion (A-3) of the acrylic resin that is internally crosslinked are (A-2) / (A- 3) It mix | blends in the range of 5 / 95-15 / 85, and is represented by the said general formula (I) with respect to 100 mass parts of total solid content of the said (A-2) and (A-3). The darkening of Claim 2 or 4 which mix | blends the betaine-type compound (B) which is mixed in the range of 1-30 mass parts, and the said acidic phosphoric acid alkylester salt (C) in the range of 1-100 mass parts. Agent.   A method for processing a textile product, comprising the step of adhering the darkening agent according to any one of claims 1 to 6 to a fiber, pre-drying, and further heat-treating under a temperature condition higher than the pre-drying temperature. .   The method for processing a textile product according to claim 7, wherein the preliminary drying temperature is in the range of 80 to 120 ° C, and the heat treatment temperature is in the range of 130 to 180 ° C. A fiber product obtained by attaching the darkening agent according to any one of claims 1 to 6 to a fiber and heat-treating the fiber.