JPH0544180A - Dyeing - Google Patents

Abstract

PURPOSE:To produce a textile goods dyed to a deep color, showing fastness to washing and rubbing and excellent in reversible color change by pretreating the textile goods made of a synthetic fiber with a cationic polymer and subsequently treating it with a dispersion containing a polymer compound and fine particles capable of revesible color change by heat or light. CONSTITUTION:A textile goods made of a synthetic fiber such as a polyester or a polyamide is preliminarily treated and cationized by a cationic polymer (preferable example; condensed material between polyalkylenepolyamine and guanidine derivative, polyethyleneimines, etc.) then immersed and treated preferably with a dispersion of reversibly color-changeable fine particles composed of a polymer binder such as an acrylic acid ester resin and a material capable of reversible color change by heat or light and contained therein, thus obtaining the objective reversibly color-changeable textile goods capable of reversible color change depending on the temperature difference or on exposure to direct sun light. This method enables a high-concentration dyeing unlike in the conventional methods without damage to touch, feeling, etc., of the textile goods.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for dyeing a fiber product having synthetic fibers with reversible color-changing fine particles containing a heat- or photo-reversible color-changing material.

[0002]

2. Description of the Related Art Conventionally, a thermoreversible discolorable material whose color reversibly changes with temperature change, that is, a thermochromic material, has three components: an acid developing substance, an acidic substance and a solvent. It is known that a composition comprising: a two-component composition comprising an acid-developing substance and an acidic substance; a cholesteric liquid crystal; a metal complex salt crystal.

The three-component composition has a wide variety of colors and a high color density, and the color changes dramatically between colored and colorless. The two-component composition has a drawback that the discoloration is relatively slow and few changes in the daily environmental temperature range, but the concentration is higher than that of the three-component composition. The cholesteric liquid crystal requires a black base and has a concentration lower than that of the three-component composition, but the color changes sharply in red, yellow, green, blue, purple, etc. in an arbitrary temperature range. Can be made These three-component compositions,
The two-component composition and the cholesteric liquid crystal exhibit an excellent discoloring function only when the components maintain a strictly constant ratio system. In order to retain their function, they are usually used, for example, in the form of a fine powder of a matrix dispersed in a synthetic resin or in a state of being encapsulated in microcapsules.

On the other hand, as a photochromic material whose color reversibly changes depending on the presence or absence of light irradiation, that is, a photochromic material, it is colored and colorless as compared with a conventional inorganic photochromic compound such as silver halide. A variety of organic photochromic compounds have been developed that change sharply between the two, have a wide variety of colors, and have excellent compatibility with various organic compounds such as synthetic resins. Such an organic photochromic compound is used, for example, in the form of a fine powder of a matrix dispersed in a suitable medium or in a state of the matrix being encapsulated in microcapsules.

The fine powders and microcapsules of the matrix that reversibly change color by heat or light, that is, the reversible color changing fine powders, have no affinity with any fibers, and thus it is impossible to directly color the fibers like dyes. Can not. Although it is possible to color by a synthetic resin printing method or synthetic resin padding method using an adhesive such as a synthetic resin binder, the coloring concentration of the reversible discolorable fine powder containing a thermochromic material or a photochromic material is a general coloring agent. Therefore, in the synthetic resin printing method, for example, to some extent only when a textile product is bulky printed using an ink containing these reversible discolorable fine powder and a synthetic resin binder in a high concentration. The color density of is obtained. In this case, especially in the case of synthetic fibers, the feel of the fibers is completely lost on the surface thereof, the texture is deteriorated, and the abrasion fastness and the washing fastness are extremely insufficient, and even if the entire surface of the fabric is colored. , Will not be of commercial value.
Therefore, conventionally, a design such as a one-point pattern is only provided on a very narrow surface of the cloth, and the quality is not good.

When the pigment resin padding method using the reversible color-changing fine powder and the synthetic resin binder at a high concentration as described above is used, the reversible color-changing fine powder has no direct contact with the fiber and is sufficiently adsorbed. However, since it cannot be expected to be physically adhered as in the pigment resin printing method, only a product having an extremely low color density can be obtained. In addition, especially in the case of synthetic fibers, the feel, feel, friction fastness, etc. of the fibers are extremely insufficient.

The present invention has been made in view of the above problems existing in the prior art, and its object is to make polyester fibers, polyamide fibers, acrylic fibers, acrylic fibers and polyurethane fibers. A fiber product having one or more kinds of synthetic fibers selected from the group consisting of a reversible color-changing fine particle containing a heat- or photo-reversible color-changing material in a polymer compound has not been conventionally used. It can be dyed at a high density which was possible, so that the color of the material when developed can be made unmatchedly thick, and the dyeing does not impair the properties of the fiber product such as feel and feel. To provide a method.

[0008]

To achieve the above object, the dyeing method of the present invention comprises one or two selected from the group consisting of polyester fiber, polyamide fiber, acrylic fiber, acrylic fiber and polyurethane fiber. A step of treating a fiber product having at least one kind of synthetic fiber by immersing it in water containing a cationic polymer, and treating the fiber product so treated with a polymer compound by thermo- or photo-reversible discoloration And a treatment step of immersing it in an aqueous dispersion liquid containing reversible color-changing fine particles containing the above material.

Synthetic Fibers The synthetic fibers of the fiber product of the present invention include polyester fibers, polyamide fibers, and acrylic fibers.
), An acrylic fiber (modified acrylic fiber) and a polyurethane fiber selected from the group consisting of 1 or 2
It is more than a seed.

[0010] As the form of a fiber product comprising a fiber product above synthetic fibers,
Examples thereof include threads, slivers, loose wool, woven fabrics, knitted fabrics, non-woven fabrics, and sewn products such as clothing using these woven fabrics, knitted fabrics, and non-woven fabrics. Specific examples of sewn products include T-shirts, sweatshirts, jumpers, jeans, socks, bags, hats, blouses, skirts, sweaters, and the like. The fiber product of the present invention may include natural fibers or semi-synthetic fibers. The textile product used in the present invention may be colored in advance by dyeing or the like.

Cationic Polymer Examples of the above cationic polymer include polyamine type compounds and polycation type compounds. Specific examples of the cationic polymer are as follows. Examples of the polyamine type compound include condensates of polyalkylene polyamines and guanidine derivatives, polyethyleneimines, polyamide polyamines and the like.

Examples of the polycation type compound include poly-4-vinylpyridine hydrochloride and JP-A-54-6.
Tertiary amine polymers such as polyacrylonitrile polymers as disclosed in Japanese Patent No. 4186;
Dimethylamine-epichlorohydrin condensation polymer as disclosed in JP-A-3-243 and the like, JP-A-57-1
2-methacryloxypropyltrimethylammonium salt polymers as disclosed in 12480,
A dimethyldiallylammonium chloride-based polymer as disclosed in JP-A-55-76177,
A polyepichlorohydrin-trimethylamine reaction product as disclosed in JP-A-51-112987.
A quaternized polymer of 1-vinylimidazole as disclosed in JP-A-57-21038,
No. 0-9979 and JP-A-60-9980, polymers of quaternary compounds of epoxy compounds of polyalkylene polyamines, JP-A-57-
Copolymers of acrylamide and cationic monomers copolymerizable therewith described in JP-A-47309, JP-A-63-2
A cationic polymer having a quaternary ammonium salt group described in JP-A-34007, a quaternary ammonium salt type polymer such as a quaternary salt of an aminoalkyl acrylamide polymer disclosed in JP-A-63-284225, and JP-A-5-
Polymers composed of monomer units of the following formula disclosed in JP-A-6-128382

[0013]

[Chemical 1]

A polymer composed of monomer units of the following formula (Charol DC (trade name) series: manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)

[0015]

[Chemical 2]

And copolymers composed of these quaternary ammonium salt polymers and other vinyl polymers. Among these cationic polymers, a polyamine type compound, a quaternary ammonium salt type polymer belonging to the polycation type, and a copolymer of the quaternary ammonium salt with another vinyl-based monomer are used in the present invention. Is especially effective for.

Thermochromic material (material having thermoreversible discoloration
Fee) Examples of thermochromic materials for the present invention, San'arawa color material, ternary mixtures of acidic substance and a solvent;
A binary mixture of an acid-developing substance and an acidic substance; cholesteric liquid crystals and the like can be mentioned.

Three-Component Mixture, Two-Component Mixture As the acid-developing substance in the above-mentioned three-component mixture and the two-component mixture, triphenylmethanephthalide compound, phthalide compound, phthalane compound, acylleucomethylene blue compound, fluorane compound, trifluoromethane compound A phenyl methane compound, a diphenyl methane compound, a spiropyran compound etc. can be illustrated. As a concrete example,
3,6-dimethoxyfluorane, 3,6-dibutoxyfluorane, 3-diethylamino-6,8-dimethylfluorane, 3-chloro-6-phenylaminofluorane,
3-diethylamino-6-methyl-7-chlorofluorane, 3-diethyl-7,8-benzofluorane, 3,
3 ', 3 "-tris (p-dimethylaminophenyl) phthalide, 3,3'-bis (p-dimethylaminophenyl) phthalide, 3-diethylamino-7-phenylaminofluorane, 3,3-bis (p- Diethylaminophenyl) -6-dimethylaminophthalide, 3- (4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide, 3- (4-diethylamino-2-methyl) phenyl -3- (1,2-Dimethylindol-3-yl) phthalide, 2 '-(2-chloroanilino) -6'-dibutylaminospirophthalide-
3.9'-xanthene etc. can be mentioned.

Examples of the acidic substance in the above-mentioned three-component mixture and the two-component mixture include 1,2,3-benzotriazoles, phenols, thiourea derivatives, oxyaromatic carboxylic acids and the like. Specific examples thereof include 5-butylbenzotriazole, bisbenzotriazole-5-methane, phenol, nonylphenol,
Examples thereof include bisphenol A, bisphenol F, 2,2′-bisphenol, β-naphthol, 1,5-dihydroxynaphthalene, alkyl paraoxybenzoate and phenol resin oligomer.

As the solvent in the above three-component mixture,
Alcohols, alcohol-acrylonitrile adducts,
Examples thereof include azomethines, esters, ketones and the like. Specific examples thereof include decyl alcohol,
Lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol / acrylonitrile adduct,
Benzylidene p-toluidine, octyl caprate,
Decyl caprate, myristyl caprylate, decyl laurate, lauryl laurate, myristyl laurate,
Decyl myristate, lauryl myristate, cesyl myristate, lauryl palmitate, cetyl palmitate, stearyl palmitate, cetyl p-t-butylbenzoate, stearyl 4-methoxybenzoate, dilauryl thiodipropionate and the like can be mentioned. it can.

Cholesteric Liquid Crystal As the cholesteric liquid crystal, for example, cholesterol acetate, cholesterol benzoate, cholesterol nonanate, cholesterol propionate,
A mixture of two or more such as cholesterol oleyl carbonate and cholesterol chloride can be used.

Photochromic material (material having photoreversible discoloration
Examples of available photochromic materials to charge) present invention, azobenzene compounds, thioindigo compounds, dithizone metal complexes, spiropyran compounds, spirooxazine compounds, fulgide compounds, Jihidoropuren compounds, Supirochiopiran compound, 1 , 4-2H-oxazine, triphenylmethane-based compounds, pyrogen-based compounds, naphthopyran-based compounds, and other organic photochromic substances are mentioned. Compounds of the type are preferred.

Specific examples of the photochromic substance include:
1,3,3-Trimethylspiro [indoline-2,3 '
-(3H) naphtho (2,1-b) (1,4) -oxazine], 6'-indolino-1,3,3-trimethylspiro [indoline-2,3 '-(3H) naphtho (2,1) −
b) (1,4) -oxazine], 5-chloro-1,3,
3-trimethylspiro [indoline-2,3 '-(3
H) naphtho (2,1-b) (1,4) -oxazine],
6'-piperidino-1,3,3-trimethylspiro [indoline-2,3 '-(3H) naphtho (2,1-b)
(1,4) -Oxazine], 1-benzyl-3,3-dimethylspiro [indoline-2,3 ′-(3H) naphtho (2,1-b) (1,4) -oxazine], 1,3 ，
5,6-Tetramethyl-3-ethylspiro [indoline-2,3 '-(3H) naphtho (2,1-b) (1,4)
-Oxazine], 1,3,3,5,6-pentamethylspiro [indoline-2,3 '-(3H) naphtho (2,1
-B) (1,4) -oxazine], 1,3 ', 3'-trimethylspiro (2H-1-benzopyran-2,2'-
Indolino), 3,3,1-diphenyl-3H-naphtho- (2,1-13) pyran, 1- (2,3,4,5,6)
-Pentathymerbenzyl) -3,3-dimethylspiro [indoline-2,3 '-(3H) -naphtho (2,1-
b) pyran], 1- (2-nitrobenzyl) -3,3-
Dimethylspiro [indoline-2,3 '-(3H) -naphtho (2,1-b) pyran], 3,3-diphenylnaphtho (2,1-b) pyran, 2,5-dimethylfuryl-trimethylflugide , 2-methyl-5-chloro-trimethylfulgide, 3-phenyl-3- (p-phenyl) phenyl-3H-naphtho (2,1-b) pyran, 3-phenyl-3- (p-methoxy) phenyl -3H-naphtho (2,1-b) pyran and the like can be mentioned.

Reversible color-changing fine particles The reversible color-changing fine particles contain a thermochromic material or a photochromic material in a polymer compound. Examples of the reversible color-changing particles are:
Microcapsules of polymer compound containing thermochromic material, fine particles of matrix in which thermochromic material is dispersed in synthetic resin, fine particles of matrix in which photochromic material is dispersed in synthetic resin, matrix in which photochromic material is dispersed in synthetic resin And a microcapsule of a polymer compound containing a mixture of a photochromic material dissolved or dispersed in a medium. It is desirable that the reversible color-change fine particles have a particle size of about 50 μm or less. This is because if it exceeds 50 μm, the exhaustion to the fiber product may not be successful in many cases.

Thermochromic Microcapsule The three-component mixture, the two-component mixture or the cholesteric liquid crystal as a thermochromic material can be encapsulated in microcapsules by the following method, for example. That is, a thermochromic material selected from the above-mentioned three-component mixture, two-component mixture or cholesteric liquid crystal and a polymer compound as a film-forming substance, and if necessary, a surfactant, a protective colloid, a pH adjusting agent, an electrolyte, etc. A known encapsulation method such as an interfacial polymerization method, an in-site polymerization method, a core selection method, an air suspension method, and an interfacial precipitation method is carried out in water. As a result, microcapsules containing the thermochromic material and having a particle size of 1 to 50 μm can be obtained in a state of being dispersed in an aqueous dispersion liquid.

Further, by encapsulating two or more times using one or more of these encapsulation methods, it is possible to form a multi-layer microcapsule.
Preferable examples of the film-forming substance include polyvalent isocyanate and polyvalent amine for forming a polyurea film, polybasic acid chloride and polyvalent amine for forming a polyamide film, for forming a polyurethane film. Polyhydric isocyanate and polyhydroxy compound, polybasic acid chloride and polyhydroxy compound for forming polyester film, epoxy compound and polyvalent amine for forming epoxy resin film, melamine resin film for forming urea resin film Examples thereof include melamine / formalin prepolymer, urea formalin prepolymer, ethyl cellulose, polystyrene and polyvinyl acetate, and anionic polymer compounds and amphoteric polymer compounds described below.

The microcapsule film is preferably a thermosetting film which is excellent in heat resistance. Examples of the surfactants and protective colloids that can be preferably used include anionic surfactants, amphoteric surfactants, anionic polymer compounds and amphoteric polymer compounds. Further, these may be used in combination with a nonionic surfactant. As the pH adjuster and the electrolyte, those usually used in the encapsulation method can be used.

In the present invention, the dispersion liquid containing the thermochromic microcapsules obtained as described above can be used as it is, and a surfactant or a protective agent can be used within the range where the dispersibility of the microcapsules can be maintained from the dispersion liquid. It can also be used after removing the colloid. It is also possible to dehydrate and dry the dispersion liquid of the microcapsules to once make the microcapsules into a powder, and to add a surfactant or a protective colloid to the microcapsules at the time of use to disperse them in the liquid for use. At that time, if the dispersibility of the microcapsules is high, it is not necessary to add a surfactant or a protective colloid.
If the polymer compound forming the film of the microcapsule is anionic or amphoteric, it often has sufficient dispersibility, and therefore it is not necessary to add a surfactant or protective colloid.

Examples of the anionic surfactant include alkylbenzene sulfonate, polyoxyethylene alkyl sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene polystyryl phenyl ether sulfate. Etc. can be illustrated. Examples of the anionic polymer compound include polyacrylic acid and poly-
α-hydroxyacrylic acid and methacrylic acid, and copolymers of these with other vinyl polymers, ethylene /
Examples thereof include maleic anhydride copolymer, butylene / maleic anhydride copolymer, vinyl ether / maleic anhydride copolymer, anion-modified polyvinyl alcohol, gum arabic, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, starch derivative and the like. Examples of the amphoteric polymer compound include gelatin and casein.

Microparticles of Thermochromic Matrix Fine particles of a matrix in which the above-mentioned three-component mixture, two-component mixture or cholesteric liquid crystal is dispersed in a synthetic resin as a thermochromic material can be produced, for example, by the following method. First, the thermochromic material and synthetic resin selected from the above are heated and melted, and stirred to disperse the thermochromic material. In this state, the mixture is put into water containing a surfactant or protective colloid with stirring to obtain a matrix in the form of fine particles in which the thermochromic material is dispersed in the synthetic resin. Alternatively, the matrix in a fine particle state can be obtained by heating and melting the thermochromic material and the synthetic resin, stirring and freeze-pulverizing the dispersion of the thermochromic material.

Examples of synthetic resins usable for this matrix include polyvinyl butyral, polyvinyl alcohol, acrylic polymers such as polymethylmethacrylate, polystyrene, styrene polymers such as ABS resin, polyester polymers such as polycarbonate, and poly Examples thereof include polyether polymers such as ethylene oxide, polyolefin polymers such as polyethylene and polypropylene, ethyl cellulose, polyvinyl acetate, polyvinyl chloride, melamine resins, epoxy resins and polyurethane resins. Into the above thermochromic microcapsules or thermochromic matrix fine particles, an ultraviolet absorber, an ultraviolet stabilizer, an antioxidant and the like can be added as required.

Photochromic Matrix Fine Particles A matrix fine particle in which the above organic photochromic substance is dispersed in a synthetic resin as a photochromic material is
For example, the thermochromic matrix fine particles can be manufactured by the same method as described above using the same synthetic resin.

Photochromic Microcapsules For encapsulating a matrix in which a photochromic material is dispersed in a synthetic resin or a mixture in which a photochromic material is dissolved or dispersed in a medium in microcapsules, for example, the thermochromic material is replaced with the matrix or mixture. Otherwise, it can be carried out in the same manner as the method described above for the thermochromic microcapsules. The medium is preferably a high-boiling type solvent, a plasticizer, a synthetic resin, a hindered amine compound, a hindered phenol compound, or the like, and among them, in improving the light resistance of the organic photochromic compound, a hindered amine It is particularly preferable to use the base compound or the hindered amine compound in combination with another medium.

Examples of the hindered phenol compounds include 2,6-di-t-butylphenol and 2,6-di-
Examples thereof include t-butyl-p-cresol, 2,5-di-t-butylhydroquinone, and 2,2′-methylene-bis (4-ethyl-6-t-butylphenol). Further, as the hindered amine-based compound,
For example, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, dimethyl succinate, 1- (2-
Hydroxyethyl) -4-hydroxy-2,2,6,6
-Tetramethylpiperidine degenerate compound, poly [{6-
(1,1,3,3-tetramethylbutyl) amino-1,
3,5-triazine-2,4-diyl} {2,2,6
6-Tetramethyl-4-piperidyl) imino} hexamethylene (2,2,6,6-tetramethyl-4-piperidyl) imino], 2- (3,5-di-t-butyl-4-hydroxybenzyl) Bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-n-butylmalonate, 1- [2- {3- (3,5-di-t-butyl-4)
-Hydroxyphenyl) propionyloxy} ethyl]
-4- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} -2,2,6,6-
Tetramethylpiperidine, 8-benzyl-7,7,9,
9-tetramethyl-3-octyl-1,3,8-triazaspiro [4.5] undencan-2,4-dione, tetrakis (2,2,6,6-tetramethyl-4-piperidine) butane carbonate, Mark LA57, Mark LA62,
Mark LA67 (trade name; manufactured by Adeka Argast) and the like can be mentioned.

Examples of the above high boiling point type solvents include alcohols, ketones, esters, ethers, aromatic (halogenated) hydrocarbons, aliphatic (halogenated) hydrocarbons, cellosolves and formamide. Among these compounds, sulfoxy compounds and the like, those having a high boiling point or a slow evaporation rate can be mentioned. As the plasticizer, all plasticizers including phthalate type, adipate type, phosphate type, polyester type and polyether type can be used. Examples of the synthetic resin include the same as those described above for the thermochromic matrix fine particles.

Dyeing process example Fiber product having one or more kinds of synthetic fibers selected from the group consisting of polyester fibers, polyamide fibers, acrylic fibers, acrylic fibers and polyurethane fibers, and the dyeing method of the present invention Dyeing with can be performed, for example, as follows. First, in a dyeing machine such as a Smith drum, paddle, jet, or jaguar, add 5 to 50 times the amount of water (bath ratio 1: 5) to the textile product.
˜1: 50), preferably 10 to 30 times by weight of water (bath ratio 1:10 to 1:30) is added to the water, and 0.1 to 20% by weight based on the untreated fiber product, Preferably about 0.3-5% by weight of cationic polymer is added.

Next, the fiber product is immersed in the thus obtained aqueous solution, and the temperature is kept at room temperature to 80 ° C. for 5 to 5 ° C.
When kept for about 30 minutes, the cellulose fiber portion of the fiber product is effectively cationized. The textile is then rinsed thoroughly to remove excess cationic polymer and other additives and then dehydrated. Then, in a dyeing machine containing the treated textile, 1: 5 to the untreated textile
Water is added in an amount of about 1:50, preferably about 1:10 to 1:30, and the reversible color-changing fine particles as described above are added in an amount of 0.1 to 50% by weight, preferably 3 ~
Add about 15% by weight and disperse. The reversible color-changing fine particles can be added as a dispersion containing the reversible color-changing fine particles.

When the dispersion thus obtained is treated at room temperature to about 90 ° C. for about 5 to 30 minutes, the cationized fiber products are completely exhausted of the reversible color-changing fine particles. The treatment temperature is 10 to 5 for the reversible color-changing fine particles.
When used at a high concentration of 0% by weight, the temperature is preferably about 60 to 90 ° C. By this treatment, the reversible color-change particles are bonded to the fiber product by chemical ionic bond and physical adsorption. Then, by dehydrating and drying this, the reversible color-change particles are firmly fixed to the fiber product. 80-180 ° C after drying for stronger adhesion
It is preferable to perform heat treatment for about 0.5 to 10 minutes.
The fiber product thus obtained is dyed at a high concentration with the reversible color-changing fine particles, the feel of the fiber product is not impaired, the texture is soft, and the fastness to rubbing and washing is excellent.

Preferred Dyeing Mode 1 Another preferred embodiment of the dyeing method of the present invention is one or more synthetic fibers selected from the group consisting of polyester fibers, polyamide fibers, acrylic fibers, acrylic fibers and polyurethane fibers. A step of treating a fiber product having a cation with a cationic polymer, and the fiber product thus treated is provided with a reversible color-changing fine particle comprising a polymer compound containing a thermo- or photo-reversible color-changing material. The method includes a step of immersing the fiber product in a dispersion liquid containing the dye, and a step of immersing the fiber product in water containing an amount of a binder that does not impair the feel and feel of the dyed product, and further treating the fiber product. The amount of the binder is generally about 0.1 to 10% by weight based on the solid content of the binder, preferably 1 to 10% by weight.
It is 5% by weight.

As the binder that can be used, acrylic ester resin, polyurethane resin, polyester resin, styrene butadiene latex, vinyl acetate resin,
Examples thereof include vinylidene chloride resin, vinyl acetate / acrylic acid ester copolymer resin, acrylic acid ester / vinylidene chloride copolymer resin, styrene / acrylic acid ester copolymer resin, or derivatives or mixtures thereof. In the present invention, among these, acrylic ester resin, copolymer resin of acrylic ester and other vinyl monomer, vinyl acetate resin, and polyurethane resin are particularly preferable. To dye textiles according to this aspect,
For example, it can be performed as follows.

After treating a fiber product having one or more kinds of synthetic fibers selected from the group consisting of polyester fibers, polyamide fibers, acrylic fibers, acrylic fibers and polyurethane fibers with a cationic polymer, The reversible color-changing fine particles are exhausted to the fiber product by immersing in the dispersion liquid containing the reversible color-changing fine particles and treated, and then dehydrated. Next, the dyeing bath containing the textile product is again poured with water in a bath ratio of about 1: 5 to 1:50, preferably about 1:10 to 1:30, and the binder solid content is 0 to the textile product. 1 to 10% by weight,
Preferably, 1 to 5% by weight of a binder is added, treated at room temperature to 90 ° C. for 5 to 30 minutes, and then dehydrated and dried. The textile product thus obtained has further improved fastness to rubbing and washing as in the case described above.

Preferred Dyeing Mode 2 Yet another preferred embodiment of the dyeing method of the present invention is one or two or more synthetic materials selected from the group consisting of polyester fibers, polyamide fibers, acrylic fibers, acrylic fibers and polyurethane fibers. The first step of treating a fiber product comprising fibers with a cationic polymer and a binder in an amount that does not impair the feel and feel of the dyed product, and the fiber product thus treated in a polymer compound. A second step of treating by immersing in a dispersion liquid containing reversible color-changing fine particles containing a heat- or photo-reversible color-changing material. As the binder, the same ones as described above can be used. The amount thereof is generally about 0.1 to 10% by weight based on the fiber product in the binder solid content, preferably 1 to
It is 5% by weight.

In the first step, a fiber product having one or more kinds of synthetic fibers selected from the group consisting of polyester fibers, polyamide fibers, acrylic fibers, acrylic fibers and polyurethane fibers, It is also possible to substitute the step of treating with a cationic binder in an amount that does not impair the feel and feel of the dyed product. Further, a cationic polymer and a cationic binder can be used together.

As the cationic binder, Boncoat SFC series (trade name; vinyl acetate or acrylic ester emulsion: Dainippon Ink and Chemicals, Inc.), Iodosol AF series (trade name; acrylic ester emulsion: Kanebo) NSC), CGC
Series (trade name; acrylic ester emulsion: manufactured by Sumitomo Chemical Co., Ltd.), cationic emulsion disclosed in JP-A-62-187702, JP-A-62-13
Cationic copolymers disclosed in Japanese Patent No. 1003, JP-A-62-62
Examples thereof include the cationic polymer disclosed in JP-A-201914 and the cationic latex disclosed in JP-A-62-263211.

In the above preferred dyeing modes 1 and 2, the binder absorbs the fiber product to the same extent as contained in the liquid, that is, the binder solid content is about 0.1 to 10% by weight of the fiber product. It is exhausted and dehydrated and dried to firmly adhere to the fiber product. As a result, the fastness to rubbing and the fastness to washing are further improved. In this case, if the binder solid content is less than 0.1% by weight, the effect tends to be insufficient, and if it exceeds 10% by weight, the feel and feel of the fiber are often impaired. In the present invention, when two or more kinds of thermoreversible discolorable fine particles having different discoloration temperatures are used, the color of the dyed product may be changed due to temperature change from yellow ← → orange ← → black,
As described above, the color can be changed in two or more steps.

When the above three-component mixture is used as the thermochromic material in the thermoreversible discolorable fine particles,
When a solvent of them is a specific ester, a clear hysteresis can be imparted to the color change. For example, the color development temperature due to the temperature decrease can be lower than the decolorization temperature due to the temperature increase by several degrees centigrade or more. Therefore, it is possible that evenly dyed parts of the same dyed product of the present invention at the same temperature have different colors due to the difference in temperature history. Further, when the dyeing method of the present invention is used with a mixture of thermoreversible color-changing fine particles and photoreversible color-changing fine particles, reversible multi-stage color change responsive to both temperature change and light irradiation is realized. can do.

Furthermore, in the above-described dyeing method of the present invention, a dispersion liquid containing reversible color-changing fine particles is also added with a daylight fluorescent pigment or other inorganic or organic pigments, and at the same time as the reversible color-changing fine particles. It is also possible to exhaust these pigments into textile products. Accordingly, it is possible to realize a reversible color change due to color mixture with the color due to the pigment depending on the temperature change and the presence or absence of light irradiation. Furthermore, the textile product may be colored in advance, and the dyeing method of the present invention described above may be applied thereto. That is, if the textile product is directly dyed with a direct dye or an acid dye in advance, or a pigment such as an organic pigment, an inorganic pigment or a daylight pigment is resin-padded and ground-dyed, and then each of the above dyeing methods is applied, the temperature change also occurs. Depending on the presence or absence of light irradiation, reversible color change due to color mixing with the color due to those dyes or pigments can be realized.

Production Example of Reversible Color-changing Fine Particles Next, a production example of reversible color-changing fine particles will be described. In the following description, "part by weight" is abbreviated as "part".

Production Example 1 ( Production of thermochromic microcapsules containing a three-component mixture) NC-R-1 (pink) (trade name; acid-developing substance: Hodogaya Chemical Co., Ltd.) 1 part Bisphenol A 2 parts bis Benzotriazole-5-methane 2 parts Lauryl palmitate 10 parts Cecil alcohol 10 parts Tinuvin 326 (trade name; UV absorber: manufactured by Ciba Geigy) 2 parts Epicoat 828 (trade name; epoxy resin: manufactured by Yuka Shell Epoxy Co., Ltd.) 6 Department

The above formulation was heated to obtain a uniform hot melt. Next, the melt was put into 200 parts of a 5% gelatin aqueous solution at 60 ° C., and dispersed with stirring in the form of oil droplets having a diameter of 5 μm. Next, a curing agent for epoxy resin (Epicure U
(Product name): Yuka Shell Epoxy Co., Ltd.)
Then, stirring was continued, the temperature was raised to 90 ° C., and the reaction was performed for 2 hours. Then, after cooling, the microcapsules thus produced are washed with water and filtered to remove 90% by weight of gelatin contained therein.
About 35 parts of thermochromic microcapsules and about 1
100 parts of a dispersion containing 1 part of gelatin was obtained.

Production Example 2 ( Production of Photochromic Microcapsules) NC-R-1, bisphenol A, bisbenzotriazole-5-methane, lauryl palmitate of Production Example 1 were prepared.
Cecil alcohol, Tinuvin 326, 1 part of 1,3,3-trimethylspiro [indoline-2,3 '-[3H] naphtho (2,1-b) (1,4) oxazine] (organic photochromic compound) and bis 100 parts of a dispersion liquid containing 35% by weight of photochromic microcapsules was obtained in the same manner as in Production Example 1 except that 26 parts of (2,2,6,6-tetramethyl-4-piperidyl) sebacate was used.

Production Example 3 ( Production of thermochromic microcapsules) NC-1 of Production Example 1, 2 parts of bisphenol A, 2 parts of bisbenzotriazole-5-methane and 10 parts of cesyl alcohol were added to Y-1 (leuco dye). (Yellow: manufactured by Yamamoto Kasei Co., Ltd.) 1 part, bisphenol A 4 parts, and myristyl alcohol 10 parts were replaced with the same procedure as in Production Example 1 to obtain 100 parts of a dispersion liquid containing 35 wt% of thermochromic microcapsules.

Production Example 4 ( Production of Photochromic Microcapsules) NC-R-1, bisphenol A, bisbenzotriazole-5-methane, lauryl palmitate of Production Example 1 were prepared.
Cecil alcohol, Tinuvin 326, 3,3-diphenyl-3H-naphtho- (2,1-b) pyran 1 part, Sanol LS-770 (trade name; hindered amine compound: Sankyosha) 2 parts, 30 % Polystyrene resin (toluene solution), and a dispersion containing 35% by weight of photochromic microcapsules in the same manner as in Production Example 1 except that the reaction time at 90 ° C. was extended to 4 hours to completely evaporate toluene. 100 parts of liquid was obtained.

Production Example 5 ( Production of Photochromic Matrix Fine Particles) 6'-Hyperidino-1,3,3-trimethylspiro [indoline-2,3 '-[3H] naphtho (21-b) (1,4) oxazine] 1 part SANOL LS-770 2 parts DIANAL SE-5377 (trade name; methylmethacrylate resin 40% by weight, xylene 60% by weight; Mitsubishi Plastics Co., Ltd.) 60 parts xylene 20 parts Separately obtained by heat-melting the above composition. While stirring the prepared 3% aqueous solution of styrene / maleic acid copolymer resin,
It was dripped into this aqueous solution. Then, when the mixture was stirred at 80 to 90 ° C. for about 2 hours while adjusting the stirring speed, xylene was almost completely evaporated and a suspension of a uniform dispersion having an average particle diameter of about 5 μm was obtained. The suspension was washed with water, filtered, and dried to obtain about 38 parts of photochromic matrix fine particles containing about 1 part of styrene / maleic anhydride.

[0055]

According to the dyeing method of the present invention, it has one or more kinds of synthetic fibers selected from the group consisting of polyester fibers, polyamide fibers, acrylic fibers, acrylic fibers and polyurethane fibers. A textile product can be dyed with a reversible color-changing fine particle containing a thermo- or photo-reversible color-changing material in a polymer compound, to a high density which has hitherto been impossible. Therefore, it is possible to make the color of the material at the time of coloring due to the change of the temperature or the amount of light incomparably rich, without impairing the properties of the fiber product such as feel and feel. Also, when a binder is used together to improve the fastness to rubbing and washing fastness of the dyed product, the amount thereof does not impair the feeling and feel, that is, an extremely small amount as compared with the conventional one.

[0056]

EXAMPLES Examples of the present invention will be described below.
The present invention is not limited to these. Example 1 In a Smith Drum dyeing machine, in a water ratio of 1:20 for a polyester shirt (broad), 1% by weight of this shirt of a cationic polymer (acrylamide and 2-methacryloxyethyltrimethyl) was used. The shirt was immersed in a liquid added with a polymer having a molecular weight of about 30,000 in which ammonium chloride was polymerized at a molar ratio of 3: 2, and treated at 60 ° C. for 10 minutes while stirring. It was then rinsed well with water to remove excess cationic polymer and other additives and dehydrated. Next, to this dyeing machine, 25% by weight of the aqueous dispersion containing 35% by weight of the thermochromic microcapsules obtained in Production Example 1 was applied to the shirt, and water having a bath ratio of 1:20 was applied to the shirt. Addition and stirring at 70 ℃ 10
Processed for minutes.

After this treatment, it was rinsed well with water and dehydrated,
Tumble drying was performed at 30 ° C. for 2 minutes. When the shirt thus obtained is worn, heat spreads due to body temperature and subtle changes in air temperature cause the temperature of the thermochromic microcapsules to rise, causing the entire surface of the T-shirt to become white, and the temperature of the thermochromic microcapsules to cause darkening. It became pink, or it was a marbled mixture of white and pink. Further, this shirt had a smooth feel, was close to the feel of the original polyester fiber cloth, and had good feeling, abrasion resistance and washing resistance.

[0058] except for changing the dispersion containing the thermochromic microcapsules obtained in Example 2 Production Example 1 to dispersion containing the photochromic microcapsules of Preparation 2 was treated polyester shirt in the same manner as in Example 1. This shirt is white in a room where it is not exposed to direct sunlight, but it has a dark blue color near a window where it is exposed to direct sunlight or outdoors. This change can be reversibly repeated many times, and the quality of the shirt was as good as in Example 1.

Example 3 Example 3 except that the dispersion containing the thermochromic microcapsules obtained in Production Example 1 was replaced with the photochromic matrix fine particles obtained in Production Example 5 (10% by weight based on the shirt of Example 1). A polyester shirt was treated as in 1. This shirt is white in a room where it is not exposed to direct sunlight, but it has a dark purple color near the window where it is exposed to direct sunlight and outdoors. This change could be reversibly repeated many times, and the quality of this shirt was as good as in Example 1.

Example 4 When the polyester shirt of Example 1 was replaced with a nylon sports shirt (knit) and treated in the same manner as in Example 1, the same color change as in Example 1 was obtained and the quality was also the same. It was

Example 5 When the polyester shirt of Example 1 was replaced with a girl's polyacrylic blouse (knit) and treated in the same manner as in Example 1, the same color change as in Example 1 and similar quality were obtained. Met.

Example 6 In Example 1, when the polyester shirt was cationized, Teisan Resin NFA-370N (trade name; acrylic resin emulsion [solid content: 50% by weight]: Teikoku Chemical Industry Co., Ltd.) 5% by weight to the shirt
(Solid content: about 2.5% by weight) A shirt was treated in the same manner as in Example 1 except that it was added and treated. The obtained shirt showed the same color change as that of Example 1, the feel and the feel were almost comparable to those of Example 1, and the abrasion resistance and the washing resistance were further better than those of Example 1. Was excellent.
Further, when this polyester shirt was treated in the same manner in place of a nylon sports shirt (knit) or a girl's polyacrylic blouse (knit), both showed the same color change as the polyester shirt, and the quality was also the same. It was similar.

Example 7 The steps up to exhaustion of thermochromic microcapsules in a polyester shirt (broad 150 parts), rinsing with water, and dehydration were carried out in the same manner as in Example 1. Next, in the dyeing machine, water having a bath ratio of 1:20 to this shirt and 6% by weight of Boncoat ES-141 (trade name; acrylic resin emulsion [solid content: 45% by weight]: Dainippon (Manufactured by Ink Kagaku Kogyo Co., Ltd.) (solid content: 2.7% by weight), charged at 70 ° C. for 10 minutes, rinsed well with water, dehydrated, and dried at 130 ° C. for 2 minutes in a cylinder for drying. It was The obtained shirt showed the same color change as in Example 1, and the quality was good as in Example 6. When this polyester shirt was treated in the same manner in place of nylon sports pants (knit) or polyacrylic polo shirt (knit), both showed the same color change as the polyester shirt and the quality was also the same. It was

Example 8 In a Smith Drum dyeing machine, water having a bath ratio of 1:20 with respect to a polyester cutter shirt (Pola) and 9% by weight of CGS102 (trade name; cationic acrylic) with respect to this shirt Resin shirt [solid content: 40% by weight]: manufactured by Sumitomo Chemical Co., Ltd. (solid content: 3.6% by weight) The shirt is dipped in a liquid and heated to 60 with stirring.
It was treated at 0 ° C. for 10 minutes. Then it was rinsed well with water and dehydrated. Next, to this dyeing machine, 25% by weight of the aqueous dispersion containing 35% by weight of the photochromic microcapsules obtained in Production Example 4 was added to the shirt, water having a bath ratio of 1:20 to the shirt, and 5 Wt% Glow Pink MIB (trade name; aqueous dispersion containing about 50 wt% of pink daylight fluorescent pigment:
Matsui Pigment Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 70 ° C. for 10
Processed for minutes.

After this treatment, it was rinsed well with water and dehydrated,
Tumble drying was performed at 30 ° C. for 2 minutes. The shirt thus obtained was pink in a room where it was not exposed to direct sunlight, but it became a deep orange color due to the color mixture of the photochromic microcapsules when it was exposed to direct sunlight or outdoors. This change could then be reversibly repeated many times and the quality of this shirt was as good as in Example 6. Further, this cutter shirt was treated in the same manner in place of a nylon taffeta sports shirt or an acrylic knit polo shirt, and both showed the same color change as the polyester cutter shirt,
The quality was similar.

Example 9 A polyester cutter shirt, a nylon sports shirt and an acrylic polo shirt were each treated as follows. Water in a liquor ratio of 1:20 for the shirt and 1% by weight of Charol DC-303P for the shirt in a Smith Drum dyeing machine (compound of formula 1 above)
And 6.4% by weight of Boncoat SFC-7-50 (trade name; cationic vinyl acetate resin emulsion: manufactured by Sumitomo Chemical Co., Ltd.), the shirt is immersed in the liquid, and the temperature is raised under stirring to 60 ° C. For 10 minutes. Then it was rinsed well with water and dehydrated. Next, in this dyeing machine, 20% by weight (solid content: 7% by weight) of the aqueous dispersion containing 35% by weight of the thermochromic microcapsules obtained in Production Example 3 was used for the shirt, and 1:20 for the shirt. Water having a bath ratio of 2 and 2% by weight of PG Blue MI-IB (trade name; aqueous dispersion of blue organic pigment: manufactured by Matsui Dye Chemical Industry Co., Ltd.) are added, and the shirt is soaked and stirred 70 It was treated at 0 ° C. for 10 minutes.

After this treatment, it was rinsed well with water and dehydrated to
Tumble drying was performed at 30 ° C. for 2 minutes. These shirts were blue at about 25 ° C. or higher, but at about 20 ° C. or lower, they changed to dark green due to the color mixture of the thermochromic microcapsules. This change could be reversibly repeated any number of times and the quality of these shirts was as good as in Example 8.

Comparative Examples 1 to 4 Example 1, except that no cationic polymer was used.
The treatment was performed in the same manner as in Example 2, Example 6 and Example 7. Each of the obtained products had a coloring density of about 5% as compared with the fabric of the example, and no commercial value was recognized.

Comparative Examples 5-8 Example 1, Example 2, Example 6 and Example 7 were repeated except that the cationic polymer was replaced with Coatamine 24P (trade name; cationic surfactant [lauryl trimethyl ammonium chloride]). Each of the obtained products had a color density of 2% as compared with the cloth of the example.
There was only about 0%, and the commercial value was not recognized.

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Claims (3)

[Claims] 1. A fiber product comprising one or more synthetic fibers selected from the group consisting of polyester fibers, polyamide fibers, acrylic fibers, acrylic fibers and polyurethane fibers, containing a cationic polymer. Immersion in water and treatment, and soaking the fiber product in an aqueous dispersion containing reversible color-changing fine particles containing a heat- or photo-reversible color-changing material in a polymer compound And a treatment step. 2. A fiber product containing one or more kinds of synthetic fibers selected from the group consisting of polyester fibers, polyamide fibers, acrylic fibers, acrylic fibers and polyurethane fibers in water containing a cationic polymer. And the fiber product thus treated is immersed in an aqueous dispersion containing reversible color-changing fine particles containing a polymer or a reversible color-changing material having heat or light. And a step of further treating by dipping the textile product in water containing an amount of a binder that does not impair the feel and feel of the dyed article. 3. A fiber product comprising one or more synthetic fibers selected from the group consisting of polyester fibers, polyamide fibers, acrylic fibers, acrylic fibers and polyurethane fibers, a cationic polymer and a dye. The process of immersing in a water containing an amount of a binder that does not impair the texture and feel of the product, and treating the fiber product so treated with a polymer compound containing a thermo- or photo-reversible discolorable material. And a step of immersing in a dispersion liquid containing the reversible color-changing fine particles.