Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/004—Dyeing with phototropic dyes; Obtaining camouflage effects
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/0096—Multicolour dyeing

Definitions

• the present invention relates to a method of dyeing a cellulose fiber textile product with reversibly color changeable fine particles which involve thermochromic or photochromic material and a dyed product.
• thermochromic material Three-component mixture of acid developing substance, acidic substance and solvent; two-component mixture of acid developing substance and acidic substance; cholesteric liquid crystals and metal complex salt crystals have been known as a kind of thermochromic material which shows reversible color changes as the temperature changes.
• the three-component mixtures offer diverse colors and high coloring densities and change dramatically between colored and colorless states.
• the two-component mixtures offer higher coloring densities in comparison with the three-component mixtures. But the two-component mixtures change their colors relatively slowly and few of the mixtures show color changes in ordinary thermal circumstances.
• the cholesteric liquid crystals are capable of changing their colors to red, yellow, green, blue, violet and so on sensitively in arbitrary range of temperature. But they need black ground and offer lower coloring densities in comparison with the three-component mixtures. Excellent color changing function of these three-component mixtures, two-component mixtures and cholesteric liquid crystals is obtained only in cases where their components form a system at a strictly constant ratio. In order to keep their function, they are used in fine particle form which contains them in synthetic resin matrix or microcapsule form which contains them.
• organic photochromic compounds are used, for example, as dispersion in appropriate medium or in the form of microcapsule containing the dispersion.
• the surface of the textile product loses its fiber texture, its appearance worsens, and its color fastness to rubbing and color fastness to washing are insufficient. For these reasons, even when the entire surface of the cloth is colored, no commercially valuable product will be obtained. Therefore, it is the conventional practice to make patterns such as one-point patterns on a very narrow area on the cloth.
• thermochromic or photochromic material in high polymer compound to high densities which could not be obtained by any conventional method and which thus provides incomparably distinct colors upon their color development with no influence on the texture, appearance or other textile product properties.
• the dyed product of the present invention is cellulose fiber textile product pretreated with cationic compound and dyed with reversibly color changeable fine particles which involve thermochromic or photochromic material in high polymer compound.
• Examples of the cellulose fiber for the present invention include natural fibers such as cotton and hemp and regenerated fibers such as rayon and cupra.
• Examples of the cellulose fiber textile product described above include cellulose fiber yarns, blended yarns of cellulose fiber with polyester fiber, acrylic fiber, wool, etc., or fabrics or knits comprising cellulose fiber yarn and/or the blended yarn described above, cellulose-containing nonwoven fabrics, and sewn products such as apparels based on these fabrics, knits or nonwoven fabrics.
• Examples of sewn products are T-shirt, trainer, jumper, pants, jeans, socks, bag, cap, hat and so on.
• the textile product for the present invention may be colored in advance.
• Examples of the cationic compound described above include quaternary ammonium salt type compounds, pyridinium salt type compounds, dicyandiamide type compounds, polyamine type compounds and polycation type compounds.
• cationic compounds are as follows.
• quaternary ammonium salt type compounds include quaternary ammonium salt type cationic surfactants such as trimethyloctadecylammonium chloride, trimethylhexadecylammonium chloride, trimethyllaurylammonium chloride, dimethyllaurylammonium chloride, laurylmethylammonium chloride, stearyltrimethylammonium chloride, lauryldimethylbenzylammonium chloride, lauryltrimethylammonium chloride, alkylbenzyldimethylammonium chloride, stearylbenzyldimethylammonium chloride, and alkyltrimethylammonium chloride;
• quaternary ammonium salt type cationic surfactants such as trimethyloctadecylammonium chloride, trimethylhexadecylammonium chloride, trimethyllaurylammonium chloride, dimethyllaurylammonium chloride, laurylmethylammonium chloride,
• Examples of the dicyandiamide type compounds include formalin condensation product of dicyanamide.
• polyamine type examples include guanidine derivative condensation product of polyalkylenepolyamine; polyethyleneimines and polyamidepolyamines.
• polycation type examples include poly-4-vinylpyridine hydrochloride; tertiary aminepolymers such as the polyacrylonitrile polymers disclosed in Unexamined Japanese Patent Publication No. 64186/1979; dimethylamine-epichlorohydrin polycondensation product disclosed in Examined Japanese Patent Publication No. 243/1967; 2-methacryloxypropyltrimethylammonium chloride polymer disclosed in Unexamined Japanese Patent Publication No. 112480/1982; dimethyldiallylammonium chloride polymers disclosed in Unexamined Japanese Patent Publication No. 76177/1980; polyepichlorohydrin-trimethylamine reaction product disclosed in Unexamined Japanese Patent Publication No.
• polyamine type compounds polyamine type compounds, dicyandiamide type compounds and quaternary ammonium salt type polymers and copolymers of quaternary ammonium salts and other vinyl monomers of polycation type are particularly effective in the present invention.
• thermochromic materials available for the present invention include three-component mixture of acid developing substance, acidic substance and solvent; two-component mixture of acid developing substance and acidic substance; cholesteric liquid crystal and metal complex salt.
• Examples of the acid developing substance of three-component mixture and two-component mixture include triphenylmethanephthalide compounds, phthalide compounds, phthalan compounds, Acyl Leucomethylene Blue compounds, fluoran compounds, triphenylmethane compounds, diphenylmethane compounds and spiropyran compounds.
• More specific examples thereof include 3,6-dimethoxyfluoran, 3,6- dibutoxyfluoran, 3-diethylamino-6,8-dimethylfluoran, 3-chloro-6-phenylaminofluoran, 3-diethylamino-6-methyl-7-chlorofluoran, 3-diethyl-7,8-benzofluoran, 3,3',3"-tris(p-dimethylaminophenyl)phthalide, 3,3'-bis(p-dimethylaminophenyl)phthalide, 3-diethylamino-7-phenylaminofluoran, 3,3-bis(p-diethylaminophenyl)-6-dimethylamino phthalide, 3-4(-diethyaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, 3-(4-diethylamino-2-methyl)phenyl-3-(1,2-dimethylindol-3
• Examples of the acidic substance of three-component mixture and two-component mixture include 1,2,3-benzotriazoles, phenols, thiourea derivatives and oxy aromatic carboxylic acids. More specific examples thereof include 5-butylbenzotriazole, bisbenzotriazole-5-methane, phenol, nonylphenol, bisphenol A, bisphenol F, 2,2'-bisphenol, -naphthol, 1,5-dihydroxynaphthalene, alkyl p-hydroxybenzoate and phenol resin oligomers.
• Examples of the solvent of three-component mixture and two-component mixture include alcohols, alcohol-acrylonitrile adducts, azomethines and esters. More specific examples thereof include decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, lauryl alcohol-acrylonitrile adducts, myristyl alcohol-acrylonitrile adducts, stearyl alcohol-acrylonitrile adducts, benzylidene-p-toluidine, benzylidene-butylamine, octyl caprylate, decyl caprylate, myristyl caprylate, decyl laurate, lauryl laurate, myristyl laurate, decyl myristate, lauryl myristate, cetyl myristate, lauryl palmitate, cetyl palmitate, stearyl palmitate, cetyl
• cholesteric liquid crystals examples include a composition of two or more kinds selected from cholesterol acetate, cholesterol benzoate, cholesterol nonanate, cholesterol propionate, cholesterol oleyl carbonate and cholesterol chloride.
• metal complex salt examples include complex compounds of silver, mercury, iodine or copper and thiodicarbamic acid derivative complexes.
• Examples of the photochromic material usable for the present invention include azobenzene compounds, thioindigo compounds, dithizone metal complexes, spiropyran compounds, spirooxazine compounds, fulgide compounds, dihydroprene compounds, spirothiopyran compounds, 1,4-2H-oxazine, triphenylmethane compounds, viologen compounds, naphthopyran compounds, with preference given to spiropyran compounds, spirooxazine compounds, fulgide compounds and naphthopyran compounds for the dyeing method of the present invention.
• photochromic material examples include 1,3,3-trimethylspiro[indoline-2,3'-(3H)naphtho(2,1-b)(1,4)-oxazine],
• thermochromic or photochromic material in high polymer compound.
• the reversibly color changeable fine particles include particles containing thermochromic material in high polymer microcapsules, particles containing dispersed thermochromic material in matrix of synthetic resin, particles containing dispersed organic photochromic substance in matrix of synthetic resin, particles containing dispersed organic photochromic substance in matrix of synthetic resin encapsulated in high polymer microcapsules and particles containing dissolved or dispersed organic photochromic substance in medium encapsulated in high polymer microcapsules. It is preferable that the diameters of the reversibly color changeable fine particles do not exceed 50 am. If the diameters exceed 50 am, exhaustion of the particles into a cellulose fiber textile product often goes badly.
• thermochromic material can be microcapsuled by, for example, the following method.
• Microcapsules of 1 - 50 /1.m in diameter containing thermochromic material which are dispersed in aqueous dispersion can be obtained by carring out a known encapsulation method such as the interfacial polymerization method, the insight polymerization method, the coacervation method, atmospheric suspension method or the interfacial precipitation method in water on thermochromic material selected from the above three-component mixture, the above two-component mixture and the above cholesteric liquid crystals and high polymer compound as coat former with surfactant, a protective colloid, a pH regulator, an electrolyte and other substances as needed.
• a known encapsulation method such as the interfacial polymerization method, the insight polymerization method, the coacervation method, atmospheric suspension method or the interfacial precipitation method in water on thermochromic material selected from the above three-component mixture, the above two-component mixture and the above cholesteric liquid crystals and high polymer compound as coat former with surfactant,
• the layers of the microcapsules can be plural by carring out one or more kind of these capsulation method two or more times repeatedly.
• preferable coat formers include polyisocyanate and polyamine for forming polyurea coat, polybasic acid chloride and polyamine for forming polyamide coat, polyisocyanate and polyhydroxy compound for forming polyurethane coat, epoxy compound and polyamine for forming epoxy resin coat, melamine-formalin prepolymer for forming melamine resin coat, urea-formalin prepolymer for forming urea resin coat, ethyl cellulose, polystyrene and polyvinyl acetate, and anionic high polymer compounds and amphoteric high polymer compounds described later.
• the coat for the microcapsule described above be thermosetting because of excellent heat resistance.
• preferably usable surfactants and protective colloids examples include anionid surfactants, amphoteric surfactants, anionic high polymer compounds, amphoteric high polymer compounds.
• nonionic surfactants can be used with these.
• microcapsules dispersed in aqueous dispersion which is obtained as mentioned above. From this aqueous dispersion, surfactant and protective colloid may be removed to such an extent that it is possible to maintain the dispersion of the microcapsules.
• Powdery microcapsules obtained by dehydration and drying are also usable. When the powdery microcapsules are used, they are dispersed in liquid with surfactant and protective colloid as needed. If the microcapsules have high dispersibility, surfactant and protective colloid are not necessary. Microcapsule whose coat is anionic high polymer compound or amphoteric high polymer compound often have enough dispersibility.
• anionic surfactant examples include alkyl sulfates, alkyl benzenesulfonates, alkyl naphthalenesulfonates, alkyl sulfosuccinates, alkyl diphenyl ether disulfonates, alkyl phosphates, polyoxyethylene alkyl sulfates, polyoxyethylene alkylallyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene polystyrylphenyl ether sulfates and polyoxyethylene alkyl phosphates.
• anionic polymer compound described above examples include polyacrylic acid, poly- ⁇ - hydroxyacrylic acid, methacrylic acid, copolymers of these substances with other vinyl polymers, ethylene/maleic anhydride copolymer, butylene/maleic anhydride copolymer, vinyl ether/maleic anhydride copolymer, anion-modified polyvinyl alcohol, gum arabic, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and starch derivatives.
• amphoteric polymer compound described above examples include gelatin and casein.
• nonionic surfactant examples include polyoxyethylene alkyl ether, polyox- yethylenealkylallyl ether and other polyoxyethylene derivatives, polyoxyethylene-polyoxypropylene block copolymer, aliphatic esters of sorbitan, fatty acid esters of polyoxyethylenesorbitol and fatty acid esters of glycerol.
• thermochromic matrix Fine particle of thermochromic matrix
• thermochromic material in matrix of synthetic resin Particles containing dispersed three-component mixture, two-component mixture or cholesteric liquid crystals as thermochromic material in matrix of synthetic resin can be prepared by, for example, the following method.
• Thermochromic material selected from the above and synthetic resin are first molten under heating conditions. The mixture is stirred until the thermochromic material is dispersed in the synthetic resin. The dispersion mixture is added to water containing surfactant and/or protective colloid with stirring the water to yield particles containing dispersed thermocromic material in matrix of synthetic resin.
• Thermochromic material selected from the above and synthetic resin are first molten under heating conditions. The mixture is stirred until the thermochromic material is dispersed in the synthetic resin. The dispersion mixture is frozen and pulverized to give particles containing dispersed thermocromic material in matrix of synthetic resin.
• Examples of the synthetic resin described above include acrylic polymers such as polyvinyl butyral, polyvinyl alcohol and polymethylmethacrylate; styrene polymers such as polystyrene and ABS resin; polyester polymers such as polycarbonate; polyether polymers such as polyethylene oxide; polyolefin polymers such as polyethylene and polypropylene, ethyl cellulose, polyvinyl acetate, polyvinyl chloride, melamine resin, epoxy resin and polyurethane resin.
• thermochromic microcapsules or fine particles of thermochromic matrix as needed.
• Particles containing dispersed organic photochromic substance as photochromic material in matrix of synthetic resin can be prepared, for example, in a similar manner as the above method of preparing fine particle of thermochromic matrix with use of similar synthetic resin.
• Particles containing dispersed organic photochromic substance in matrix of synthetic resin encapsulated in high polymer microcapsules or particles containing solved or dispersed organic photochromic substance in medium encapsulated in high polymer microcapsules can be prepared, for example, in a similar manner as microcapsulation of thermochromic material except that organic photochromic substance dispersed in matrix of synthetic resin or organic photochromic substance solved or dispersed in medium is used in place of thermochromic material.
• the medium is preferably high boiling solvent, plasticizer, synthetic resin, hindered amine compound or hindered phenol compound, with further preference given to hindered amine compound or combination of hindered amine compound and another medium from the view point of improvement in the color fastness to light of the organic photochromic compound.
• hindered phenol compound examples include 2,6-di-t-butylphenol, 2,4,6-t-butylphenol, 2,6-di-t-butyl-p-cresol, 4-hydroxymethyl-2,6-di-t-butylphenol, 2,5-di-t-butyl hydroquinone, 2,2'-methylene-bis(4-ethyl-6-t-butylphenol) and 4,4'-butylidene-bis(3-methyl-6-t-butylphenol).
• hindered amine compound described above examples include bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, polycondensation product of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[ ⁇ 6-(1,1,3,3-tetramethylbutyl)-amino-1,3,5-triazine-2,4-diyll ⁇ 2,2,6,6-tetramethyl-4-piperidyl)iminol hexamethylene(2,2,6,6-tetramethyl-4-piperidyl)imino], 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonic acid bis(1,2,2,6,6-pentamethyl-4-piperidyl), 1-[2-[3-(3,5-di-t-butyl-4-hydroxyphen
• high boiling solvent examples include high-boiling or slow-evaporating kinds of alcohols, ketones, esters, ethers, aromatic (halogenated) hydrocarbons, aliphatic (halogenated) hydrocarbons, ethylene glycol ethers, formamides and sulfoxy compounds.
• plasticizers described above include all plasticizers such as phthalate-based plasticizers, adipate-based plasticizers, phosphate-based plasticizers, polyester-based plasticizers and polyether- based plasticizers.
• Examples of the above synthetic resin include similar synthetic resins as in fine particles of thermochromic matrix described above.
• Dyeing of a cellulose fiber textile product by the dyeing method of the present invention can be achieved for example as follows:
• An acid such as acetic, tartaric, oxalic or malic acid may be added to adjust the pH to the acidic side, or a wetting agent such as urea, glycerol, ethylene glycol, polyethylene glycol or diethylene glycol may be added to improve the permeability of the cationic compound into the textile product.
• the textile product described above is immersed in the aqueous solution thus obtained, and the temperature is maintained at normal temperature to about 80 ° C for about 5 to 30 minutes, whereby the cellulose fiber of the textile product is efficiently cationized.
• this textile product is thoroughly rinsed to wash down the excess portion of the cationic compound and other additives and then dehydrated.
• water is added in a ratio of about 1:5 to 1:50, preferably 1:10 to 1:30, relative to the pretreatment textile product, and the reversibly color changeable fine particles as described above are added and dispersed in a ratio of about 0.1 to 50% by weight, preferably 1 to 25% by weight, relative to the pretreatment textile product. It is possible to add the fine particles in the form of aqueous dispersion containing them.
• the dispersion thus obtained is treated at normal temperature to about 90 ° C for 5 to 30 minutes, whereby the reversibly color changeable fine particles are completely exhausted into the cationized textile product described above.
• This treating temperature is preferably about 60 to 90 ° C when using the fine particles described above at a high concentration of 10 to 50% by weight.
• This treatment results in the binding of the reversibly color changeable fine particles described above to the textile product described above by chemical ion bond and physical adsorption.
• This product is then dehydrated and dried and heated at preferably about 80 to 180°C for about 0.5 to 10 minutes, whereby the fine particles described above are firmly fixed to the textile product.
• the textile product thus obtained has been dyed with the reversibly color changeable fine particles to a high density and in addition, it maintains a good texture and soft handling touch, and it is excellent in color fastness to rubbing and color fastness to washing.
• the binder solid content can be 0.1 to 10% by weight of the textile product in general.
• the binder solid content is more preferably 0.3 to 5% by weight.
• the usable binder examples include acrylic resin, methacrylic acid resin, vinyl acetate resin, polyurethane resin, polyester resin, styrene-butadiene latex and polyolefin resin; polyacrylic acid, methacrylic acid and their derivatives and copolymers of these substances with other vinyl polymers.
• acrylic ester resin and polyurethane resin are especially preferable.
• Dyeing a textile product by this method can be achieved, for example, as follows: The cellulose fiber textile product is treated with a cationic compound and immersed in dispersion containing reversibly color changeable fine particles. The fine particles are thereby exhausted into the textile product. To the dispersion, a binder is added in a ratio of 0.1 to 10% by weight of binder solid content relative to the textile product, followed by treatment at normal temperature to about 90 ° C for 1 to 30 minutes and dehydration and drying.
• the textile product thus obtained shows further improvements in the color fastness to rubbing and color fastness to washing.
• This binder can be the same as above.
• the binder solid content can be 0.1 to 10% by weight to the textile product in general.
• the binder solid content is more preferably 0.3 to 5% by weight.
• Dyeing a textile product by this method can be achieved, for example, as follows: The cellulose fiber textile product is treated with a cationic compound and immersed in dispersion containing reversibly color changeable fine particles. The fine particles are thereby exhausted into the textile product, followed by dehydration. To the bath, water is added in a bath ratio of 1:5 to 1:50, preferably 1:10 to 1:30. A binder is added in a ratio of 0.1 to 10% by weight of binder solid content relative to the textile product, followed by treatment at normal temperature to about 90 ° C for 5 to 30 minutes and dehydration and drying.
• the textile product thus obtained shows further improvements in the color fastness to rubbing and color fastness to washing similarly in the case described above.
• This binder can be the same as above.
• the binder solid content can be 0.1 to 10% by weight to the textile product in general.
• the binder solid content is more preferably 0.3 to 5% by weight.
• Dyeing a textile product by this method can be achieved, for example, as follows: The cellulose fiber textile product is treated with a cationic compound and immersed in dispersion containing reversibly color changeable fine particles and a binder in a ratio of 0.1 to 10% by weight of binder solid content relative to the textile product and treated at normal temperature to about 90 ° C for 5 to 30 minutes, followed by dehydration and drying.
• the textile product thus obtained shows further improvements in the color fastness to rubbing and color fastness to washing similarly in the case described above.
• This binder can be the same as above.
• the binder solid content can be 0.1 to 10% by weight of the textile product in general.
• the binder solid content is more preferably 0.3 to 5% by weight.
• the first process can be replaced by the process of treating a cellulose fiber textile product with cationic binder in an amount insufficient to spoile the appearance and touch of the dyed product.
• cationic binder examples include VONCOAT SFC series (trade name, emulsion of vinyl acetates or acrylic esters, product of Dainippon Ink and Chemicals, Inc.), YODOSOL AF series (trade name, emulsion of acrylic esters, product of Kanebo NSC Co., Ltd.), CGC series (tradename, emulsion of acrylic esters, product of Sumitomo Chemical Industry Co., Ltd.), cationic emulsion disclosed in Japanese Patent Publication Open to Public Inspection No. 187702/1987, cationic copolymer disclosed in Japanese Patent Publication Open to Public Inspection No. 131003/1987, cationic polymer disclosed in Japanese Patent Publication Open to Public Inspection No. 201914/1987 and cationic latex.
• VONCOAT SFC series trade name, emulsion of vinyl acetates or acrylic esters, product of Dainippon Ink and Chemicals, Inc.
• YODOSOL AF series trade name, emulsion of acrylic esters
• the binder is exhausted into the textile product in an amount approximately equal to the content of the dispersion, i.e. in a ratio of about 0.1 to 10% by weight of binder solid content relative to the textile product, the binder is strongly fixed to the textile product by dehydration and drying. As a result, further improvements in the color fastness to rubbing and color fastness to washing are obtained.
• the binder solid content is less than 0.1 % by weight relative to the textile product, the obtained effect is likely to be insufficient. If the binder content exceeds 10% by weight, the appearance and touch of the textile are often spoiled.
• thermochromic fine particles whose color changing temperatures are different, it is possible that the dyed products of the present invention change color in two or more stages, like "yellow- - orange- - black”.
• thermochromic fine particles By the use of specific esters as solvent of the three-component mixture in thermochromic fine particles, it is possible that the dyed product shows obvious hysteresis in changing color. For example, the temperature of development of the color with a drop in temperature can be lower by some centigrade degrees than the temperature of disappearance of the color with a rise in temperature. Accordingly, it is possible for a uniformly dyed textile product of the present invention to show different colors in parts at equal temperature.
• Dyeing a textile product by the present dyeing method with mixture of thermochromic fine particles and photochromic fine particles the dyed product changes color in plural stages reversibly by changing the temperature or in the presence or absence of light irradiation.
• the dispersion containing reversibly color changing fine particles may further contain daylight fluorescent pigment and/or other inorganic or organic pigments, which may be exhausted into the textile product simultaneously with the reversibly color changing fine particles.
• any addition amount of the pigment described above can be selected as long as the total amount of the reversibly color changing fine particles and pigment does not exceed 50% by weight of the textile product. It is preferable to use the pigment in a ratio of 0.5 to 10% by weight in the case of daylight fluorescent pigments, or 0.1 to 2% by weight in the case of other inorganic pigments or organic pigments.
• daylight pigments examples include those prepared by coloring a formaldehyde condensation product of cyclic aminotriazine compound and aromatic monosulfamide compound as the base resin with a fluorescent cation dye or dispersion dye.
• Other pigments include inorganic pigments such as iron oxide, chromium yellow, ultramarine blue, titanium dioxide and carbon black, and organic pigments such as azo pigments, anthraquinone pigments, lake pigments, dioxazine pigments and phthalocyanine pigments.
• pigments can be used in the form of a dispersion of fine grains having a diameter of 0.05 to 10 /1.m prepared by wet milling in water containing the anionic surfactant described above and the nonionic surfactant and wetting agent described above added as needed.
• a daylight fluorescent pigment obtained by coloring an aqueous emulsion polymer or suspension polymer of acrylonitrile and another polymerizable unsaturated vinyl compound with a fluorescent cationic dye or dispersion dye upon or after polymerization can be used as such, since it is about 0.05 to 10 /1.m in grain diameter.
• any one of the dyeing methods described above is carried out after dyeing the textile product with a direct dye or acid dye or after basically dyeing the textile product with a pigment such as an organic pigment, inorganic pigment or daylight fluorescent pigment by resin padding, it is possible to cause reversible color changes, which are developed by color mixture of the pigment and the fine particles, by changing temperature or in the presence or absence of light irradiation.
• thermochromic microcapsule containing three-component mixture preparation of thermochromic microcapsule containing three-component mixture --
• NC-R-1 pink
• acid developing substance product of Hodogaya Chemical Industry Co.
• a hot uniform molten mixture of the formulation described above was obtained by heating it.
• the molten mixture was added to 200 parts of a 5% aqueous solution of gelatin at 60 ° C and dispersed in the form of oil drops of 5 ⁇ m in diameter with stirring.
• the solution was thereafter cooled, and the resulting microcapsules were washed with water and filtered to remove 90% by weight of the gelatin contained therein to yield 100 parts of a dispersion containing about 35 parts of thermochromic microcapsules and about 1 part of gelatin.
• thermochromic microcapsule containing three-component mixture preparation of thermochromic microcapsule containing three-component mixture --
• Citric acid was added dropwise to adjust the liquid to a pH of 5, and the liquid was stirred at 70 ° C for 2 hours. Citric acid was further added dropwise to adjust the liquid to a pH of 3, and the solution was stirred at 80 ° C for 2 hours, followed by washing with water, filtration and drying to yield about 40 parts of microcapsules.
• microcapsules described above were added to 100 parts of 2% carboxymethyl cellulose, and this mixture was stirred to yield a uniform dispersion.
• the liquid was stirred at 40 ° C for 3 hours, followed by washing with water, filtration and drying to yield about 42 parts of microcapsules whose outer layer were coated with carboxymethyl cellulose.
• Tinuvin 622LD (trade name, hindered amine compound, product of Chiba-Geigy AG) 2 parts
• Polystyrene resin 24 parts
• Polymethylenephenyl isocyanate [MILLIONATE MR (trade name, product of Nippon Polyurethane Industry Co., Ltd.)] 10 parts
• This formulation was stirred in a sand grinder to yield a uniform liquid mixture.
• Photochromic microcapsules were obtained in the same manner as in Preparation Example 4 except that 1 part of 6'-piperidino-1,3,3-trimethylspiro[indoline-2,3'-[3H]naphtho(2,1-b)(1,4)oxazine] and 26 parts of SANOL LS-770 were used in place of 1 part of 2,2-diphenyl-3H-naphtho-(2,1-b)pyran, 2 parts of Mark LA-67, 24 parts of polystyrene resin and 56 parts of toluene used in Preparation Example 4.
• the molten mixture of the formulation described above was added dropwise to a 3% aqueous solution of styrene/maleic anhydride copolymer with stirring.
• Aqueous solution containing DEMOL N (trade name, anionic surfactant, product of Kao Co.) was heated to 90 °C. To this solution, the molten uniform mixture of the formulation described below was added dropwise with stirring the solution.
• Sanwax 151 P (trade name, low molecular weight polypropylene, product of Sanyo Kasei Kogyo Co.) 5 parts STAFLENE E-715(trade name, polyethylene resin, product of Nippon Sekiyu Kagaku Kogyo Co.) 50 parts Xylene 20 parts
• thermochromic matrix having about 10 ⁇ m average grain size with the almost all portion of the xylene evaporated.
• the suspension was concentrated by water evaporation to yield 150 parts of suspension containing about 60 parts of the fine particles of thermochromic matrix with the xylene perfectly evaporated.
• thermochromic microcapsules containing three-component mixture having character of hysteresis was obtained in the same manner as in Preparation Example 1 except that 15 parts of stearyl benzoate and 5 parts of lauryl myristate were used in place of 10 parts of lauryl palmitate and 10 parts of cetyl alcohol used in Preparation Example 1.
• a cotton T-shirt (grey sheeting, 120 parts) was scoured to remove the sizing and impurities.
• the scoured T-shirt described above was immersed in this aqueous solution and gradually heated to 70 ° C, at which temperature it was treated for 15 minutes.
• the T-shirt was thoroughly rinsed with water to remove the excessive portion of the cationic compound and other additives, followed by dehydration.
• thermochromic microcapsules obtained in Preparation Example 1 were added to this vat, and this liquid was gradually heated to 80 ° C, at which temperature it was treated for 15 minutes.
• thermochromic microcapsules were completely exhausted into the cotton T-shirt.
• this T-shirt was thoroughly rinsed and dehydrated, after which it was allowed to dry and then subjected to heat treatment at 140 ° C in a tumbler drier for 1 minutes.
• a cotton T-shirt was treated in the same manner as in Example 1 except that the suspension containing the fine particles of thermochromic matrix of Preparation Example 7 was used in place of the dispersion containing thermochromic microcapsules obtained in Preparation Example 1.
• the treated T-shirt showed same color changes as in Example 1, and the quality of the T-shirt was as good as in Example 1.
• a cotton T-shirt was treated in the same manner as in Example 1 except that the dispersion containing the photochromic microcapsules of Preparation Example 2 was used in place of the dispersion containing thermochromic microcapsules obtained in Preparation Example 1.
• This treated T-shirt was found to be white under indoor conditions free of direct sun light, while it became dark blue at windows and outdoors under direct sun light. This change could be reversibly repeated in cycles, and the quality of the T-shirt was as good as in Example 1.
• a cotton T-shirt was treated in the same manner as in Example 1 except that the fine particles of photochromic matrix of Preparation Example 6 were used in place of the thermochromic microcapsules obtained in Preparation Example 1.
• This treated T-shirt was found to be white under indoor conditions free of direct sun light, while it became deep purple at windows and outdoors under direct sun light. This change could be reversibly repeated in cycles, and the quality of the T-shirt was as good as in Example 1.
• thermochromic microcapsules of Preparation Example 1 A cotton T-shirt was treated in the same manner as in Example 1 except that 20 parts of the dispersion containing the thermochromic microcapsules of Preparation Example 1 and 30 parts of the dispersion containing the photochromic microcapsules of Preparation Example 2 were used in place of 50 parts of the dispersion containing thermochromic microcapsules obtained in Preparation Example 1.
• thermochromic microcapsules of Preparation Example 1 A cotton T-shirt was treated in the same manner as in Example 1 except that 10 parts of the dispersion containing the thermochromic microcapsules of Preparation Example 1 and 8 parts of the photochromic microcapsules of Preparation Example 3 were used in place of 50 parts of the dispersion containing thermochromic microcapsules obtained in Preparation Example 1.
• This treated T-shirt was found to be white at temperatures over about 30 ° C, while it became pink at about 25 C, and it became deep orange at temperatures about below 20 °C, i.e. changed color in two stages. This change could be reversibly repeated in cycles, and the quality of the T-shirt was as good as in Example 1.
• a cotton T-shirt scoured in the same manner as in Example 1 was immersed in an aqueous solution of a bath ratio of 1:20 prepared by adding a direct dye (trade name, KAYARUS YELLOW F8G, product of Nippon Kayaku Co., Ltd.) to water in a ratio of 0.1 %, and treated at 90 °C for 3 minutes to yield a yellow dyed T-shirt.
• a direct dye trade name, KAYARUS YELLOW F8G, product of Nippon Kayaku Co., Ltd.
• thermochromic microcapsules of Preparation Example 8 was used in place of the dispersion containing thermochromic microcapsules obtained in Preparation Example 1.
• This T-shirt was found to be deep orange which is developed by mixing pink of the thermochromic microcapsules and yellow of the ground color at temperatures about below 25 ° C, while it changed its color to yellow at temperatures about over 30 ° C as the color of the microcapsules disappeared.
• the color of the T-shirt remained yellow at temperatures about over 20 ° C; as the temperature decreased the color changed to deep orange again at temperatures about below 15 C.
• this T-shirt shows yellow and deep orange simultaneously at temperatures ranged 20 to 25 ° C by partial difference of temperature hysteresis.
• the quality of the T-shirt was as good as in Example 1.
• a cotton T-shirt (smooth knit, 150 parts) was scoured to remove the sizing and impurities.
• AMIGEN NF tradename, aqueous solution containing quaternary ammonium salt type cationic polymer compound about 30% by weight, product of Dai-ichi Kogyo Seiyaku Co., Ltd.
• 10 parts of ethylene glycol were added to a 5- vat.
• the T-shirt described above was immersed in this solution and gradually heated to 60 °C, at which temperature it was treated for 20 minutes.
• this T-shirt was thoroughly rinsed with water and dehydrated.
• 3000 parts of water and 22.5 parts of the photochromic microcapsules obtained in Preparation Example 4 were added to this vat and dispersed. This dispersion was gradually heated to 70 °C, at which temperature it was treated for 15 minutes to exhaust the photochromic microcapsule into this T-shirt.
• this T-shirt was thoroughly rinsed with water and dehydrated, after which it was subjected to tumbler drying for 1 minute.
• the obtained T-shirt was found to be totally white under indoor conditions free of direct sunlight, while it changed its color to deep yellow at windows and outdoors under direct sun light by developing color of the photochromic microcapsules. This change could be reversibly repeated in cycles, and the quality of the T-shirt was as good as in Examples 1 through 7.
• Photochromic microcapsules were exhausted into a cotton T-shirt (150 parts, smooth knit), and the T-shirt was rinsed with water and dehydrated in the same manner as in Example 8.
• MATSUMINSOL MR-10 trade name, acrylic ester resin binder, product of Matsui Shikiso Chemical Co., Ltd.
• the obtained T-shirt showed the same color changes as in Example 8 and had alomost equal appearance and touch to those of the T-shirt of the Example 8. Moreover, the color fastness to rubbing and color fastness to washing were better than those of the T-shirt of Example 8.
• a T-shirt as used in Example 8 was scoured and then immersed in a padding solution comprising 1300 parts of water, 300 parts of the photochromic microcapsules of Preparation Example 4 and 400 parts of MATSUMINSOL MR-10 by the two-dip two-nip method and then dehydrated and allowed to dry.
• this T-shirt was found to be white under indoor conditions free of sufficient light. When irradiated with sufficient light, this T-shirt changed its color to pale yellow, but this change was too minute to notice without careful watching, and it seemed to have no commercial value.ln addition, the color fastness to rubbing and color fastness to washing were poorer than those of the T-shirt of Example 8.
• This T-shirt was found to be totally white under indoor conditions free of direct sunlight, while it changed its color to deep purple at windows and outdoors under direct sun light.
• a T-shirt was cationized in the same manner as in Example 8.
• this T-shirt was thoroughly rinsed with water and then dehydrated. Then, 3000 parts of water, 17.5 parts of the photochromic microcapsules of Preparation example 4 and 7.5 parts of Glow Pink M12G (trade name, water dispersion of pink daylight fluorescent pigment in the presence of anionic surfactant, product of Matsui Shikiso Chemical Co., Ltd.) were added to this vat and dispersed, followed by the same procedure as in Example 8 to yield a T-shirt on the entire surface of which the photochromic microcapsule and the daylight fluorescent pigment were fixed.
• Glow Pink M12G trade name, water dispersion of pink daylight fluorescent pigment in the presence of anionic surfactant, product of Matsui Shikiso Chemical Co., Ltd.
• This T-shirt was found to be totally pink under indoor conditions free of direct sun light, while it changed its color to deep orange at windows and outdoors under direct sunlight by mixing pink of the pigment and yellow of the photocromic microcapsules. This change could be reversibly repeated in cycles, and the quality of the T-shirt was as good as in Example 8.
• SANFIX 70 (trade name, dicyanamide type cationic polymer compound, product of Sanyo Kasei Co., Ltd.) and 15 parts of ethylene glycol were added, and the trainer described above was immersed in this liquid and treated at 60 ° C for 15 minutes and then thoroughly rinsed and dehydrated.
• thermochromic microcapsule of Preparation example 3 were added and dispersed.
• HYDRIN AP-20 trade name, polyurethane resin emulsion, product of Dainippon Ink and Chemicals, Inc.
• a cotton trainer (300 parts) was scoured and cationized in the same manner as in Example 12, after which it was thoroughly rinsed and dehydrated.
• thermochromic microcapsules of Preparation example 3 and 30 parts of HYDRIN AP-20 were added and dispersed.
• This dispersion was gradually heated to 80 ° C, at which temperature the cotton trainer was treated for 15 minutes, after which it was dehydrated and allowed to dry thoroughly.
• This trainer showed the same color changes as in Example 12, and its appearance, touch, color fastness to rubbing and color fastness to washing were as good as in Example 12.
• thermochromic microcapsules of Preparation Example 3 45 parts of the thermochromic microcapsules of Preparation Example 3 and 6 parts of PG BLUE-MI-IB (tradename, aqueous dispersion containing blue organic pigment about 20% by weight, product of Matsui Shikiso Chemical Co., Ltd.) were added and dispersed.
• PG BLUE-MI-IB tradename, aqueous dispersion containing blue organic pigment about 20% by weight, product of Matsui Shikiso Chemical Co., Ltd.
• This dispersion was gradually heated to 80 °C, at which temperature it was treated for 15 minutes, after which it was thoroughly rinsed, dehydrated and allowed to dry. And then, it was subjected to heat treatment at 130 ° C for 3 minutes.
• This trainer was found to be dark green at temperatures below about 20 ° C by mixing blue of the organic pigment and yellow of the thermochromic microcapsules, but it became blue at temperatures about over 25 °C as the color of the microcapsules disappeared.
• a trainer as used in Example 12 was scoured. 6000 parts of water and 6 parts of KAYARUS Black G conc (trade name, direct dye, product of Nippon Kayaku Co., Ltd.) were added to a vat, and this trainer was immersed therein and heated to 90 ° C, at which temperature it was treated for 5 minutes and then rinsed with water and dehydrated to dye this trainer black.
• KAYARUS Black G conc trade name, direct dye, product of Nippon Kayaku Co., Ltd.
• Example 12 the black trainer was treated in the same manner as in Example 12 except that the dispersion containing 40% by weight of the thermochromic microcapsules involving below described liquid crystals.
• This trainer reversibly changed its color clearly among red, yellow, green, blue and purple at temperatures ranged about 18 to 30 °C.
• the quality of the trainer was as good as that of the trainer of Example 12.
• thermochromic microcapsule involving above described liquid crystals can be obtained by carrying out coacervation method using the liquid crystals consisting of cholesterol nonanate, cholesterol benzoate and cholesterol oleyl carbonate whose ratio is 1:1:1 by weight, gelatin and gum arabic.
• Cotton jeans were scoured in a Smith drum dyeing machine.
• the jeans were subjected to heat treatment at 140 ° C for 3 minutes.
• the jeans were found to be striped white and dark green at temperatures below about 20 ° C by mixing blue of the organic pigment and yellow of the thermochromic microcapsules, but became striped white and blue at temperatures about over 25 °C as the color of the microcapsules disappeared.
• hindered amine compound and "hindered phenol compound”, as used in this description, refer to compounds in which the amine or phenolic hydroxy groups are surrounded by bulky groups (for example, plural methyl groups).

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• 1991
  • 1991-08-02 NZ NZ23923191A patent/NZ239231A/en unknown
  • 1991-08-29 DE DE199191114585T patent/DE480162T1/de active Pending
  • 1991-08-29 EP EP91114585A patent/EP0480162A1/fr not_active Ceased
  • 1991-08-29 ES ES91114585T patent/ES2044826T1/es active Pending
  • 1991-09-09 CA CA002051000A patent/CA2051000A1/fr not_active Abandoned
  • 1991-09-17 AU AU84500/91A patent/AU642529B2/en not_active Ceased
  • 1991-09-30 NO NO91913817A patent/NO913817L/no unknown
  • 1991-10-02 FI FI914630A patent/FI914630A/fi not_active Application Discontinuation
  • 1991-10-08 PT PT99173A patent/PT99173A/pt not_active Application Discontinuation
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• 1992
  • 1992-12-30 GR GR92300086T patent/GR920300086T1/el unknown

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