CA2051000A1 - Dyeing method and dyed product - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
A dyeing method comprising:
a process of treating a cellulose fiber textile product with cationic compound; and another process of treating the thus-treated textile product by immersing it in a dispersion containing reversibly color changeable fine particles which involve thermochromic or photochromic material in high polymer compound.

Description

- 20~00~

DYEING METHOD AND DYED PRODUCT

BACKGROUND OF THE INVENTION
1. Field of the Invention The present inventlon relates to a method of dyeing a cellulose fiber teYtile product with reversibly color changeable fine particles which involve thermochromic or photochromic material and a dyed product.

2. Description of the Prior Art Three-component mixture of acid developing sub~tance, acidic substance and solvent; two~component mixture of acid : 15 developing substance and acidic substance; cholesteric liquid crystal and metal complex salt crystal 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 ,: . . , .. : : . , , - ., :::, : ,. ~ , .

~: , . ,: . -,:: ~ . .: , :

,: ' ' ,,: , ~, , ' ,, ,: .: :, :".. :,::, ': : ,::'.: ., ': :
::, : : ,,~:: ~ : ~ : : , , , . , . : ~ :,: : .
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- ... , ., ,, :

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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 changeng 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.
Many of metal complex salt crystals are not suitable for applying on textile product because of thier toxicity.
With respect to photochromic materials, which show reversible color changes in the presence or absence of light, a wide variety of organic photochromic compounds have been developed which show more sensitive color changes between colored and colorless states, which offer more diverse colors and which are more compatible with various :: - ,, -:: . ,.. - . .... .... . . .. .

::: , .. .:, : ,: , ,.. . . . . ,. . .. ~ ,.

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:, :.;, :, .:
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organic compounds such as synthetic resins in comparison with conventional inorganic photochromic compounds such as silver halides.
Such organic photochromic compounds are used, for example, as dispersion in appropriate medium or in the form of microcapsule containing the dispersion.
None of these reversibly color changeable fine particles, i.e. particles of matrix or microcapsules which show reversible color changes by temperature or light are capable of directly dyeing fiber because of a lack of affinity with fiber. Although dyeing is possible by the synthetic resin printing method, the synthetic resin padding method and other methods using an adhesive such as synthetic resin binder, the coloring density obtained with reversibly color changeable fine particles involving thermochromic material or photochromic material is extremely lower than that obtaine~ with an orainary coloring agent. For example, in the case of the synthetic resin printing method, a fair coloring density is obtained only when bulky printing is conducted on a textile product using an ink containing such fine particles and synthetic resin binder at high concentrations. In this case, the surface of the textile product loses its fiber t0xture, its appearance worsens, and its color fastness to rubbing and ~5 color fastness to washing are insufficient For these : :. . : .. ...

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reasons, even when the entire surface of the cloth is colored, no commercially valuable product will be obtained.
Therefor, it is the conventional practice to make patterns such as one~point patterns on a very narrow area on the cloth.
Also, when using the pigment resin padding method with high concentrations of reversibly color changeable fine particles and synthetic resin binder, these fine particles are not capable of being thoroughly adsorbed because of a lack of substantivity with fiber, and physical adhesion as in the pigment resin printing method cannot be expected;
therefore, nothing more than extremely low coloring density can be obtained. Moreover, the obtained fibsr texture, appearance, color fastness to rubbing, and other properties are insuficient~

SUMMARY OF THE INVENTION
It it an object of the present invention to provide a dyeing method which permits dyeing of a cellulose fiber textile product with reversibly color changeable fine particles which involve 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 : ' ", ~: , 2 ~

other textile product properties.
It is another object of the invention to provide dyed product which is dyed with reversibly color changeable fine particles to high densities which could not be obtained formerly with no influence on the texture, appearance or other textile product properties.
The object described above can be accomplished by the dyeing method of the present invention, which comprises:
a process of treating a cellulose fiber textile product with cationic compound; and another process of treating the thus-treated textile product by immersing it in a dispersion containing reversibly color changeable fine particles which involve thermochromic or photochromic material in high polymer compound.
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.

DETAILED DESCRIPTION OF THE INVENTION
Cellulose fiber Examples of the cellulose fiber for the present - .. ~ : , ~ ::, : , :,. . .
: . . : :. . , .,.: .; : .~ ,... .
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invention include natural fibers such as cotton and hemp and regenerated fibers such as rayon and cupra.
Cellulose fiber textile product Examples oE 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 abrics. 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.
Cationic compound 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.
Specific examples of the cationic compounds are as ~ollows.
Examples of the quaternary ammonium salt type compounds include quaternary ammonium salt type cationic surfactants such as trimethyloctadecylammonium chloride, trimethylhexi~decylammonium chloride, :-: '' ': :: , , :

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trimethyllaurylammonium chloride, dimethyllaurylammonium chloride, laurylmethylammonium chloride, stearyltrimethylammonium chloride, lauryldimethylbenzylammonium chloride, lauryltrimethylammonium chloride, alkylbenzyldimethylammonium chloride, stearylbenzyldimethylammonium chloride, and alkyltrimethylammonium chloride;
pyridinium salt type surfactant such as laurylpyridinium chloride and stearylamide methylpyridinium chloride;
2,3-epoxypropyltrimethylammonium chloride;

3-chloro-2-hydroxypropyltrimethylammonium chloride;
quaternary ammonium salt compounds having a triazine ring as disclosed in Unexamined Japanese Patent Publication Nos.
155285/1977 and 155286/1977.
Examples of the dicyandiamide type compounds include formalin condensation product of dicyanamide.
Examples of polyamine type include guanidine derivative condensation product of polyalkylenepolyamine;
polyethyleneimines and polyamidepolya~ines.
Examples of the polycation type 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 ~ . .,, ., ~ : , ,: : ~ :, ., :

,~. , : :, ; . , , . ,, :, .: ,: , .

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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.
76177/19~0; polyapichlorohydrin-trimethylamine reaction product disclosed in Unexamined Japanese Patent Publication No. 112987/1976; quaternary l-vinylimidazole polymer disclosed in Unexamined Japanese Patent Publication No.
210083/1982; polymer of quaternary epoxypolyalkylenepolyamines disclosed in Unexamined Japanese Patent Publication Nos. 9979/1985 and 9930/1985;
copolymers of acrylamide and cationic monomers which can copolymerize with the acrylamide disclosed in Unexamined Japanese Patent Publication No. 47309/1982; cationic polymer containing quaternary ammonium salt disclosed in Unexamined Japanese Patent Publication No. 234007/1983;
quaternary ammonium salt polymers such as quaternary salts o~ aminoalkylacrylamide polymers disclosed in Une~amined Japanese Patent Publication No. 284225/1988; the polymer comprising the ~ollowing monomer unit:

:; ' ' ~ r , .. ''' . ,,',: ' ;' ' "' '': .: ', ,:.' ,'' , .

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~; J
Cl-l3 Cl13 n disclosed in Unexamined Japanese Patent Publication No.
12~382/1981; the polymer comprising the following monomer unit:

f X

\~/ l (SHALLOL DC (trade name~ series, product of Dai-ichi Kogyo Seiyaku Co., Ltd ) and copolymers of quaternary ammonium salts and other vinyl polymers.
Of these cationic 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 on the present invention.
Thermochromic material Example of 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 rnetal complex salt.
Three-component mixture, two-component mixture 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, ~luoran 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',3n-tris(p-dimethylaminophenyl)phthalide, 3,3'-bis(p-dimethylaminophenyl)phthalide, 3-d:iethylamino-7-phenylaminofluoran, 3,3-bis(p-diethylaminophenyl~-6-dimethylamino phthalide, 3-4(-diethylammophenyl)-3-(l-ethyl-2-methylindol-3 yl)phtalide, .
3-(4-diethylamino-2-methyl)phenyl-3-~1,2-dimethylindol-3-yl)phtalide and 2'-(Z-chloroanilino)-6'-dibu-tylaminospiro[phthalide-3,9'-xanthen]
~xamples of the acidic substance of three-component mixture and two-component mixture include ;

,~ 1 0 .".,;

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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 thereo~ 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 p-t-butylbenzoate, stearyl 4-methoxybenzoate, dilauryl thiodipropionate, dimyristylthiodipropionate, stearyl benzoate, benzyl stearate, benzyl thiodipropionbenzoate, distearyl thiodipropionate and benzyltrilaurate benzoate.
Cholesteric liquid crystal Z5 Examples of the cholesteric liquid crystal include ' ~ '' " ' ' . ' ' ' ~ '. ~ !',' ' :

~ ` ~ ' ' "' ' " `' ' ' " '' ~ ' '. . , ' ' ': , ` " " ~, ;,' ,' , " ., '~ ' . ` . ';", ` '' . ` . ` " ' ' ~1"''' ' , i ' ' '. ' ' : ' ' ' `': ~

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composition of two or more kinds selected from cholesterol acetate, cholesterol henzoate, cholesterol nonanate, cholesterol propionate, cholesterol oleyl carbonate and cholesterol chloride.
Metal complex salt Examples of the metal comple~ salt include complex compound of silver, mercury, iodine or copper and thiodicarbamic acid derivative complex.
Photochromic material __ 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, naphtopyran compounds, with preference given to spiropyran compounds, spirooxazine compounds, fulgide compounds and naphtopyran compounds for the dyeing method of the prasent invention.
Specific examples of photochromic material include 1,3,3-trimethylspiro[indoline-2,3'-(3H)naphtho(2,1-b)(1,4)- s 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'-(3H)naphtho(2, , . , ' : ",'.!.`i'' .: '.

, : , ", ~ . . .

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20~l00a l-b)(1,4)-oxazine], 6'-piperi.dino-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)(l ,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], 1,3,5,6-tetramethyl-3-ethylspiro[.indoline-2,3'-(3H)pyrido(3,2-f)(1,4)-benzooxazine], 1,3',3'-trimethylspiro(2H-l-benzopyran-2,2'-indoline), 1,3,3-triphenylspiro[indoline-2,3'-(3H)naphtho(2,1-b)pyran], 1-(2,3,4,5,6-pentamethylbenzyl)-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], 2,2-diphenylnaphtho(2,1-h)pyran, 2,2-di(p-methoxyphenyl)naphtho(2,1-b)pyran, 2,5-dimethylfuryl-trimethylfulgide and 2-methyl 5-chloro-trimethylfulgide.
Reversibly color changeable fine particle Reversibly color chanyeable fine particle involve thermochromic or photochromic material in high polymer compound.
, , ~ 1 3 -:, .. : ,, " .

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Examples of the reversibly color changeable fine particle include particles containing thermochromic material in high pol~mer 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 which capsulated in high polymer microcapsules and particles containing sol~ed or dispersed organic photochromic substance in medium which capsulated in high polymer microcapsules. It is preferable that the diameters o~ the reversibly color changeable fine particles do not exceed 50u m. If the diameters exceed 50 ~ m, exhaustion of the particles into a cellulose fiber textile product often go badly.
Thermochromic microcapsule The three-component mixture, the two-component mixture or the cholesteric liquid crystal as thermochromic ~aterial can be microcapsuled by, for example, the following method.
Microcapsules of 1 - 50 ~ m in diameter containing thermochromic material which are dispersed in aqueous dispersion can be obtained by carring out a known capsulation method such as the interfacial polymerization method, the insight polymerization method, the ,. . - ; - ~ ~
,.: : ~ , ~ ,; ' ;: . ., -.
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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 crystal and high polymer compound as coat former with surfactant, a protective colloid, a pH regulator, an electrolyte and other substances as needed.
The layers of the microcapsules can be plural by carring out one or more kind of these capsulation method two or more times repeatedly.
Examples of preferable coat former include polyisocyanate and polyamine for forming polyurea coat, polybasic acid chloride and polyamine fo~ forming polyamide coat, polyisoGyanate and polyhydro~y compound ~or forming polyurethane coat, epoxy compound and polyamine for forming epoxy resin coat, melamine-formalin prepolymer for forming melamine resin coat, urea-~ormalin prepolymer for forming urea resin coat, ethyl cellulose, polystyrene and polyvinyl acetate, and anionic high polymer compounds and amphoteric 2U high polymer compounds described later.
It is preferable that the coat for the microcapsule described above be thermosetting because of excellent heat resistance.
Examples of preferably usable surfactant and protective colloid include aniorlid surfactants, amphoteric surfactants, .: -.. ::. . :
.: , , .. : :. ;: :: :
; ~ . , , .,: , . .
,, , , , ~, .

anionic high polymer compounds, amphoteric high polymer compounds. In addition, nonionic surfactants can be used with these.
Usual electrolytes and pH regulators used in above capsulation methods are usable.
In the present invention, it is possible to use the 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 e~tent 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 15 microcapsules have high dispersibility, surfactant and ~' protectiv~ colloid are not necessary. Microcapsule whose coat is anionic high polymer compound or amphoteric high polymer compound often have enough dispersibility.
Examples of the anionic surfactant described above include alkyl sulfates, alkyl benzenesulfonates, alkyl naphthalenesulfonates, alkyl sulfosuccinates, alkyl diphenyl ether disulfonates, alkyl phosphates, polyoxyethylene allcyl sulfates, polyoxyethylene alkylallyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene polystyrylphenyl :

2~S100~

ether sulfates and polyoxyethylene alkyl phosphates.
Examples of the anionic polymer compound described above include polyacrylic acid, poly-a -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 derivativesA
Examples of the amphoteric polymer compound described above include gelatin and casein.
Examples of the nonionic surfactant described above include polyoxyethylene alkyl ether, polyoxyethylenealkylallyl ether and other polyoxyethylene derivatives, polyoxyethylene~polyoxypropylene block copolymer, aliphatic esters of sorbitan, fatty acid esters of polyoxyethylenesorbitol and fatty acid esters of glycerol.
Fine particle of thermochromic matrix Particles containing dispersed three-component mixture, two-component mixture or cholesteric liquid crystal as thermocromic 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.

.. ~" ",.,, ,,,, , ~ , ,- ,. . .. ... . .
- , , :.: . ,:, : - ::: . , -: , :: , , , : ,., : -:, , , , ~
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The mix-ture is stirred untill 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 yeild 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 untill the $hermochromic material is dispersed in the synthetIc resin. The dispersion mixture is free~ed and pulverized to give particles containing dispersed thermocromic material in matrix of synthetic -~
resin.
Examples o~ the synthetic resin described above include acrylic polymers such as polyvinyl butyral, polyvinyl alcohol and polymethylmethacrylate; styrene polymers such as polystyrane and ABS resin; polyester polymers such as polycarbonate; polyether polymers such as polyethylene oxide; polyoletin polymers such as polyethylene and polypropylene, ethyl cellulose, polyvinyl acetate, polyvinyl chloride, melamine resin, epoxy resin and polyurethane resin.
It is possible to add ultraviolet absorber, ultraviolet stabilizer, antioxidant, antireductant, surfactant, fluorescent brightening agent and so on to the above ,-.
', '~ ' ',: ' , ': ~ .':
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thermochromic microcapsules or fine particles of thermochromic matrix as needed.
~ine particle of photochromic matrix Particles containing dispersed organic photocromic substanse as photocromic material in matri~ 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.
Photochromic microcapsule , Particles containing dispersed organic photochromic substance in matrix of synthetic resin which capsulated in high polymer microcapsules or particles containing solved or dispersed orqanic photochromlc substance in medium which capsulated in high polymer microcapsules can be prepared, for exampla, 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 : ,.,. , ~ , : .. , ,. . : , ;,., ., , " ~ : , ,: , , ,. ,:

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: . ,: .

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photochromic compound. In the context of thi.s invention, "hindered amine compound" means a compound having amino group which is surrounded by bulky radicals (for example, plural methyl groups) as follows:

HJ~ CH3 N-H
H ~ CH3 and "hindered phenol compound" means a phenol compound having hydroxy group which is surrounded by bulky radicals.
Examples of the hindered phenol compound described above - include 2,6-di-t-butylphenol, 1,4,6-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).
Examples of the hindered amine compound described above include bis(2,2,6,6-tetramethyl-4-p:iperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, poly-condensation product of dimethyl succinate and ~.-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, 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)-2-n-butylmalonic acid bis(l,2,2,6,6-pentamethyl-4-piperidyl), 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]undecane-2,4-dione, tetrakis(2,2,6,6-tetramethyl-4-piperidine)butanecarbonate and mark LA57, mark LA62 and mark LA67 (trade marks , product of Adeka Argusl Co.).
Examples of the high boiling solvent described above 20a ~."~., ,, ... . ,, , , .. ,.. j .~, .. -,, ".. , ~, .
. - . , . . . . : . :;" : .. ;, , , . ~,,: , , ,,. : . .
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include high-boiling or slow-evaporating kinds of alcohols, ketones, esters, ethers, aromatic (halogenated) hydrocarbons, aliphatic (halogenated) hydrocarbons, ethylene glycol ethers, formamides and sulfoxys (sulfoxy compounds).
Examples of the plastici~er described above include all plasticizers such as phthalate-based plasticizers, adipate-based plastici~ers, phosphate-based plasticizers, polyester-based plastici~ers and polyether-based plastici~ers.
Examples of the above synthetic resin include similar synthetic resins as iIl fine particle of thermochromic matrix described above.
Examples of dyeing process -Dyeing of a callulose fiber textile product by the dyeing method of the present invention can be achieved for example as follows:
The textile product described above is first scoured to remove sizing and impurities. "Scouring" means purifying the product by removing natural impurikies, chemical agents, etc., and is of course unnecessary when the textile product is clean.
Next, to an appropriata dyeing bath, water in an amount 5 to 50 times the amount of the textile product (bathratio = 1:5 to 1:50), preferably 10 to 30 times (bath ratio =
1:10 to 1:30), is added, and a cationic compound is added thereto in a ratio of about 0.1 to 20% by weight, preferably about 0.3 to 5% by weight, to the pretreatment textile product. An acid such as acetic, tartaric, oxalic or malic .
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~5~ ~oa 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.
Next, the textile product described above is immersed in the aqueous solution thus obtained, and the temperature is maintained at normal temperature to about 80C for about 5 to 30 minutes, whereby the cellulose fiber of the textile product is efficiently cationi~ed.
Subsequently, this textile product is thoroughly rinsed to wash down the excess portion of the cationic compound and other additives and then dehydrated.
Next, to the bath containing the treated textile product, 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 :: . .- .: . . . . .
::: : ~ , - . , - -, :, ::,.. .. ,. , :

:, , , ,~ ' , , ,. ":' , : . ~ , : ., .: , ~, : , , : ::. ,. :,:: :: :

~5~ 0~

exhausted into t-he cationized textile produci described above. This treating temperature is preferably about 60 to 90C when using the fine particles described above at a high concentration of 10 to 50% by weiyht. The term "exhausted" relates to the proportion of dye or other substance taken up by a substrate at a given stage of a process to the amount originally available.
This treatment results in the binding of the Leversibly 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 180C for about 0.5 to 10 minutes, whereby the fine particles described above is 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 iIl color fastness to rubbing and color fastness to ~ashing.
Example of preferable dyeing process 1 A preferred mode of the dyeing method of the present invention comprises:
a process of treating a cellulose fiber textile product with cationic compound;
another process of treating the thus-treated textile product by il~mersing it in a dispersion containing reversibly color changeable fine particles which involve thermochromic or photoc~lromic material in high polymer , ~- , . , ., : :
.

, . .

. . , : , , " : .. , , : . . : .. , . . .

2~10~) compound; and still another process of further treating the textile product by adding binder to the dispersion in an amount insufficient to spoile the appearance and touch oE the dyed product.
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.
Examples of the usable binder include acrylic resin, metacrylic acid resin, vinyl acetate resin, polyurethane resin, polyester resin, styrene-butadiene latex and polyolefin resin; polyacrylic acid, methacrylic acid and their derivatives and copolymers oE these substances with other vinyl polymers. For the present invention, acrylic ester resin and polyurethane resin are especially preferable.
~ yein~ a textile product by this method can be achieved, f~r example, as follows: The cellulose fiber textile product is treated with a cationic compound and immersed in dispersion containing reversibly color chan~eable 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~ for 1 to 30 mlnutes and 2 ~

` ' . ' ', : ' ', ' : ' ' ' ' ' ' .: " ': " : ' " " `' ' : ' ' ' : .

: , ' ,, " ~'; ' :" . '~

.:, : : , -,":`,., ,.: : ;: ' ~

2~S~

dehydration and drying.
The textile product thus obtained shows further improvements in the color fastness to rubbing and color fastness to washing.
Example of preferable dyeing process 2 Another preferred mode of the dyeing method of the present invention comprises:
a process of treating a cellulose fiber textile product with cationic compound;
another process of treating the thus-treated textile product by immersing it in a dispersion containing reversibly color changeable fine particles which involve thermochromic or photochromic material in high polymer compound; and still another process of further t:reating the textile product by immersing it in water containing binder in an amount insufficient to spoile the appearance and touch of the dyed product.
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 :., ~ . :

2 ~

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 pro~uct, 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 imprvvements in the color fastness to rubbing and color fastness to washing similarly in the case described above.
Example of preferable dyeing process 3 A still another preferred mode of the dyeing method of the present invention comprises:
a process of treating a cellulose fiber textile product with cationic compound; and another process of treating the thus-treated textile product by immersing it in a dispersion containing a) reversibly color changeable fine particles which involve thermochromic or photochromic material in high polymer compound and b) binder in an amount insufficient to spoile the appearance and touch of the dyed product.
This binder can be the same as above. The binder solid ,, , ~ ,~ ;,,: "; ,,: ,,:, - , :

" ,:

2~10~

content can be 0.1 to 10% by weight to the textile product in general. The binder solid content is more preEerably 0.3 to 5% by weight.
Dyeing a textile product by this method can be 5 achieved, for e~ample, 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 90C for 5 to 30 minutes, followed by dehydration and drying.
I'he textile product thus obtained shows further improvements in the color fastness to rubbing and color fastness to washing similarly in the case described above.
Example o preferable~dyeing process 4 A still another preferred mode of the dyeing method of the present invention comprises:
a first process of treating a cellulose fiber textile product with c~tionic compound and binder in an amount insufficient to spoile the appearance and touch of the dyed product; and a second process of treating the thus-treated textile product by immersing it in a dispersion containing reversibly color changeable fine particles which involve .

`' "' " ''' ' thermochromic or photochromic material in high polymer compound.
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.
In the first process, neutralization of cationic compound by adding soda ash or caustic soda is carr~ie out at need.
The first process can be replaced by the process of treating a cellulose fiber textile product with cationic binder in an amount insuficient to spoile the appearance and touch o~ the dyed product.
Examples of cationic binder include VONCOAT SFC series (trade mark, emulsion of vinyl acetates or acrylic esters, product of Dainippon Ink and Chemicals, Inc.), YODOSOL AF seriPs (trade mark, emulsion of acrylic esters, product of Kanebo NSC Co., Ltd.), CGC series (trade mark, 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 ,i ~ 2 8 . . .

:.
:,~, ~ , ;, ,; :

2.~ 000 cationic latex.
In the above described preferable dyeing processes 1 to 4, the binder is exhausted into the textile product in 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.
By the use of two or more kinds of thenmochromic fine particles whose color changing temperatures are different, it is possible that the dyed product of the present invention change color in two or more stages, like "yellow , ,orange~ ~black".
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 ,- ~, , ~ , . . .

. :' "
:' ' ' ' .', ' ' .

. . ' , , , ' 0 ~

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 chanye color in plural stages reversibly by changing the temperature or in the presence or absence of light irradiation.
Fu~thermore, in the dyeing method of the present invention described above, the dispersion containing reversibly color changing fine particles may further contain daylight fluorescent pi~ment and/or other inorganic or organic pigments, which may be exhausted into the textile product simultaneously with the reversibly color changing fine particles.
This makes it 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.
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 ,:, . : , . . ,., :
,: , : , ., ,. ~:, ::

~ ~ ~ -2 ~

case of daylight fluorescent pigments, or 0.1 to 2% by weight in the case of other inorganic pigments or organic pigments.
Examples of daylight pigments 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.
These pigments can be used in the form of a dispersion of fine grains having a diameter oE 0.05 to 10~ m prepared by wet milling in water containing the anionio surfactant described above and the nonionic surfactant and wetting agent described above added as needed.
Also, in the presence of an anionic surfactant and if necessary noninonic surfactant, 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 ~ m in grain diameter.

,., ,, , , : , . :
: .. :: .. , : , ~ . .

Furthermore, it is also possible to color the textile product in advance and subject it to any one mode of the dyeing method of the present invention described above.
Accordingly, when any one of the dyeing methods described above is carried out after dyeing the textile produc~ with a direct dye or acid aye or after basically dyeing the te~tile 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.
PREPARATION EXAMPLES OF REVERSIBLY COLO~ CHANGING FINE
PARTICLES
Some preparation examples for reversibly color changing fine particles are given below. In the following description, "part(sj by weight~ are simply referred to as "part(s)".

-- preparation of thermochromic microcapsule containing three-component mixture --NC-R-l(pink) (trade mark, acid developing substance, product of Hodogaya Chemical Industry Co.) 1 par-t Bisphenol A 2 parts ~ ~ 3 2 ....

, :: .. , , .. . , . ,.,. .,: .

Bisbenzotriazole-5-methane 2 parts Lauryl palmitate 10 parts Cetyl alcohol 10 parts Tinuvin 326 (trademark , ultraviolet absorbent, product of Chiba-Geigy AG) 2 parts Epikote 828 (trade mark, epoxy resin, product of Yuka Shell Epoxy Co.) 6 parts A hot uniform molten mixture of the formulation described above was obtained by heating it. The molten mi~ture 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.
Then, 4 parts of an epoxy resin hardener (EPICURE U
(trad~n~rk), product of Yuka Shell Epoxy Co.) was added, and stirring was continued and the temperature was increased to 90 C , followed by reaction for 2 hours.
The solution was thereafter cooled, and the resulting microcapsule was 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.

-- preparation of photochromic microcapsule --100 parts of a dispersion containing 35% by weight of photochromic microcapsules was obtained in the same manner ~ ~, 3 3 . " ~
- ': , : ,.,, :: : ',,:, . : :
." ' '` "' , ,~ :'.~ ''.;'" : ~

- , , : .. , . , :
,,, ~ , .... . -: .: .
`.

2 0 ~

as in Preparation Example 1 except that 1 part of 1,3,3-trimethylspiro~indoline-2,3'-[3H]naphtho(2,1-h)(1,4)oxazine]
(organic photochromic compound) and 26 parts of bis(2,2,6,6-tetramethyl-4-piperidyl~sebacate were used in place of the NC-R-1, bisphenol A, bisbenzotriazole-5-methane, Lauryl palmitate, cetyl alcohol and Tinuvin 326 used in Prepara-tion Example 1.
PR~PA~ATION EXAMPLE 3 -- preparation of thermochromic microcapsule containing three-compo~ent mixture --150 parts of water, 7.5 parts of urea and 20 parts of37% formalin were mixed. This mixture was adjusted to a pH
of ~ with 10% sodium carbonate and stirred at 70~C or 1 hour to yield an aqueous solution containing an initial condensation product of urea and formaldehyde.
Then, to this solution, the molten mixture of the formulation described below was added dropwise with stirring, and stirring was continued at a stirring rate adjusted so that the grain diameter of this mixture became about 5 ~ m.
Y-1 (leuco dye (yellow), product of Yamamoto Kasei Co.) 1 part Bisphenol A 4 parts Myristyl alcohol 10 parts Lauryl palmitate 10 parts , ; :: :: ~: . . : :

- ,: ~ ~ ,. ;.:, :, :,. . . . ,. , .::: : ., , . :. .
. . : :;. . :.:, . : : : ~:
, : -. : ... : , : , :, ., :: : :: .
. .
, ~ . '- ' :
, ..... ... . . . . . .
.
.. .. .. .. .. . ...
:: :- '.

Tinuvin 326 2 parts 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, filtratio~ and drying to yield about 40 parts of microcapsules.
Next, the microcapsules described above was added to 100 parts of 2% carboxymethyl cellulose, and this mixture was stirred to y:ield a uniform dispersion.
To this dispersion, 100 parts of 2% polyvinyl alcohol was added. After the temperature was increased to 40C , 100 parts of 25% sodium chloride was gradually added with stirring, and the dispersion was subsequently cooled to 10C
, and 50% glutaraldehyde was added with additional stirring, followed by stirring for 15 hours.
After the temperat~re was increased to 40 ~C , the liquid was stirred at 40C 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.

-- preparation of photochromic microcapsule --2,2-diphenyl-3H-naphtho-(2,1-b)pyran 1 part Tinuvin 622LD (trademark , hindered amine compound, product , ~ 3 5 , ., -., ' ,,'~' !, ' ' '~
' ::`~
:.

of Chiba-Geigy AG) 2 parts Polystyrene resin 24 parts Toluene 56 parts Polymethylenephenyl isocyanate [MILLIONATE MR (trade mark, product of Nippon Polyurethane Industry Co., Ltd.)] 10 parts This formulation was stirred in a sand grinder to yield a uniform liquid mixture.
Separately, 500 parts of an aqueous solution containing 2 parts of colloidal calcium phosphate was prepared, to ~hich the uniform liquid mixture described above was added dropwise with stirring, followed by stirrin~ for about 1 hour at an adjusted stirring rate to yield a suspension of uniform dispersion of about 5 ~ m in average grain size with the almost all portion o~ the toluene evaporated.
Stirring was continued and 2 parts of xylylenediamine was added dropwise and the suspension was stirred for 3 hours, after which it was filtered, washed with water, and dried to yield about 38 parts of photochromic microcapsules.

-- preparation of photochromic microcapsule --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,l-b)(1,4)oxazine] a.nd 26 parts of SANOL
25 LS-77Cl (trade mark, hindered ami.ne compound, product of Sankyo Co., Ltd. ) were used in place of l part of . r~ ~

: . ,, : , ,, .. " . ,: ,, : ., :~

,,., , ,, . :
. . , . , , i : . ':: ' ,: ' ' ' ', ! ' -~: ' . ,: , , . ' ' ,. , . i , ' ': '.,, ' ~!, :: ' ' , ' ' '~ ' " " , ' .", : ' ' ':', . .: ' :: ' ," j ~ ,~ .. ,.,, ., : : ,: , , ' , ; . . , ,, , ' , '~, ': ': ' '' : ' ' '~,: ,' " ': ' " :: ' '~ ,,, :: :, :

2,2-diphenyl-3H-naphth o-(2,1-b)pyran, 2 parts of Tinuvin 622LD, 24 parts of polystyrene resin and 56 parts of toluene used in Preparation Example 4.

-- preparation of fine particle of photochromic matrix --8'- piperidino-1,3,3 trimethylspiro[indoline-2,3'-[3H]
naphtho(2,1-b)(1,4~oxazine] (organic photochromic compound) 1 part Mark LA-67 2 parts 10 DIANOL SE-5377 (trade mark, 40% by weight of polymethyl methacrylate resin, 60% by weight of xylene, product of Mitsubishi Resin Co., Ltd.) 60 parts ~ylene 20 parts The molten mixture of the formulation described above was added dropwise to a 3% aqueous solution of styrene/maleic anhydride copolymer with stirring.
And the mixture was stirred at 80 to 90 ~C for about 2 hours at an adjusted stirring rate to yield a suspension of uniform dispersed phase having about 5~ m average grain siza with the almost all portion of the xylene evaporated. The suspension was washed with water, filtrated and dried to yield 38.5 parts of fine particles of photochromic matrix involve about 0.5 part of styrene/maleic anhydride copolymer.

~ 3 7 ~,, ', , . . . ..

~- preparation of fine particle of thermochromic matrix Aqueous solution containing DEMOL N (trade mark, anionic surfactant, product oE Kao Co.) was heated to 90C .
To this solution, the molten uniform mixture of the formulation described below was added dropwise with stirring the solution.
NC-R-1 0.4 part ~isphenol A 1~6 part behenyl alcohol 3 parts Sanwax 151P (trade mark, low molecular weight polypropylene,~
product of Sanyo Kasei Kogyo Co.) 5 parts STAF~ENE E-715(trade , polyethylene resin, product of Nippon Sekiyu Kagaku Kogyo Co.) 50 parts Xylene 20 parts And the mixture was stirred at 90 ~C for a~out 2 hours to yield a suspension containing fine particles of 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.

-- preparation of thermochromic microcapsule containing three-component mixture having character of hysteresis --~ ,' 3 8 . ~,, :, ,, ... . . ,.: .

; . . , ~ ... . .; . , :
.. ,: . ,. . . , , , . : : . . .: : -:.. , . - : : . ~ :, ~ . .
~, ,... , . ~ , :. . . : , . ... . .
' , ' '",' ' ': ' .. ::

A dispersion involving 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.

EXAMPLES
Some examples are given below. But the present invention is not limited by these examples.

A cotton T-shirt (grey sheeting, 120 parts) was scoured to remove the sizing and impurities.
Next, 2400 parts of water (bath ratio = 1:20), 2 parts of SANFIX PAC-7 (trade mark, aqueous solution of quaternary ammonium salt type cationic polymer compound, product of Sanyo Kasei Kogyo Co.) and 10 parts of ethylene glycol were added to a 5-~ vat.
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.
Subsequently, the T-shirt was thoroughly rinsed with water to remove the excessive portion of the cationic compound and other additives, followed by dehydration.

=J~ 3 9 . ., ,.;-,.~, ,:

, .. : ~ .: ;

, .,, , . , , ;, . . .
~, , , , . ~ , ~5~

Next, 2400 parts oE water and 50 parts of a dispersion containing the 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.
This dispersion was pink before treatment, but it became a transparent colorless liquid after treatment (observation was made at 25~ ). This Einding demonstrates that the thermochromic microcapsules were completely exhausted into the cotton T-shirt.
Subsequently, this T-shirt was thoroughly rinsed and dehydrated, after which it was allowed to dry and then subjected to heat treatment at 140C in a tumbler drier for 1 minutes.
When the T-shirt thus obtained was worn, its entire surface changed in its color among white, distinct pink, pinkish white, etc. according to heat transmission from body temper~ture and minute changes in atmospheric temperature.
The appearance, handling touch, color fastness to rubbing and color fastness to washing of the T-shirt were all good.

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 i ~s O

-: . : : . .. . .. . - . :

:: , . .. . . .. . .
:, . . . .
:, ,: , , 20al~0~

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 irl Example 1.

A cotton T-shirt was treated in the same manner as in Example 1 except that the dispersion containing the photochromic microcaps~les 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 lS 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 was usea 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 ' , ' ,, ~ ; , , !,~ ~
' ~ ' , " ' " , ' ' ' ,' . '' ~ " " ' , '' , ' , ;' ` ' :, ' ' ~' ' / ."' ' ' ,;, . "' ', .' ' ' () 0 3 quality oE 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 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.
Color of this treated T-shirt changed among white~
blue, pink and deep purple reversibly through various paths by changing t~mperature or in the presence or absence of light irradiation. The guality 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 10 parts of the dispersion containing the thermochromic microcapsules o Preparation E~ample 1 and 8 parts o~ the photochromic microcapsules of Preparation Example 3 were used in pla~e 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 30C , while it became pink at about 25C , and it became deep orange at temperatures about below - :. ~, . : .
,. - :: , :: ..

.. .:; . ., . :, , . : ; , . . ', ., :: . , :-:
:, .~., , .. . ..

20C , 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.

First, 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 mark, 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.
The T-shirt was obtained in the same manner as in Example 1 except that the yellow dyed T-shirt was used in place of the scoured cotton T-shirt of Preparation Example 1 and the dispersion containlng the: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 maintained yellow at temperatures about over 20C as the temperature descend, ~ 1 4 3 ~. , ., , , ~ - ~

the color changed to deep orange again at temperatures about below 15C .
Accordingly, this T-shirt shows yellow and deep orange simultaneously at temperatures ranged 20 to 25C 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.
Next, an aqueous solution containing 3000 parts of water (bath ratio = 1:20), 1.5 parts of AMIGEN NF (trade mark, aqueous solution containing quaternary ammonium salt type cationic polymer compound about 30% by weight, product of Dai-ichi Kogyo Seiyaku Co., Ltd.) and 10 parts of ethylene glycol were added to a 5-~ vat. The T-shirt described above was i~mersed in this solution and gradually heated to 60C , at which temperature it was treated for 20 minutes.
Subsequently, this T-shirt was thoroughly rinsed with water and dehydrated. Next, 3000 parts of wa-ter 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 70C , at which temperature it was treated for 15 minutes to exhaust the photochromic microcapsule into this T-shirt.
Subsequently, this T-shirt was thoroughly rinsed with ' . , "' ' .,. .'.'. ' ' ~ , ' .,` , ' ' ' '' ' , , ,' " ' ' . ' ' ' "~ ' ',',' ' "' " ' ' , '' '' '' . "' .' ' ,,, '', ,' ~ " ' '' " ' ' ' . '' ' ' " '' . ~ ' '' ' ~ ' ; . ~ ' ' ' ,, ' ., "' ' ' ', , ~' ' .
, ' , ' ' ' ' " '~' ' ' ", ", . ,, ' . . . ; ', ' ' . ~ ~ ' , ' " , ' '1 ., ' ' ' ' ' ' ' water and dehydrated, after which it was subjected to tumbler drying for l 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.

A 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.
Next, 3000 parts of water and 15 parts (solid content =
about 4.5 parts) of MATSUMINSOL MR--10 (trade mark, acrylic ester resin binder, product of Matsui Shikiso Chemical Co., Ltd.) were added to the vat containing the T-shirt and this mixture was gradually heated to 70 C , at which temperature it was treated 15 minutes and then dehydrated and dried.
The obtained T-~hirt showed the same color changes as in Example 8 and had alomost equal appearance and touch to those oE the T-shirt of the Example 8. Moreover, the color fastness to rubbing and color fastness to washing were ~ j' 4 5 , "

,:
.
..

~OalOO~

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.
However a lot of photochromic microcapsules and binder were used in the water, 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.In addition, the color fastness to rubbing and colorfastness to washing were poorer than those of the T shirt ofExample 8.
Results of comparison of this T-shirt with the T-shirts obtained in Examples 8 and 9 are given in Table 1.

, , , - , , : : : :,: : . , , : :

::, ,. ,:: ,: . :.
- :
::,. . " . : , ,, :.; .
: ::, ..

2 0 ~

Table 1 _ Color Color Coloring Touch and fastness fastness density appearance to to . _ rubbing washing Nearly the touch and Example 8 100 appearance Grade 3 Grade 3 of cotton, ;~
with soft Almost the Example 9 100 same as in Grade 4 Grade 4 Example 8 Compara- Grade 2 Grade 2 tive 20 Hard to 3 to 3 Example 1 In Table 1, the color fastness to rubbing and color fastness to washing were evaluated on the basis of Japan Industrial Standard JIS L-0849 and L-0844 Method A-2, respectively.

A photochromic microcapsule was exhausted into a cotton T-shirt (150 parts, smooth knit) in the same manner as in Example 8 except that the photochromic microcapsules of Preparation example 5 was used in place of the photochromic microcapsules of Preparation example 4.
Subsequently, 15 parts (solid content = about 4.5 parts) of MATSUMINSOL MR-10 was added to the bath and the T-shirt was treated at 60 C for 15 minutes, after which it was dehydrated and dried.

. .

This T-shirt was found to be totally white under indoor conditions free of direct sun light, while it changed its color to deep purple at windows and outdoors under direct sun light.
This change could be reversibly repeated in cycles, and in addition the appearance, handling touch, color fastness to rubbing and color fastness to washing were as good as in Example 9.

A T-shirt was cationized in the same manner as in Example 8.
Subsequently, 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 MI2G (trade nark, 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.
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 - . , .: , : -:. : ,.

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sun light 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.

First, a cotton trainer (300 parts) was scoured to remove the sizing and impurities.
Next, to a 10-~ vat, 6000 parts of water, 2.7 parts of SANFIX 70 (trade mark, 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 ~ for 15 minutes and then thoroughly rinsed and dehydrated.
Next, 6000 parts of water was added to this vat, and 15 parts of the thermochromic microcapsule of Preparation example 3 were added and dispersed.
This dispersion was gradually heated to 70C , at which temperature it was treated for 15 minutes, after which it was thoroughly rinsed and dehydrated. Then, 6000 parts of water was added and 30 parts (solid content = about 9 parts) of HYDRIN AP~20 ~trade mark polyurethane resin emulsion, product of Dainippon Ink and Chemicals, Inc.) was added, and this solution was gradually heated to 70 C , at which temperature it was treated for 15 minutes, after which it was dehydrated and allowed to dry.

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This trainer was found to be yellow at temperaturesbelow about 20c , but it became white at about 25 C . This change could be reversibly repeated in cycles. In addition, the appearance, handling touch, color fastness to rubbing and color fastness to washing oE the trainer were as good as in Example 9.

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.
Next, 6000 parts of water was added to the vat containing this dehydrated cotton trainer, and 45 parts of the thermochromic microcapsules of Preparation example 3 and 30 parts of HYDRIN AP-20 were added and dispersed.
This dispersion was gradually heated to 80C , 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.

First, a cotton trainer (300 parts) was scoured to remove the sizing and impurities.
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(solid content - about 12 parts~ of CGC-102 (~rade mark, acrylate resin emulsion, product of Sumitomo Chemical Co., Ltd.) and 15 parts of ethylene glycol were added, and the trainer described above was immersed in this liquid and treated at 70 C for 15 minutes and then thoroughly rinsed and dehydrated.
Next, 6000 parts of water was added to this vat, and 45 parts of the thermochromic microcapsules of Preparation example 3 and 6 part of PG BLUE-MI-IB (trademark, aqueous dispersion containing blue organic pigment about 20% by weight, product of Matsui Shikiso Chemical Co., Ltd.) were added and dispersed.
This dispersion was gradually heated to 80C , 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 25C as the color of the microcapsules disappeared.
This change could be reversibly repeated in cycles. In addition, the appearance, handling touch, color fastness to rubbing and color fastness to washing of the trainer were ! 5 1 ~s~

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as good as in Example 12.

A trainer as used in Example 12 was scoured. 6000 parts of water and 6 parts of KAYARUS Black G conc (trade mark, 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.
Next, 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 crystal.
This trainer reversibly changed its color clearly among red, yellow, green, blue and purple at temperatures ranged about 18 to 30C . The quality of the trainer was as good as that of the trainer of Example 12.
The thermochromic microcapsule involving above described liquid crystal can be obtained by carrying out coacervation method using the liquid crystal consisting of cholesterol nonanate, cholesterol benzoate and cholesterol oleyl carbonate whose ratio is 1:1:1 by weight, gelatin and gum arabic.

Cotton jeans was scoured in a Smi-th drum dyeing machine.

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Next, this jeans was squeezed and was immersed in an aqueous liquid (bath ratio = 1:15) containing 2% by weight of AMIGEN NF relative to the jeans and 10% by weight (solid content = about 4% by weight relative to the jeans) of CGC-102, it was treated for 2 minutes at 30C .
Subsequently, 0.3% by weight of NaOH relative to the jeans was added to the liquid, after treated for 10 minutes at 30 C , rinsed and dehydrated.
Next, this jeans was immersed in an aqueous liquid (bath ratio = 1:15) containing 10% by weight of thermochromic microcapsules of Preparation example 3 relative to the jeans and 4% by weight of PG BLUE-MI-IB relative to the jeans, treated for about 10 minutes at 75 C , rinsed and allowed to dry. In addition, the jeans was subjected to heat treatment at 140 C for 3 minutes.
This jeans was found to be stripe pattern of white and dark green at temperatures below about 20 C by mixing blue of the organic pigment and yellow of the thermochromic microcapsules, but it became stripe pattern o~ white and blue at temperatures about over 25C as the color of the microcapsules disappeared.
This change could be reversibly repeated in cycles. The appearance and handling touch were almost equaly good to untreated jeans, color fastness to rubbing and color fastness to washing thereof were as good as in Example 12.

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The same procedures as in E~amples 1, 6, 8 and 10 were followed e~cept that no cationic compound was used.
The respective products thus obtained were found to have no commercial value because their coloring density was as low as about 10% in comparison with the clothes of Examples.

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Claims (36)

1. Dyeing method comprising:
a process of treating a cellulose fiber textile product with cationic compound; and another process of treating the thus-treated textile product by immersing it in a dispersion containing reversibly color changeable fine particles which involve thermochromic or photochromic material in high polymer compound.

2. Dyeing method comprising:
a process of treating a cellulose fiber textile product with cationic compound;
another process of treating the thus-treated textile product by immersing it in a dispersion containing reversibly color changeable fine particles which involve thermochromic of photochromic material in high polymer compound; and still another process of further treating the textile product by adding binder to the dispersion in an amount insufficient to spoile the appearance and touch of the dyed product.

3. Dyeing method comprising:
a process of treating a cellulose fiber textile product with cationic compound;
another process of treating the thus-treated textile product by immersing it in a dispersion containing reversibly color changeable fine particles which involve thermochromic or photochromic material in high polymer compound; and still another process of further treating the textile product by immersing it in water containing binder in an amount insufficient to spoile the appearance and touch of the dyed product.

4. Dyeing method comprising:
a process of treating a cellulose fiber textile product with cationic compound; and another process of treating the thus-treated textile product by immersing it in a dispersion containing a) reversibly color changeable fine particles which involve thermochromic or photochromic material in high polymer compound and b) binder in an amount insufficient to spoile the appearance and touch of the dyed product.

5. Dyeing method comprising:
a process of treating a cellulose fiber textile product with cationic compound and binder in an amount insufficient to spoile the appearance and touch of the dyed product; and another process oftreating the thus-treated textile product by immersing it in a dispersion containing reversibly color changeable fine particles which involve thermochromic or photochromic material in high polymer compound.

6. Dyeing method comprising:
a 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; and another process of treating the thus-treated textile product by immersing it in a dispersion containing reversibly color changeable fine particles which involve thermochromic or photochromic material in high polymer compound.

7. Dyeing method of claim 1, 2, 3, 4, 5 or 6 wherein said textile product is colored in advance.

8. Dyeing method of claim 1, 2, 3, 4, 5 or 6 wherein said particles consist of fine particles involving thermochromic material in high polymer compound and fine particles involving photochromic material in high polymer compound.

9. Dyeing method of claim 1, 2, 3, 4, 5 or 6 wherein said particles contain dispersed thermochromic material selected from the group consisting of a) three-component mixture of acid developing substance, acidic substance and solvent, b) two-component mixture of acid developing substance and acidic substance and c) cholesteric liquid crystal in matrix of synthetic resin.

10. Dyeing method of claim 1, 2, 3, 4, 5 or 6 wherein said particles contain thermochromic material selected from the group consisting of a) three-component mixture of acid developing substance, acidic substance and solvent, b) two-component mixture of acid developing substance and acidic substance and c) cholesteric liquid crystal in high polymer microcapsules.

11. Dyeing method of claim 1, 2, 3, 4, 5 or 6 wherein said particles contain dispersed organic photochromic substance in matrix of synthetic resin.

12. Dyeing method of claim 1, 2, 3, 4, 5 or 6 wherein said particles contain dispersed organic photochromic substance in matrix of synthetic resin which capsulated in high polymer microcapsules.

13. Dyeing method of claim 1, 2, 3, 4, 5 or 6 wherein said particles contain solved or dispersed organic photochromic substance in medium which capsulated in high polymer microcapsules.

14. Dyeing method of claim 1, 2, 3, 4, 5 or 6 wherein the diameters of said particles are not exceeding 50µ m.

15. Dyeing method of claim 1, 2, 3, 4, 5 or 6 wherein said particles are contained in the dispersion in a ratio of 0.1 to 50% by weight relative to the textile product.

16. Dyeing method of claim 1, 2, 3, 4, 5 or 6 wherein the cationic compound is selected from the group consisting of quaternary ammonium salts, pyridinium salts, dicyandiamides, polyamines and polycations.

17. Dyeing method of claim 10, 12 or 13 wherein the coat former for the high polymer microcapsule is one or more kinds of high polymer compound selected from the group consisting of polyurea, polyamide, polyester, polyurethane, epoxy resin, urea resin, melamine resin, gelatin, ethyl cellulose, ethylene/maleic anhydride copolymer, butylene/maleic anhydride copolymer, vinyl ether/maleic anhydride copolymer, anion-modified polyvinyl alcohol, gum arabic and carboxymethyl cellulose.

18. Dyeing method of claim 13 wherein said medium is one or more kinds selected from the group consisting of high boiling solvents, plasticizers, synthetic resins, hinderedamine compounds and hindered phenol compounds.

19. Dyeing method of claim 1, 2, 3, 4, 5 or 6 wherein said dispersion further contains pigment.

20. Dyeing method of claim 2, 3, 4, 5 or 6 wherein said binder is selected from the group consisting of acrylic resin, vinyl acetate resin, polyurethane resin, polyester resin, styrene-butadiene latex and polyolefin resin.

21. Dyeing method of claim 2, 3, 4, 5 or 6 wherein the amount of said binder is 0.1 to 10% by weight of binder solid content relative to the textile product.

22. A dyed product, said product being 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.

23. A dyed product, said product being cellulose fiber textile product pretreated with cationic compound, dyed with reversibly color changeable fine particles which involve thermochromic or photochromic material in high polymer compound and treated with binder in an amount insufficient to spoile the appearance and touch of the dyed product.

24. A dyed product, said product being cellulose fiber textile product pretreated with cationic binder in an amount insufficient to spoile the appearance and touch of the dyed product and dyed with reversibly color changeable fine particles which involve thermochromic or photochromic material in high polymer compound.

25. The dyed product of claim 22, 23 or 24 wherein said textile product is colored in advance.

26. The dyed product of claim 22, 23 or 24 wherein said particles consist of fine particles involving thermochromic material in high polymer compound and fine particles involving photochromic material in high polymer compound.

27. The dyed product of claim 22, 23 or 24 wherein said particles contain dispersed thermochromic material selected from the group consisting of a) three-component mixture of acid developing substance, acidic substance and solvent, b) two-component mixture of acid developing substance and acidic substance and c) cholesteric liquid crystal in matrix of synthetic resin.

28. The dyed product of claim 22, 23 or 24 wherein said particles contain thermochromic material selected from the group consisting of a) three-component mixture of acid developing substance, acidic substance and solvent, b) two-component mixture of acid developing substance and acidic substance and c) cholesteric liquid crystal in high polymer microcapsules.

29. The dyed product of claim 22, 23 or 24 wherein said particles contain dispersed organic photochromic substance in matrix of synthetic resin.

30. The dyed product of claim 22, 23 or 24 wherein said particles contain dispersed organic photochromic substance in matrix of synthetic resin which capsulated in high polymer microcapsules.

31. The dyed product of claim 22, 23 or 24 wherein said particles contain solved or dispersed organic photochromic substance in medium which capsulated in high polymer microcapsules.

32. The dyed product of claim 22, 23 or 24 wherein the diameters of said particles are not exceeding 50µ m.

33. The dyed product of claim 22, 23 or 24 wherein the cationic compound is selected from the group consisting of quaternary ammonium salts, pyridinium salts, dicyandiamides, polyamines and polycations.

34. The dyed product of claim 28, 30 or 31 wherein the coat former for the high polymer microcapsule is one or more kinds of high polymer compound selected from the group consisting of polyurea, polyamide, polyester, polyurethane, epoxy resin, urea resin, melamine resin, gelatin, ethyl cellulose, ethylene/maleic anhydride copolymer, butylene/maleic anhydride copolymer, vinyl ether/maleic anhydride copolymer, anion-modified polyvinyl alcohol, gum arabic and carboxymethyl cellulose.

35. The dyed product of claim 31 wherein said medium is one or more kinds selected from the group consisting of high boiling solvents, plasticizers, synthetic resins, hinderedamine compounds and hindered phenol compounds.

36. The dyed product of claim 23 or 24 wherein said binder is selected from the group consisting of acrylic resin, vinyl acetate resin, polyurethane resin, polyester resin, styrene-butadiene latex and polyolefin resin.