Note: Descriptions are shown in the official language in which they were submitted.
- 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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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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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
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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
,
.. ''' . ,,',: ' ;' '
"' '': .: ', ,:.' ,'' , .
2 ~
~; 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
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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
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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
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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,
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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.
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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,
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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
1 6
:
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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- , , :.: . ,:, : - ::: . ,
-: , :: , , ,
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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
1 9
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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]-
2 0
,
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
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,, : ,
20~0~
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
.
. . .
,:,', . . :
': ' ' : , : '
. :, . : .
~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
2 2
:: . .- .: . . . . .
::: : ~ ,
- . , - -, :, ::,.. .. ,. , :
:,
, , ,~ ' , , ,. ":' ,
: . ~ , : ., .: ,
~, : , , : ::. ,. :,:: :: :
~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 3
, ~- , . , ., : :
.
,
. .
. . , : , , " : .. ,
, : . . : .. ,
. . .
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 5
:., ~ . :
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 6
,, , ~ ,~ ;,,: "; ,,: ,,:, - , :
" ,:
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
2 9
,- ~, , ~ ,
. . .
. :' "
:' ' ' '
.', ' ' .
. . ' , , , '
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
3 0
,:, . : , . . ,., :
,: , : ,
., ,. ~:, ::
~ ~ ~ -
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 EXAMPLE 1
-- 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 EXAMPLE 2
-- 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
3 4
, ; :: :: ~: . . : :
- ,: ~ ~ ,. ;.:,
:, :,. . . . ,. , .::: : ., , . :. .
. . : :;. . :.:, . : : : ~:
, : -. : ... : , : , :, ., :: : :: .
. .
, ~ . '- ' :
, ..... ... . . . . . .
.
.. .. .. .. .. . ...
:: :- '.
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 EXAMPLE 4
-- 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 EXAMPLE 5
-- 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 EXAMPLE 6
-- 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.
PREPARATION EXAMPLE 7
~ 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 EXAMPLE 8
-- 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.
EXAMPLE 1
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.
EXAMPLE 2
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.
EXAMPLE 3
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.
EXAMPLE 4
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
4 1
' , ' ,, ~ ; , , !,~ ~
' ~ ' , " ' " , ' ' ' ,' . '' ~ " " ' , '' , ' , ;' ` '
:, ' ' ~' ' / ."' ' ' ,;, . "' ', .' '
'
() 0 3
quality oE the T-shirt was as good as in Example 1.
EXAMPLE 5
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.
EXAMPLE 6
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
4 2
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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.
EXANPLE 7
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
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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.
EXANPLE 8
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
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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.
EXAMPLE 9
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
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better than those of the T-shirt of Example 8.
COMPARATIVE EXAMPLE 1
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.
4 6
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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.
EXAMPLE 10
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.
4 7
. .
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.
EXAMPLE 11
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
4 8
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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.
5EXAMPLE 12
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.
4 9
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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.
EXAMPLE 13
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.
EXAMPLE 14
First, a cotton trainer (300 parts) was scoured to
remove the sizing and impurities.
Next, to a 10-~ vat, 6000 parts of water, 30 parts
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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
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as good as in Example 12.
EXAMPLE 15
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.
EXAMPLE 16
Cotton jeans was scoured in a Smi-th drum dyeing machine.
~ 5 2
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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.
5 3
, . . .
2~ oa~
COMPARATIVE EXAMPLES 2 THROUGH 5
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.
5 4
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