Note: Descriptions are shown in the official language in which they were submitted.
2 ~
Aroma~imparting method and aroma-emitting textile product
_
The present invention relates to an aroma-imparting
method for making a textile product emit an aroma, and an
aroma-emitting textile product.
To make a textile product emit an aroma, there can be
employed a method whereln the textile product is printed
with a printing paste which contains a synthetic resin and
which is supplemented with a perfume as such, and a method
wherein the textile product is padded with a dispersion
liquid containing a synthetic resi~ and a perfume as such.
However, the aroma emitted by the thus-obtained textile
products is rapidly lost due to volatilization, though it
is initially strong. In addition, there have been trouble
of staining of ~ther textile products with the volatilized
perfume during product storage (perfume transfer) and
drawback of loss of almost all perfume component in a
single time of washing in the consumption stage.
A perfume-containing microcapsule, wherein a perfume is
contained in a microzapsule which is to be broken by an
external force such as friction, emits an aroma upon
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capsule break; the aroma is hardly lost due to
volatilization before capsule break.
Thus, if it is possible to strongly fix such
perfume-containing microcapsules to a textile product and
allow an appropriate amount of microcapsules to break
relatively constantly over a long period of time during use
of the textile product, a textile product can be obtained
which emits an appropriate aroma relatively constantly
over a long period of time, which is free of the problem of
aroma transfer during storage and which is excellent in
washing fastness.
When a textile product is padded with a dispersion liquid
containing perfume-containing microcapsules and a synthetic
resin, the amount of microcapsules fixed to the textile
product is relatively low, but the degree of spoilage of
the appearance of the obtained textile product is also
relatively low. Also~ when a textile product is printed
with a printing paste WhiCh contains a large amount of
synthetic resin and which is supplemented with
perfume-containing microcapsules, in accordance with the
method disclosed in Japanese Patent Examined Publication
No. 47440/1978, a large amount of microcapsules can be
fixed to the textile product, but the degree of spoilage of
the appearance of the obtained textile product is also
great. Moreover, none of these methods makes it possible to
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produce a textile product which emits a satisfactory aroma
relatively constantly over a long period of time.
The object of the present invention is to provide an
aroma-imparting method which makes it possible to strongly
fix a large amount of perfume-containing microcapsules
to a textile product and allow an appropriate amount of
microcapsules to break and emit an appropriate aroma
relatively constantly over a long period of time during use
of the textile product, and an aroma-emitting textile
product wherein perfume-containing microcapsules are
fixed strongly and in a large amount and an appropriate
amount of microcapsules break to emit an appropriate aroma
relatively constantly over a long period of time during use
of the textile product.
The aroma-imparting method of the present invention
comprises the steps of:
cationizing a textile product with a liquid containiny a
nitrogenous cationic compound; and
subjecting the cationized textile product to a
capsule-fixing treatment with a capusule-dispersion liquid
wherein perfume-containing microcapsules are dispersed, the
perfume-containing microcapsule containing at least a
perfume in a microcapsule which is made essentially of a
polymer compound, to fix the perfume-containing
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microcapsules to the textile product.
Also, the aroma-emitting textile product of the
present invention is a textile product cationized by a
nitrogenous cationic compound and fixed with
perfume-containing microcapsules, the perfume-containing
microcapsule containing at least a perfume in a
microcapsule which is made essentially of a polymer compound.
According to the aroma-imparting method of the present
invention, a large amount of perfume-containing
microcapsules can be strongly fixed to a textile product
without spoiling the appearance and touch thereof, very few
perfume-containing microcapsules drop from the textile
product due to washing, and there .is no problem of aroma
transfer during storage of the textile product. The textile
product emits an appropriate aroma as an appropriate
amount of microcapsules break due to friction etc. during
use relatively constantly over a long period o$ time.
Also, when the textile product is subjected to a binder
treatment in addition, perfume-containing microcapsules
fixation to the textile product is enhanced with scarcely
spoiling the appearance or touch thereof, and the
aroma-emitting action of the textile product, almost
equivalent to that without the binder treatment, is
retained for a long period of time.
The aroma-emitting textile product of the present
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invention emits an appropriate aroma as an appropriate
amount of microcapsules break due to friction etc. during
use relatively constantly over a long period of time, very
few perfume-containing microcapsules drop due to washing,
and there is no problem of aroma transfer during storage.
In addition, the appearance and touch of the original
te~tile product is retained.
Also, in case that the aroma-emitting textile product of
the present invention is treated with a binder in an amount
such that the appearance or touch of the textile product is
not spoiled, perfume-containing microcapsule fixation to the
textile product is enhanced, and the aroma-emitting action,
almost equivalent to that without the binder treatment, is
retained for a long period of time.
Textile products
~ xamples of fiber used in the textile product of the
present invention include cellulose fibers such as cotton
and hemp, protein fibers such as wool and silk, regenerated
fibers such as viscose rayon fiber, semi-synthetic fibers
such as acetate fiber, and synthetic fibers such as
polyamide fiber, polyester fiber, acrylic fiber and
polyurethane fiber.
Examples of the textile product for the present
invention include yarns, slivers, loose fiber, fabrics,
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knittings, unwoven fabrics, and sewed products such as
clothings using these fabrics, knittings or unwoven
fabrics. Examples of sewed products include T-shirts, sweat
shirts, jumpers, jeans, socks, bags and caps. The textile
product of the present invention need not consist of a
single kind of fiber. For example, the yarn may be a mixed
yarn of one or more kinds of fiber selected from the
above-mentioned fibers, and the fabric may be an interwoven
product of two or more kinds of yarn.
Also, the textile product for the present invention may
have previously been colored by dyeing etc.
Nitrogenous cationic compounds
The nitrogenous cationic compound for the present
invention is exemplified by
alkylammonium salt type compounds,
pyridinium salt type compounds,
dicyandiamide type compounds,
polyamine type compounds and
polycation type compounds.
Examples of nitrogenous cationic compounds are given
below.
Examples of alkylammonium salt type compounds include
alkylammonium salt type cationic surfactants such as
trimethyloctadecylammonium chloride,
trimethylhexadecylammonium chloride,
- 7 ~ ~1016~
trimethyllaurylammonium chloride,
dimethyllaurylammoniumchloride,
laurylm~thylammonium chloride,
lauryldimethylbenzylammonium chloride,
alkylben~yldimethylammonium chloride,
stearylbenzyldimethylammonium chloride and
alkyltrimethylammonium chloride;
2,3-epoxypropyltrimethylammonium chloride;
3-chloro-2-hydroxypropyltrimethylammonium chloride; and
triazine-ring-containing alkylammonium salt compounds such
as those disclosed in Japanese Patent Unexamined
Publication Nos. 155285/1977 and 155286/1977.
Examples of pyridinium salt type compounds include
pyridinium salt type cationic surfactants such as
laurylpyridinium chloride and
stearylamidomethylpyridinium chloride.
Examples o~ dicyandiamide type compounds include
formalin condensation products of dicyanamide.
Examples of polyamine type compounds include
condensation products of polyalkylenepolyamine and
guanidine derivative,
polyethyleneimines and
polyamidopolyamines.
Examples of polycation type compounds include
poly-4-vLnylpyridine hydrochlorlde,
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1:
polyacrylonitrile polymers and other tertiary amine
polymers such as those disclosed in Japanese Patent
Unexamined Publication No. 64186/1979,
dimethylamine-epichlorohydrin condensation products such as
those disclosed in Japanese Patent Examined Publication No.
243/1968,
2-methacryloxypropyltrimethylammonium salt polymers such
as those disclosed in Japanese Patent Une~amined
Publication No. 112480/1982,
dimethyldiallylammonium chloride polymers such as those
disclosed in Japanese Patent Unexamined Publication No. :
76177/1980,
polyepichlorohydrin-trimethylamine reaction products such
as those disclosed in Japanese Patent Unexamined .
Publication No. 112987/1976,
quaternary l-vinylimi~azole polymers, e.g. as disclosed in
Japanese Patent Unexamined Publication No. 210083/1982,
polymers of quaternary epoxypolyalkylenepolyamines e.g.
as disclosed in Japanese Patent Unexamined Publication Nos.
9979/1985 and 9980/1985,
copol~mers of acrylamide and cationic monomers which can
copolymerize with the acrylamide, e.g. as disclosed in
Japanese Patent Unexamined Publication No. 47309/198~,
cationic polymers containing a quaternary ammonium base
d1sclosed in Japane~ Patent Vnexamined ~ublicatlon No.
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234007/~88,
quaternary ammonium salt type polymers such as quaternary
salts of aminoalkylacrylamide polymers disclosed in Japanese
Patent Unexamined Publication No. 284225/1988,
the polymer comprising the following monomer unit:
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H2~ ~H2
\~/
CÇa CH3 n
wherein X is halogen such as Cl, Br, etc., n is 50-20,000,
and Rl and R2 is each an alkyl group having up to 20 carbon
atoms,
disclosed in Japanese Patent Unexamined Publication No.
128382/1981,
the polymer comprising the following monomer unit:
[ /N\
R, Rz n
wherein X is halogen such as Cl, Br, etc., n is 50-20,000,
and Rl and Rz is each an alkyl group having up to 20 carbon
atoms,
(SHALLOL DC (trade name) series, product of Dai-ichi Kogyo
Seiyaku Co., Ltd.), and
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and copolymers of quaternary ammonium salts and other vinyl
monomers.
Of these nitrogenous cationic compounds,
polyamine type compounds;
dicyandiamide type compounds; and
polycation type compounds such as
quaternary ammonium salt type polymers, and
copolymers of quaternary ammonium salts and other vinyl
monom~rs
are particularly effective in the present invention.
Liquids containing a nitro~enous cationic compound
=
Examples of liquids containing a nitrogenous cationic
compound include aqueous solutions or aqueous dispersions
containing a nitrogenous cationic compound and printing
pastes containing a nitrogenous cationic compound.
C onizing treatment
Cationization can be conducted for a part or all
portion oE the textile product, for example, in a state
wherein the textile product is immersed in an aqueous
solution containing a nitrogenous cationic compound. The
treatment can also be carried out by spraying such an
aqueous solution on the textile product or by printing a
printing paste containing a nitrogenous cationic compound
on the textile product.
Perfumes
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Pexfumes which can be used for the present invention
include water-insoluble or sparingly water-soluble natural
and synthetic perfumes. These perfumes may be used in
optional combinations, with auxiliaries ~.g.
perfume-liEe-extending fixatives and modifiers added as
necessary. By combining one or more kinds of perfumes and
auxiliaries, it is possible to obtain aromas of natural
flowers such as lily of the valley, lavender, violet, rose,
jasmine, carnation, lilac, hyacinth, lily, gardenia and
heliotrope;
aromas of fruits such as banana, apple, pineapple, cherry
and grape;
musk;
and other imaglnary or 111usionary refreshing aromas.
Examples of the above-mentioned natural perfumes
include
animal perfumes such as musk, civet, castreum and ambergris;
vegetable perfumes such as pinene, citronellol, geraniol,
linalool, citral, citronellal, eugenol, safrole and
menthol; and
essential oils such as anise oil, kuromoji oil, abies oil,
citronella oil, camphor oil, cinnamon oil, jasmine flower
oil, spearmint oil, cedar oil, geranium oil, clove oil,
tuberose oil, turpentine oil, neroli oil, peppermint oil,
palmarosa oil, hiba oil and rosemary oil~
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Examples of the above~mentioned synthetic perfume~
include terpene-based synthetic perfumes such as myrcene,
carvone, oxycitronellal, terpineol, hydrated terpin,
1-menthol, borneol, camphor, ionone and methylionone; and
aromatic and alicyclic synthetic perfumes such as benzyl
alcohol, ~ -phenylethyl alcohol, phenylacetaldehyde,
cinnamaldehyde, a -amylcinnamaldehyde, cyclamen aldehyde,
anisaldehyde, anethole, ~ -naphthol methyl ether,
heliotropin, ethylvanillin, coumarin, isoamyl salicylate,
methyl anthranilate, methyl methylanthranilate, vanillin,
methylvanillin, rosephenone, alpha phenylpropyl acetate,
musk ketone, musk amblet, leaf alcohol, jasmone,
r -undecalactone and Versalide (trademark~.
Examples of the above-mentioned fixatives include ethyl
benzoate, ethyi phthalate, benzyl salicylate, heliotropin,
ethylene brassylate, iris oil and 10-oxahexadecanolide.
Exampleæ of the above-mentioned modifiers include
higher aliphatic aldehydes and isoeugenol.
Perfume-containing microcapsules
Containing of at least a perfume in microcapsules
made essentially of a polymer compound can be achieved by,
for example, the method described below.
By carrying out a known capsulation method on a perfume
described above with auxiliaries and a polymer compound as
coat former, and where necessary a surfactant, a
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protective colloid, a pH regulator, an electrolyte and
other additives, perfume-containing microcapsules can be
obtained in the form of, for example, an aqueous dispersion.
Microcapsulation methods include chemical methods such
as interfacial polymerization, in situ polymerization and
in-liquid setting coating; physicochemical methods such as
phase separation, coacervation and interfacial separation;
and mechanical methods such as spray drylng, air suspension
coating, the powder bed method and vacuum deposition.
Also, multiple-layere~ microcapsules can be obtained by
carrying out one or more kinds of these capsulation
methods two or more times repeatedly. In any case, it is
necessary to appropriately adjust microcapsule strength so
that an appropriate amount of microcapsules break due to
friction etc. during use of the textile product to emit an
appropriate aroma relatively constantly over a long period
of time, according to the application, with microcapsule
particle size, coat thickness and coat material in mind.
The particle size of the perfume-containing
microcapsules is preferably 0.1 to 100~ m. Particle sizes
of under 0.1~ m result in difficulty in capsule break; in
ordinary uses of the textile product, such as motion of the
worn clothing, the textile product hardly emits aroma in
many cases. If the particle slze exceeds 100~ m, most
capsules are broken by a minor external force, often
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resulting in perfume diffusion during production
processes. More preferably, the particle size of the
perfume-containing microcapsul2s is 1 to 50 ~ m. Within
this particle size range, capsules break relatively easily
in ordinary use of the textile product to emit an
appropriate aroma, and perfume diffusion due to capsule
break during production processes is hardly caused.
Examples of preferred coat formers include
polyisocyanate and polyamine for forming a polyurea coat,
polybasic acid chloride and polyamine for forming a
polyamide coat,
polyisocyanate and polyhydroxyl compound for forming a
polyurethane coat,
polybasic acid chloride and polyhydroxyl compound for
forming a polyester coat,
epoxy compound and polyamine for forming an epo~y resin
coat,
melamine-formalin prepolymer for forming a melamine coat,
uréa-formalin prepolymer for forming a urea resin coat,
ethyl cellulose,
polystyrene,
polyvinylacetate, and
later described anionic polymer compounds and amphoteric
polymer compounds.
It is preferable that the coat for the microcapsules
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described above be thermosetting because of the excellent
heat resistance thereof.
Examples of prefe~ably usable surfactants and
protective colloids include
anionic surfactants,
amphoteric surfactants,
anionic polymer compounds and
amphoteric polymer compounds. In addition, non-ionic
surfactants can be used in combination with these.
The usual pH regulator and electrolyte used in the
above capsulation methods are usable herein for the same
purposes.
In the present invention, it is possible to use the
perfume-containing microcapsules dispersed in an liquid
dispersion which is obtained as mentioned above. From this
aqueous dispersion, the surfactant and protective colloid
may be removed to such an extent that it is possible to
maintain the dispersion of the microcapsules. Powdery
microcapsules obtained by dehydration and drying are also
usable. When the powdery microcapsules are used, they are
dispersed in the liquid with the surfactant and protective
colloids as needed. If the microcapsules have high
dispersibility, the surfactant and protective colloid are
not necessary. Microcapsules, whose coat is formed of an
anionic polymer compound or amphoteric polymer compound,
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often have enough dispersibility.
Examples of the above-mentioned anionic surfactants
include
alkyl sulfates,
alkyl henzene sulfonates,
alkyl naphthalene sulfonates,
alkyl ulfosuccinates,
alkyl diphenyl ether disulfonates,
alkyl phosphatesj - :
polyoxyethylene alkyl sulfates,
polyoxye~hylene alkylaryl sulfates,
polyoxyethylene alkyl ether sulfates,
polyo~yethylene alkylphenyl ether sulfates,
polyoxyethylene polystyrylphenyl ethPr sulfates, and
polyoxyethylene alkyl phosphates.-
Examples o~ the above-mentioned anionic polymer
compounds 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,
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gum arabic,
carboxymethyl cellulose,
hydroxyethyl cellulose,
hydroxypropyl cellulose, and
starch derivatives.
Examples of the above-mentioned amphoteric polymer
compounds include gelatin and case~n.
Examples of the above-mentioned nonionic surfactants
include
polyoxyethylene alkyl ethers-,
polyoxyethylene alkylaryl ethers, and
other polyoxyethylene derivatives;
polyoxyethylene-polyoxypropylene block copolymers,
aliphatic esters of sorbitan,
~atty acid esters of polyoxyethylene sorbito1J and
fatty acid esters of glycerol.
The perfume-containing microcapsules may be colored
with a coloring agent so that the perf~me-containing
microcapsules impart color simultaneously with aromaf, to
the textile product. The coloring of the perfume-containing
microcapsules can be achieved by, for example, adding a
coloring agent to the coat former in production process of
the perfume-containing microcapsules.
Examples of the coloring agent include various organic
pigments such as insoluble azo pigments, phthalocyanine
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pigments, vat dye pigments, basic dye lakes and acid dye
lakes; inorganic pigments such as titanium white, chromium
yellow, cadmium red, iron oxide, carbon black and
ultramarins; direct dyes; acid dyes; reactive dyes; and
basic dyes. It is also possible to use, for example,
fluorescent pigments, oil-soluble dyes, disp~rse dyes,
solid-solution type daylight fluorescent pigmPnts.
Capsule-dispersion liquids
Capsule dlspersion liquids include aqueous dispersion
containing perEume-containing microcapsules dispersed
therein and printing pastes containing perfume-containing
microcapsules dispersed therein.
Capsule-fixing treatment
Capsule-fixing treatment can be conducted for a part or
all portion of the textile product, for example, in a
manner wherein the textile product is immersed in an aqueous
dispersion containing perfume-containing microcapsules
dispersed therein. The treatment ca~ also be achieved by
spraying such an aqueous dispersion on the textile product
or by printing a printing paste containing perfume-containin
microcapsules dispersed therein on the textile product.
Examples of aroma-imparting process
.
A textile product can be imparted with an aroma by the
aroma-imparting method of the present invention for example
as follows:
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The textile product described above is first scoured,
i.e. scrubbed vigorously, to remove thickening agent and
impurities. Scouring i5 of course unnecessary when the
textile product is clean.
Next, to an appropriate immersion bath vat, water is
added in a weight amount 5 to 50 times the weight amount of
the textile product (bath ratio 5:1 to 50:1), preferably 10
to 30 times (bath ratio 10:1 to 30:1), followed by addition
of a nitrogenous cationic compound in a ratio o~ 0.1 to 20%
by weight, preferably about 0.3 to 5% by-weight, relative
to the untreated textile product. An acid such as acetic,
tartaric, oxalic or malic acid may be added to adjust the
pH to the acidic side, or an alkali such as caustic soda or
sodium carbonate may be added to adjust the pH to the
alkaline side. A wetting agent such as urea, glycerol,
eth~lene glycol, polyethylene glycol and diethylane glycol
may also be added as necessary 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 (an example liquid
containing a nitrogenous cationic compound), and the
temperature is maintained at normal to about 80 C for
about 5 to 30 minutes, whereby the textile product is
efficiently cationized, i.e. it is cationically modified to
render its surface receptive to adsorption and adherence of
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the perfume-containing microcapsules.
Subsequently, this textile product is thoroughly rinsed
to wash down the excess portion of th~ nitrogenous cationic
compound and other additives, and then dewatered, i.e.
squeezed to damp condition.
Next, to the meanwhile emptied vat containing the
thus-treated textile product, water is added in a weight
ratio of about 5:1 to 50:1, preferably 10:1 to 30:1,
relative to the untreated te~tile product, and the
perfume-containing microcapsules as described above are
added and dispersed in a ratio of 0.1 to 50% by weight,
preferably 1 to 2;5% by weight, relative to the untreated -
textile product. The perfume~containing microcapsules may
be added in the form of a dispersion 1iquid containing them.
The cationized textile product is treated in the
dispersion liquid thus obtained (an e~ample
capsule-dispersion liquid) at normal temperature to about 90
C for about 5 to 30 minutes, whereby the perfume-containing
microcapsules are almost completely exhausted into the
cationized textile product, in that the dispersed
microcapsules are taken up by the textile product so that
essentially no perfume containing microcapsules are left in
the liquid remaining in the vat. This treating temperature
is preferably about 60 to 90C when using the
perfume-containing microcapsules described above at high
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concentrations of 10 to 50~ by weight.
This -treatment results in the binding of the
perfume-containing microcapsules described above to the
textile product described above by chemical ionic bonding
and physical adsorption. This product is then dewatered
(squeezed damp) and dried, whereby the perfume-containing
microcapsules are firmly and in a large amount fixed to the
textile product. For enhancing this fixation, it is
preferable that the textile product is conducted a heat
treatment at about 80 to 180C for about 0.5 to 10 minutes
after drying.
The textile product thus obta:ined has a large amount of
perfume-containing microcapsules fixed thereto, retains
the soft touch of the orig1nal textile product, and has
good appearance and excellent washing fastness.
Preferabl~ embodiments of aroma imparting
A preferable embodiment of the aroma-imparting method
ot the present invention comprises the step of treating a
textile product with a binder in an amount insufficient to
spoile the appearance and touch of the textile product.
The textile product obtained via this binder treatment
step has improved washing fastness as a result of enhanced
fixation of perfume-containing microcapsules to the tex-tile
product.
The amount of binder, as of the binder solid content,
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is about 0.1 to 10~ by weight in general, preerably 0.3 to
5% by weight, relative to the textile product.
Examples of the usable binders include
acrylic acid ester resin,
methacrylic acid ester resin,
vinyl acetate resin,
polyurethane resin,
polyester resi.n,
styrene-buthdiene latex,
polyolefin resin; and
of the above-mentioned anionic polymer compounds,
polyacrylic acid,
methacrylic acid, and
derivatives thereof; and
copolymers of these substances with other vinyl monomers.
For the present invention, acrylic acid ester resin and
polyurethane resin are especially preferable.
The binder treatment can be carried out by, for example,
immersing the textile product in a binder-containing
aqueous liquid:
spraying a binder-containing aqueous liquid on the textile
product; or
printing a binder-containing printing paste on the textile
product.
An aroma can be imparted to the textile product by this
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embodiment as follows for example:
Aroma-imparting Process 1
.
After a textile product is treated (cationized) with an
aqueous solution containing a nitrogenous cationic
compound, it is immersed for a treatment (fixing-treatment)
in a dispersion containing the above-described
perfume-containing microcapsules so that the
perfume-containing microcapsules are exhausted into the
textile product. To this liquid, a binder is added in a
ratio of 0.1 to 10% by weight, as of the binder solid
content, relative to the textile product, followed by a
treatment (binder treatment) at a normal temperature to 90C
for 1 to 30 minutes, after which the textile product is
dewatered and dried.
Aroma-lmparting Process 2
After a textile product is treated (cationized) with an
aqueous solution containing a nitrogenous cationic
compound, it is in~ersed for a treatment (fixing-treatment)
in a dispersion containing the above-described
perfume-containing microcapsules so that the
perfume-containing microcapsules are exhausted into the
textile product, followed by dewatering. Then to a
container containing the textile product, water is added
in a bath ratio of about 5:1 to 50:1, preferably 10:1 to
30 :1, and a binder is added in a ratio of 0.1 to 10% by
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weight, as of the binder solid content, relative to the
textile product, followed by a treatment (binder
treatment) at a normal temperature to 90C for 5 to 30
minutes, after which the te~tile product is dewatered and
dried.
Aroma-imparting Process 3
After a textile product is treated (cationized) with an
aqueous solution containing a nitrogenous cationic
compound, it is immersed in a dispersion containing the
above-described perfume-containing microcapsules and a
binder in a ratio of 0.1 to 10% by weight, as of the binder
solid content, relative to the textile product and treated
(fixing-treatment and binder treatment) at a normal
temperature to 90 C for 5 to 30 minutes, after which the
textile product is dewatered and dried.
Aroma-imparting Process 4
After a textile product is treated with an aqueous
solution containing a nitrogenous cationic compound and a
binder in a ratio of 0.1 to 10~ by weight, as of the
binder solid content, relative to the textile product
(first step, cationization and binder treatment), it is
immersed for a treatment at a normal temperature to 90C
for 1 to 30 minutes (second step, fixing-treatment) in a
dispersion containing the above-described
perfume-containing microcapsules so that the
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perfume-containing microcapsules are exhausted into the
textile product. After this treatment, the textile product
is dewatered and dried.
In the first step, neutralization of the cationic
compound by adding soda ash, caustic soda, etc is carried
out as needed.
Also, in the first step, the combination of nitrogenous
cationic compound and binder can be replaced by a
cationic binder which is nitrogenous cationic compound, in
an amount such that the appearance and touch of the textile
product is not ~poiled,.
Examples of such cationic binders include
Voncoat SFC Series (trade name, emulsion of vin~l acetates
or acrylic esters, product of Dainippon Ink & Chemicals,
Inc.),
Yodosol AF Series (trade name, emulsion of acrylic esters,
product of Kanebo N.S.C. Limited),
the CGC Series (trade name, emulsion of acrylic e~ters,
product of Sumitomo ChQmical Co., Ltd.),
cationic emulsions disclosed in Japanese Patent Unexamined
Publication No. 187702/1987,
cationic copolymer disclosed in Japanese Patent Unexamined
Publication No. 131003/1987,
cationic polymer disclosed in Japanese Patent Unexamin~d
Publication No. 201914/1987, and
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cationic latex disclosed in Japanese Patent Unexamined
Publication No. 263211/1987.
In the above described preferable aroma-imparting
processes 1 through 4, the binder is exhausted, i.e. taken
up, into the textile product in an amount approximately
equal to the content of the binder-containing liquid, i. e.
in a ratio of about 0.1 to 10% by weight of binder solid
content relative to the textile product, and the binder is
strongly fixed to the textile product by dewatering and
drying. As a result, further improvements in the fastness
to rubbing and washing are obtained. If the binder solid
content is less than 0.1% by weight, the obtained effect is
likely to be insufficient. If the binder solid content
exceeds 10% by weight, the appearance and touch of the
textile product are often spoiled.
In the aroma-imparting method of the present invention
described above, a coloring agent including the coloring
agents exempliEied for coloring the perfume-containing
microca~sule, another coloring agent such as a
thermochromic material or a photochromic material, may be
incorporated in the capsule~dispersion liquid wherein
perfume-containing microcapsules are dispersed, so that
these coloring agents are exhausted into the textile
product simultaneously with the exhaustion of the
perfume-incorporating microcapsules. This makes it
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possible to realize constant coloring and reversible color
changes depending on temperature change or on presence or
absence of light irradiation, simultaneously with aroma
imparting.
Examples oE thermochromic materials include materials
disclosed in EP-A-0480162, such as three-component mixtures
of an acid developing substance, an acidic substance and a
solvent; two-component mixtures of an acid developing
substance and an acidic substance; cholesteric liquid
crystals; and metal complex salts.
Examples of photochromic materials include
organic photochromic materials such as
azobenzene compounds,
thioindigo compounds,
dithizone metal complexes,
spiropyran compounds,
spirooxazine compounds,
fulgide compounds,
dihydroprene compounds,
spirothiopyran compounds,
1,~-2H-oxazine,
triphenylmethane compounds,
viologen compounds, and
naphthopyran compounds.
Specifically, materials disclosed in the same publication `~
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EP-A-0480162 may be mentioned. In the present invention,
spiropyran compounds, spirooxazine compounds, fulgide
compounds and naphthopyran compounds are particularly
preferable.
Also, the textile product, previously colored, may be
subjected to the aroma-imparting method of the present
invention described above.
PREPARATION EXAMPLES OF PERFUME-CONTAINING MICROCAPSULES
Some preparation examples of perfume-containing
microcapsules are given below. In the description below,
"part(s) by weight" is referred to as "part(s)".
Preparation Example 1
To 30 parts of an aqueous solution of 10% (w/w3 gelatin
being kept at 40C , 12 parts of WOODY 4319 (trade name or
synthetic perfume, product of Kotobuki Perfumery Co., Ltd.)
was added, followed by emulsification at a stirring speed
adjusted to have a particle size oE about 10~ m.
Subsequently, 30 parts of an aqueous solution of 10% (w/w)
gum arabic being kept at 40 C was added to this mixture,
followed by stirring ~or 10 minutes. To this mixturP, 128
parts of 40 C water was added. After acetic acid was added
drop by drop to reduce the pH below 4 to 4.3, the mixture
was cooled to 5 r,, and 1 part of 30% (w/w) formalin and
several drops of an aqueous solution of 10% (w/w) caustic
soda were added to obtain a pH of 9. Then the temperature
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was increased to 50 C at a rate of 1 or per minute. After
this temperature was maintained for 1 hour, the mixture was
left to cool to yield about 200 parts of dispersion liquid
wherein perfume-containing microcapsules were dispersed.
Preparation E~ample 2
_
To 300 parts of an aqueous solution of 3~ (w/w) EMA31
(trade name for ethylene-maleic acid copolymer, product of
Monsanto Company) being kept at 60C , 20 parts of LEMON
4314 (trade name for a synthetic perfume, product of
Kotobuki Perfumery Co., Ltd.) and 60 parts of cetyl
alcohol, previously heated and mixed at 60C , were added,
followed by emulsification at a stirring speed adjusted to
have a particle size of about 5 ~ m. To this emulsion was
added drop by drop a melamine prepolymer prepared by
reacting 30 parts of 37~ (w/w) formalin and 10 parts of
melamine at 60C for 10 minutes. After completion of the
dropwise addition, the liquid temperature was increased to
80C , followed by heating and stirring for 30 minutes, to
yield 420 parts of dispersion liquid wherein
perfume-containing microcapsules were dispersed.
Preparation Example 3
To 300 parts of an aqueous solution containing 3 parts
of DEMOL N (trade name for an anionic surfactant, product
of Kao Corporation), mixture of 30 parts of ROSE 4316
(trade name for synthetic perfume, product of Kotobuki
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Perfumery Co., Ltd.), 40 parts of DINP (plasticizer) and 30
parts of SUMIDUR N75 (trade name for aliphatic
polyisocyanate, product of Sumitomo Bayer Urethane Co.,
Ltd.), kept at 80 C , was added drop by drop, followed by
emulsification at a stirring speed adjusted to have a
particle size of about 2~ m. About 15 minutes later, the
liquid temperature was increased to 95C , followed by
heating and stirring for 2 hour-s, to yield about 400 parts
of dispersion liquid wherein perfume-containing
microcapsules were dispersed.
Preparation Example 4
To 196 parts of an aqueous solution of 2% polyvinyl
alcohol, mixture of 35 parts of PEPPERMINT 4234 (trade
name for synthetic perfume, product of Kotobuki Perfumery
Co., Ltd.), 55 parts of CRYSTOL 352 (trade name for liquid
paraffin, product of Esso Sekiyu K.K.), 29 parts of
EPIKOTE 828 ~trade name for epoxy resin, product of Yuka
Shell Epoxy Co.) and 2 parts of FLEX BLUE BASE (trade name
for phthalocyanine, product of Matsui Shikiso Che~ical Co.,
Ltd.), kept at 80 C , were added drop by drop, followed by
emulsification at a stirring speed adjusted to have a
particle size of about 15 ~ m. Next, 12 parts of EPICURE U
(trade name for hardener, product of Yuka Shell Epoxy Co.)
was added drop by drop, followed by a reaction for 2 hours
with heating and stirring, to yield about 320 parts of
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di,~pers:iorl.1i,qu:id whereLn b].ue~colored perfume~contairl.ing
microc;lpsllles were clispersed.
F,XAMPLES
Some exramples are ~iven below to i.llu~trate, without
limit~tion, the present inverltion.
Exa_pl~ 1
First, a cotton T-~hirt (~heeting, 120 parts) was
scoured, i.e. ~crubhed vigvrously, to remove the thickening
agenks ancl lmpuritie~.
Next, to a 5-liter vat were ad~led 2400 parts of water
(bath ratlo ~0:1), 2 parts o~ SANFIX PAC-7 ~trade name for
aqueous solutlon o~ nitrogeneous cationic polymer compound,
produGt: of Sanyo Chemical Industrias, Ltd.) and l0 parts of
ethyle~e glycol.
The scoured T shirt was immers~3d in this aqueous
solution ~ollGwed by ~radual temperature rise and
tr~atment at 70 C for 15 minutes.
The T-æhirt was thoroughly rinæed with water to remove
the excess portion o the nitrogenous cationlc polymer
compound and other additive~ and then dewat~red, l.e.
~queezed to damp conditlon.
Next, to ~ 5-liter vat, the dewatered T--shirt, 2400
part~ of water, 10 parts of the perfume-containing
mlcrocap~ule di~persion liquid obtained in Prepara-tion
~xample 1 and 25 part~. of C~IROMICOLOR A~UALI~E INK FAST
21~16~
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~BLUE AQ-27 (trade name for thermochromic color, product of
Matsui Shikiso Chemical Co., Ltd.) were added. The liquid
temperature was gradually increased, followed by treatment
at 80 C for 15 minutes. The perfume-containing
microcapsules were completely taken up by the T-shirt.
Subsequently, this T-shirt was thoroughly rinsed and
dewatered, after which it was allowed to dry
and then subjected to heat treatment at 140 C in a tumbler
drier for 1 minute.
The T-shirt thus obtained was found to retain the
original appearance and touch. When a person wearing this
T-shirt ~ogged lightly, wood aroma was emitted and the
joggex felt refreshing as if running in woods. Also, with
the rise in body temperature, the T-shirt changed its color
from blue to white. -
This aroma-emitting and ~eversibly color changing
function was not lost even after repeated washing.
Example 2
Process from a cotton T-shirt's (sheeting 120 parts)
taking up of CHROMICOLOR AQUALITE INK FAST BLUE AQ-27 and
perfume-co~taining microcapsules to water rinsing and
dewatering of the T-shirt was carried out in the same
manner as in Example 1.
Next, to a vat containing the T-shirt, 2400 parts of
water and 12 parts (solid content about 3.6 parts) of
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MATSUMINZOL MR-10 (trade name for emulsion of acrylic ester
resin, product of Matsui Shikiso Chemical Co., Ltd.) were
added, followed by gradual temperature rise and treatment
at 70 C for 15 minutes, after which the T-shirt was
dewatered and dried.
The T-shirt thus obtained showed the same function with
that in Example 1, and had good appearance and touch,
comparable to those in Example 1, and further improved
washing fastness.
Example 3
A cotton T-shirt was treated in the same manner as in
Example 1 except that CHROMICOLOR AQUALITE INK FAST BLUE
AQ 27 was replaced by 25 parts of PHOTOPIA AQUALITE INK
PURPLE AQ-R (trade name for photochromic color, product of
Matsui Shikiso Chemical Co., Ltd.)-
The T-shirt thus obtained emitted wood aroma as the
wearer made gentle motions, and the wearer felt refreshing -~-~
as if staying in woods. Also, when the wearer went
outdoors, the portions exposed to sunlight became deep
purple. The appearance, touch, washing fastness and other
quality factors were as good as those in Example 1.
Example 4
First, a cotton sweat shirt 1300 parts) was scoured to
remove thickening agent and impurities.
Next, to a 10-liter vat, 6000 parts of water, 2.7 parts
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of SANFIX 70 (trade name for a nitrogenous cationic polymer
compound, product of Sanyo Chemical Industries, Ltd.) and
15 parts of ethylene glycol were added. The sweat shirt was
immersed in this li~uid, followed by treatment at 60C Eor
15 minutes, after which the sweat shirt was thoroughly
rinsed and then dewatered.
Next, to a 10-liter vat containing this sweat shirt,
6000 parts of water were added, and 45 parts oE the
perfume-containing microcapsule dispersion liquid obtained
in Preparation Example 2 was added therPin and dispersed.
The liquid temperature was gradually increased, followed by
treatment for 15 minutes, after which the cotton sweat
shirt was thoroughly rinsed and then dewatered.
Next, to a lO~liter container containing this sweat
shirt,- 6000 parts of water were added, and 30 parts of
HYDRAN AP-20 ~trade name for polyurethane resin emulsion,
product of Dainippon Ink & Chemicals, Inc.~ was added.
After the liquid temperature was gradually increased,
followed by treatment at 70 C for 15 minutes, the cotton
sweat shirt was dewatered and allowed to dry well.
When the wearer of this sweat shirt made light
exercise, the microcapsules were broken by friction, and
lemon aroma was emitted. The touch, appearance and washing
fastness of the sweat shirt were all good.
Example 5
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An acrylic shirt (120 parts) was scoured to remove
thickening agent and impurities.
Next, to a 5-liter container, 2400 parts of water (bath
ratio 20:1), 4 parts of SANFI~ PAC-7 (trade name for
aqueous solution of nitrogenous cationic pol~mer compound,
product of Sanyo Chemical Industries, Ltd.) and 6 parts of
MATSUMINZOL MR-C (trade name for emulsion of acrylic ester
resin, product of Matsui Shikiso Chemical Co., Ltd.) were
added. In this mixture the scoured shirt was immersed,
followed by gradual temperature rise and treatment at 70C
for 15 minutes.
Subsequently, the shirt was thoroughly rinsed and then
dewatered.
Next, to a 5-liter container, 2400 parts of water and 10
parts of the perfume-conta1ning microcapsules obtained in
Preparation Example 4 were added, and the dewatered shirt
was immersed therein.
The liquid temperature was gradually increased,
followed by treatment at 70 C for 15 minutes. This
treating solution changed from blue to colorless
transparent, demonstrating complete exhaustion.
Next/ this shirt was thoroughly rinsed and dewatered,
after which it was dried well.
The shirt thus obtained was found to retain the
original touch and appearance and have a blue color. As the
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wearer of this shirt made gentle motions, a refreshing
peppermint aroma hung around. This function was not lost
even after repeated washing.
Example 6
To a 5-liter vat, 2400 parts of water (bath ratio
20:1), 2 parts of SANFIX PAC-7 (trade name for aqueous
solution of nitrogenous cationic polymer compound, product
of Sanyo Chemical Industries, Ltd.) and 10 parts of
ethylene glycol were added.
In this aqueous solution was immersed
a polyester/cotton mixed yarn browse (120 parts) previously
printed with rose flower patterns with an ordinary printing
ink by means of a screen, followed by gradual temperature
rise and treatment at 70C for 15 minutes.
Subsequently, the browse was rinsed with water to
remove the exce s portion of nitrogenous cationic compound
and other additives and then dewatered.
Next, to a 5-liter vat containing the dewatered browse
2400 parts of water and 20 parts of the perfume-containing
microcapsule dispersion liquid obtained in Preparation
Example 3 were added, followed by gradual temperature rise
and treatment at 80 C for 15 minutes.
The browse thus obtained was found to retain the
original touch and appearance. As the wearer made gentle
motions or upon friction with a sofa, for instance, the
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microcapsules were broken and a fragrant rose aroma hung
around.
This function was not lost even after repeated washing.
Comparative Example 1
A T-shirt was treated in exactly the same manner as in
Example 1 except that the perfume-containing
microcapsule dispersion liquid obtained in Preparation
Example 1 was replaced by 10 parts of an emulsion of 12
parts of Woody 4319 in 188 parts of surfactant-containing
water. This T-shirt was of no commercial value; the perfume
was almost completely lost during the drying process, and
the trace residual aroma was totally lost in one tima of
washing.
Comparative Example 2
A T-shirt treated in exactly the same manner as in
Example 1 except that no nitrogenous cationic compound was
used was of no commercial value; the aroma was weak and no
aroma was emitted after several times of friction because
the perfume-containing microcapsules were not completely
exhausted into the T-shirt.
Comparative Example 3
The same T-shirt as used in Example 1 was scoured to
remove thickening agents and impurities.
Next, to a 5-liter vat, 2400 parts of water, 100 parts
of the perfume-containing microcapsule dispersion liquid
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obtained in Preparation Example 1 and 120 parts o~
~TSUMINZOL MR-10 were added. Using this mixture liquid,
the above-mentioned T-shirt, not cationized, was treated by
the two-dip two-nip method.
In this treatment, the perfume-containing microcapsules
were hardly exhausted into the T-shirt. The obtained
T-shirt was of no commercial value because it was poor in
aroma emission and had a rough touch.
Next, the products obtained in Example 1 and
Comparative E~amples 1, 2 and 3 were compared with respect
to aroma strength, aroma-emitting function retainability,
appearance and touch, and washing fastness. The results are
given in Table 1.
In Table 1, O indicates a good result, and x
indicates a poor result.
TABLE 1
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aroma aroma-emitting appearance washing
strength function reta and touch fastness
inability
Example 1 O O O
Comparative x x O x
. Example 1
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Comparative x x O x
Example 2 _
Comparative x x x x
: Example 3
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