JPH02133666A - Fabric capable of reversible change of color tone - Google Patents

Abstract

PURPOSE:To provide the subject fabric capable of reversible change of color tone thereof corresponding to the intensity of ultraviolet rays and excellent in light resistance and cleaning resistance by using a treatment composed of a fine-particle polymer containing a photochromic compound and an organic binder. CONSTITUTION:An aqueous dispersion consisting of a mixture of a fine-particle polymer (0.05-100mum average radius) such as a styrene-based resin containing a photochromic compound such as a spirooxazine compound bonded thereto through a covalent bond, preferably by radical polymerization, an organic binder, preferably consisting of a thermoset acryl resin, etc., is coated on a fabric and heat treatment is carried out to obtain the objective fabric capable of reversible change of color tone thereof and excellent in light resistance, color- development properties and feeling. In addition dry-cleaning resistance is improved by using copolymerization method for bonding the photochromic compound to the polymer.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a photoreversible color-changing fabric whose color tone changes reversibly depending on the intensity of ultraviolet rays, and which has particularly excellent light fastness and dry cleaning resistance. It is.

[Prior Art] From a fashion point of view, there is a strong demand for photoreversible color-changing fabrics for use in clothing, whose color development changes depending on the intensity of light and which can produce original and unique color tones.

In response to these demands, various attempts have been made in the past, such as a description of the prospects for the potential of chameleon fiber (Kosei Monthly Vol. 28, December issue, p. 50-19).
According to 1975), a compound exhibiting photoreversible color change is contained in a resin, and the mixture is (3) mixed during fiber spinning, (b) coated on the fiber surface, and (C) dyed. Techniques for use in such methods are shown.

Furthermore, Japanese Patent Application Laid-open No. 62-289684 discloses a technology related to a fiber fabric imparted with photoreversible discoloration (=J) using microcapsules in which a spirooxazine derivative is encapsulated in a spherical porous hollow powder. ing.

[Problems to be solved by the invention] However, in these conventional technologies, durability,
It had a problem of poor dry cleaning resistance.

The present invention aims to provide a photoreversible color-changing fabric with good durability and dry cleaning resistance.

[Means for Solving the Problems] In order to achieve the above object, the present invention has the following configuration.

[A photoreversible color-changing fabric characterized in that a fiber fabric is provided with a mixture having a small amount of photochromic properties consisting of fine particles of a polymer containing a photochromic compound and an organic binder.'' The present invention By incorporating a photochromic compound into a polymer and using it as fine particles, durability and dry cleaning resistance can be improved.

Specific examples of the photochromic compound in the present invention include spiropyran compounds such as spirobenzopyran, spirooxazine compounds such as spironaphthoxazine, spiropyridobenzoxazine, and spirobenzoxazine, viologen, triarylmethane, and fulgide compounds. .

Examples of polymers include, but are not limited to, styrene resins, acrylic resins, vinyl resins, polyester resins, urethane resins, epoxy resins, polyamide resins, and cellulose derivatives. . These polymers may be used alone or in combination of two or more.

In the present invention, methods for incorporating the photochromic compound into the polymer matrix include (1) simply dispersing the photochromic compound in the polymer, and (2) incorporating the photochromic compound into the polymer by covalent bonding.

In method (2), the photochromic compound and polymer described above can be used.

Furthermore, method (2) is particularly suitable for improving the durability and dry cleaning resistance of the fabric imparted with photoreversible discoloration. As a method for making this covalent bond, a method using radical polymerization is advantageous in terms of the performance of the photochromic polymer and the manufacturing cost.

For radical polymerization, a compound obtained by adding a polymerizable unsaturated functional group to the photochromic compound is preferably used. Examples of such compounds include photochromic compounds represented by the following general formula [I].

(In the formula, the α ring is a type selected from a pyrrolidine ring, a pyrrole ring, a piperidine ring, a tetrahydropyridine ring, a dihydropyridine ring, an indoline ring, a benzindoline ring, a tetrahydroquinoline ring, an acridine ring, a benzoxazoline ring, and a benzothiazoline ring. , and the nitrogen atom in the α ring is YrriI<2 or is bonded to an organic group R. Here, R is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkenyl group having 7 to 20 carbon atoms. represents a substituent selected from 20 aralkyl groups and aryl groups having 6 to 19 carbon atoms.

The β ring is a benzene ring, a naphthalene ring, an anthracene ring,
One type selected from a phenanthrene ring, a quinoline ring, a dibenzofuran ring, a dibenzothiophene ring, a carbazole ring, and a benzonaphthothiophene ring.

R1 is hydrogen, an amino group, an alkoxy group having 1 to 20 carbon atoms, an aralkoxy group having 7 to 20 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. represents a substituent selected from a group, an aralkyl group having 7 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms.

R2 represents a radically polymerizable functional group.

n is an integer of 1 or more.

Y represents an organic group having 1 to 20 carbon atoms.

m represents O or 1. However, when Y m R'' is bonded to the nitrogen atom in the α ring, ■η represents 1.

) Here, in the spirooyasazine compound represented by the general formula (I), the α ring refers to a pyrrolidine ring, a virol ring,
It is one selected from a piperidine ring, a tetrahydropyridine ring, a dihydropyridine ring, an indoline ring, a benzindoline ring, a tetrahydroquinoline ring, an acunodine ring, a benzoxazoline ring, and a benzothiazoline ring.

The nitrogen atom contained in this α ring exists bonded to 7mR2 or an organic group R, and is represented by .

Here, specific examples of the substituent R include a chain alkyl group having 1 to 20 carbon atoms such as a methyl group, a methyl group, and an octadecyl group, and a chain alkyl group having 3 carbon atoms such as a 1ert-butyl group and a 2-methylpentyl group. ~20 branched alkyl groups, cyclohexyl groups, norbornyl groups, aralkyl groups, etc. with 3 or more carbon atoms
10 cycloalkyl groups, vinyl It/groups, allyl groups, hexenyl groups, 1,3-butadienyl groups, alkenyl groups having 2 to 20 carbon atoms such as isopropenyl groups, benzyl groups,
It represents an aralkyl group having 7 to 20 carbon atoms such as a phenethyl group or a (2-naphthyl)methyl group, or an aryl group having 6 to 1-9 carbon atoms such as a phenyl group or a 2-naphthyl group.

R may be substituted, and in such a case, specific examples of the substituent include a hydroxy group; an amino group such as an amino group and a dibenzylamino group; an alkoxy group such as a methoxy group, an ethoxy group, and a propoxy group; Acyloxy groups such as benzoyloxy; alkyl groups such as methyl, ethyl, trifluoromethyl, butyl; benzyl, 4-(
Aralkyl groups such as 2,3-epoxypropyl) phenethyl groups; Aryl groups such as phenyl groups; Halogen groups such as fluoro and chloro groups; Cyano groups; Carboxy groups; Nitro groups;
Acyl group such as acetyl group; ethoxycarbonyl group, 3.
Alkoxycarbonyl groups such as 4-epoxybutyloxycarbonyl groups; Carbamoyl groups such as carbamoyl groups and N-phenylcarbamoyl groups; Carbamoyloxy groups such as (N-(acetoxy)propylcarbamoyl)oxy groups; sulfonic acids, metal salts thereof ( Examples include sulfonic acid groups such as sodium and lithium salts.

Y in 7mR2, which is another substituent that can be bonded to the nitrogen atom of the α ring, is an organic group having 1 to 20 carbon atoms,
Specific examples thereof include alkylene groups such as medilene group and propylene group,
Examples include alkyleneoxy groups such as -←r, aryl non groups such as phenylene groups, and naphthylene groups.

a is a symbol indicating the number of repeating units, and takes an integer of 1 or more within the range where the number of carbon atoms in Y is 1 to 20. here,
The substituent represented by Y is contained in the α ring. Also, m must be 1. moreover,
■<2 is a radically polymerizable functional group, and specific examples thereof (7) include acryloxy group, methacryloxy group,
methacrylamide group, p-vinylbenzoyloxy group, m
-vinylbenzyl group, (2-methacryloxyalkyl)
Examples include an amino group, an N-(2(meth)acryloxy)alkylcarbamoyl group, and an (N-(31meth)acryloxy)alkylcarbamoyl)oxy group.

It goes without saying that the Y m R2 group described below can be substituted on atoms other than the nitrogen atom in the α ring and on each atom in the β ring, but in that case, even if m is O, It may be 1. In addition, the number of functional groups contained in the general formula (I) of 7mR2, I], is an integer of 1 or more, but if n is 2 or more, the 7mR2 may be of the same type or different types. There is no problem.

Next, other constituent elements included in general formula (I) will be explained.

R1 is hydrogen; an amino group such as an amino group, a dimethylamino group, or a di(2-hydroxyethyl) amino group; an alkoxy group having 1 to 20 carbon atoms such as a methoxy group, a propoxy group, a butoxy group; Aralkoxy groups having 7 to 20 carbon atoms such as benzyloxy group and phenethyloxy group; Aryloxy groups having 6 to 14 carbon atoms such as phenoxy group and naphthoxy group; 2 to 20 carbon atoms such as benzoyloxy group
Acyloxy group; methyl group, ethyl group, propyl group,
Alkyl groups with 1 to 20 carbon atoms such as butyl group, tert-butyl group, and octadecyl group; Aralkyl groups with 7 to 20 carbon atoms such as benzyl group, phenethyl group, and naphthylmethyl group; carbon atoms such as phenyl group and naphthyl group Number 6-20
The following aryl groups are mentioned.

On the other hand, β included in general formula (1) like the α ring
The rings consist of a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a quinoline ring, a dibenzofuran ring, a dibenzothiophene ring, a carbazole ring, and a benzo-1-phthodiophene ring.

Various substituents can be introduced into the α ring and β ring,
By introducing a substituent, it is possible to control the rate of color development and fading, which is one of the photochromic properties, and also control the color tone of the color. Specific examples of substituents that can be introduced and are preferably applied include those having 1 to 2 carbon atoms;
0 alkyl group, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 19 carbon atoms, and a cycloalkyl group or hydroxy group having 3 to 10 carbon atoms including the 3-position carbon in the α ring, Amino group, organic substituted amino group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, 7 carbon atoms
-20 aralkoxy group, C6-19 aryloxy group, C2-20 acyloxy group, halogen group,
cyano group, carboxy group, nitro group, acyl group having 2 to 20 carbon atoms, alkoxycarbonyl group having 2 to 20 carbon atoms,
Substituents selected from carbamoyl groups, carbamoyloxy groups, and sulfonic acid groups can be mentioned.

Furthermore, those containing a heteroatom in the β ring are particularly effective as a means for shortening the wavelength of the coloring species or for including a plurality of maximum absorption wavelengths.

Among them, a carbazole ring containing a nitrogen atom and a dibenzofuran ring containing an oxygen atom are preferably used from the viewpoint that they are relatively easy to synthesize and exhibit the above-mentioned properties significantly.

Spirooxazine compounds having a polymerizable functional group represented by the above general formula (I) are disclosed in JP-A-63-93788, JP-A-63-199279, and JP-A-63-2.
No. 503H and the like, and naturally these are also photochromic compounds that can be used in the present invention.

Moreover, as a copolymerization component with these photochromic compounds having a radically polymerizable unsaturated functional group, monomers having a radically polymerizable functional group are also preferable. Specific examples of such monomers include styrene, styrene, 1.・
derivatives, (meth)acrylic acid alkyl esters, (meth)acrylic acid hydroxyalkyl esters, (meth)
Acrylic acid, (meth)acrylamide, alkyl-substituted (
meth)acrylamide, N-substituted maleimide, maleic anhydride, (meth)acrylonitrile, methyl vinyl ketone, vinyl acetate, vinylidene chloride, divinylbenzene,
Examples include ethylene glycol di(meth)acrylate, other polyfunctional (meth)acrylic acid ester compounds, and the like. Furthermore, for the purpose of improving light resistance, various binder (meth)acrylic monomers having an amino group are preferably used as copolymerization components.

A polymer containing the above photochromic compound through a covalent bond can be used alone as a polymer having photochromic properties in the present invention, but it can also be used in combination with other polymers. As such a polymer, a polymer applied to the non-polymerizable photochromic compound described above can be used. Especially (dialkyl)aminoalkyl group-containing (meth)
Acrylic polymers containing acrylic monomers are preferred from the viewpoint of light resistance.

The photochromic compound-containing polymer I7 in the present invention is used by making it into fine particles, and the particle size is 0°05 to 1.0011 m from the viewpoint of dispersion stability and uniform color development. Preferably, the range is . Methods for producing such particles include dispersion polymerization and mechanical dispersion.

Dispersion polymerization methods include emulsion polymerization, soap-free emulsion polymerization, non-aqueous dispersion polymerization, seeded emulsion polymerization, or suspension polymerization of a photochromic compound (non-polymerizable compound or polymerizable compound) as the main component mixed with other monomers. Examples include a method of turbid polymerization.

On the other hand, in the mechanical dispersion method, a polymer copolymerized with a photochromic compound is dissolved in a solvent with low solubility in water, and then a dispersion stabilizer is added and then added to water and mixed to disperse a polymer solution. Thereafter, the solvent in the polymer is removed by heating and reduced pressure (17) to obtain photochromic polymer particles.

In the above polymer particles, the stability of the particles is maintained.
It is desirable to add a dispersion stabilizer.

The dispersion stabilizer mentioned here is used to impart dispersion stability to polymer particles, and includes cationic surfactants, anionic surfactants, nonionic surfactants, suspending agents, Examples include emulsifiers and protective colloids. Such a dispersion stabilizer can be added at the same time as the photochromic compound-containing polymer is made into fine particles, but there is no problem if it is added after the photochromic compound-containing polymer is made into fine particles.

The amount of dispersion stabilizer added varies depending on the type of polymer fine particles, particle size, type of dispersion stabilizer, usage conditions, etc., but usually 0.5 to 30 parts by weight is used per 100 parts by weight of polymer fine particles. properly applied.

In the present invention, the organic binder means a thermo-FiJ plastic resin or a thermosetting resin, and there is no problem with either of them. Binders, urea-based binders, alkyd-based binders, acrylic-based binders, phenolic binders, etc. can be used, but in particular,
Thermosetting resins are preferred in order to provide cleaning properties. Furthermore, in terms of affinity for fiber fabrics, that is, good adhesion, preferred resins and 17 include acrylic resins, vinyl resins, polyester resins, urethane resins, epoxy resins, styrene resins, and polyamide resins. Examples include resins, cell openings and -su derivatives. Among them,
From the viewpoint of weatherability and heat resistance, acrylic resins are particularly preferred. When manufacturing, superior properties can be obtained in terms of workability and other aspects.

The addition ratio of polymer particles containing a photochromic compound and resin should be determined depending on the required photochromic properties, the type of fiber fabric, and the intended use, but usually・
Polymer fine particles 100 containing a chromic compound
It is desirable that the amount of resin is 5 to 2000 parts by weight.

In other words, in the case of five senior ministers, they have poor adhesion to fiber fabrics and are prone to problems such as falling off due to abrasion or washing.9. On the other hand, if it exceeds 2000 parts by weight, there are problems such as insufficient color density in photochromic properties.

In the present invention, a mixture of the polymer fine particles and an organic binder is applied onto a fiber fabric. Methods of dispersing such a mixture and, if necessary, a composition comprising a dispersion stabilizer in a suitable dispersion medium, are applied to a fiber fabric, or gravure or screen method. Examples include printing methods such as Here, the dispersion medium may be any medium as long as it is capable of retaining the polymer fine particles in a substantially fine particle state. In view of the above, it is preferable to use water as a main component.

A method of three-dimensionally crosslinking the polymer itself is also preferably applied for the purpose of further enhancing the properties of the photochromic fabric of the present invention. Crosslinking effectively improves the durability of clothing fabrics, especially during dry cleaning, by preventing the tochromic compounds and polymers from eluting, and improving the repeatability of color development. This crosslinking of the polymer can be carried out by a general method in the step of forming polymer fine particles together with vinyl polymerization, or during drying of the polymer applied to the fiber fabric. That is, this can be achieved by introducing into the polymer functional monomers having reactivity with isocyanate groups, epoxy groups, melamine, etc., such as droxy groups, alkoxy groups, and carboxyl groups.

In addition to the previous components, the composition of the present invention has a pre-colored hue7, and it is also possible to add pigments and dyes as coloring agents for the purpose of changing the hue to a different hue upon irradiation with light. It is. By doing so, more free color tones can be obtained, which is useful from a fashion point of view. These pigments and dyes are not particularly limited, and include azo pigments, phthalocyanine pigments, 21- and nitroso pigments, disperse dyes, basic dyes, acid dyes, vat dyes, and mordant dyes. and organic pigments and dyes such as natural dyes, and inorganic pigments such as ocher, barium yellow, navy blue, cadmium red, barium sulfate, titanium oxide, red iron black, iron black, aluminum hydroxide, calcium carbonate, and carbon black, either singly or in combination. It is preferable that the ffi used be in the range of 0.0005 to 3% by weight based on the total amount of the polymer because the photochromic effect becomes remarkable.

Furthermore, it is also preferable to add an antioxidant, a sensitizer, etc. to the polymer particles and organic binder for the purpose of improving the durability and coloring density of the photoreversible color-changing fabric.

[Example] Examples of the present invention are listed below, but the present invention is not limited thereto.

Example 1 (1) Photochromic compound-containing polymer fine powder.

45 parts by weight of methyl methacrylate, 40 parts by weight of n-butyl methacrylate, 1.3. :3-1-rifutyl-5
Methacryloxymethyl indolinospironaphthoxazine 10 parts by weight, ethylene glycol dimethacrylate No. 1
-5 parts by weight were added to 150 parts by weight of water in which sodium dodecylbenzene sulfate was dissolved, and emulsion polymerization was carried out using an azo initiator at 80° C. for 10 hours in a nitrogen atmosphere. The resulting photochromic polymer fine particles had an average particle size of about 1-10 μm and a maximum particle size of 10 μm.

(2) Preparation of photoreversible color-changing fabric A coating solution for fiber fabric was prepared according to the compounding ratio described in 4. This coating solution was printed on 100% cotton cloth using 1000 mesh gauze. , 160℃ for 3 minutes in a heating pot ('1
1 was processed. Note that an acrylic acid ester water emulsion was used as the organic binder, and a blocked isocyanate water emulsion was used as the crosslinking agent.

The blending ratio is 80 parts by weight of acrylic ester water emulsion (solid content: 25% by weight) and 20 parts by weight of photochromic water-dispersed polymer fine particles (solid content: 40% by weight).
Ffi part, blocked isocyanate-based water emulsion (solid content: 30% by weight) was divided into two cities and one part.

The resulting fabric was evaluated for color development, light fastness, washability, and resistance to Perclean and dry cleaning, and the results are shown in the table. In addition, the evaluation method and the judgment of the test results were performed by the methods shown below.

(1) Color development/decolorization The rate of color development and fading and color density were observed by irradiation with sunlight and an ultraviolet lamp, and cases with sufficient color development were indicated by a 0 mark.

(2) Light resistance Tested according to JIS L-0842 (20 hours of carbon arc irradiation).

(3) Washability After washing for 10 minutes at 40° C. using a household washing machine, rinsing for 3 minutes at room temperature was performed three times, followed by centrifugal dehydration. After washing, fabrics with good color development were marked with a circle, and fabrics with poor color development were marked with an X.

(4) Put perclene and photoreversible color-changing fabric in a cleanable airtight container for 40 minutes.
The mixture was continuously stirred at ℃ and dry cleaned. After this, fabrics with good color development were marked with a circle, and fabrics with poor color development were marked with an X.

Example 2 The same procedure as in Example 1 was carried out except that the components of the photochromic compound-containing polymer particles were changed to the following. The evaluation results of the fabrics produced are shown in the table.

40 parts by weight of methyl methacrylate I, 40 parts by weight of n-butyl methacrylate, 10 parts by weight of 2-hydroxyethyl methacrylate, 1.3.3-) Umethyl-5'-methacryloxymethyl indolinospironaf I - Gradually add 10 parts of oxazine to 100 parts by weight of benzene,
Radical polymerization was carried out using an azo initiator under nitrogen atmosphere at 80° C. for 1 to 0 hours. This polymer solution was added to 150=Itm parts of water in which 7.5 parts by weight of polyvinyl alcohol had been dissolved and dispersed by stirring, and then benzene was distilled off by heating and reduced pressure. The obtained dispersed polymer was stable, and its particle size was approximately 7 μm on average and 15 μm in diameter.

Comparative Examples 1 and 2 Comparative Examples 1 and 2 were carried out in exactly the same manner as in Examples 1 and 2, respectively, except that no organic binder was added.

As is clear from the table, the photoreversible color-changing fabrics of Comparative Examples 1 and 2 showed good performance in the evaluation results of color development and light resistance by carbon arc irradiation, but they had poor performance in both washability and dry cleaning resistance. There were also problems with evaluation.

Comparative Example 3 Nylon resin pellets! , 3.3-1=limethylspiro[indoline-2,3'-[3111-nut[2,1-b] (14) oxazine] was added in an amount of 10% by weight, mixed uniformly, and then spun. , photochromic nylon fibers were prepared. The obtained fibers were yellowish in color, had a low color density, and could not satisfy the characteristics of a photoreversible color changing fabric (7).

[Effects of the Invention] The photoreversibly color-changing fabric of the present invention has good light resistance and dry cleaning resistance, and excellent color development and texture.

Furthermore, by incorporating a photochromic compound into the polymer through copolymerization, dry cleaning resistance can be further improved.

Further, in the present invention, by making the photochromic polymer fine particles and the organic binder water-dispersible, they can be applied to the fiber fabric and can be easily manufactured.

Patent applicant Higashishi Co., Ltd.

Claims (2)

[Claims] (1) A photoreversible color-changing fabric comprising a fiber fabric provided with a photochromic mixture comprising at least fine particles of a polymer containing a photochromic compound and an organic binder. (2) The photochromic compound is covalently bonded to
Claim (1) characterized in that it is contained in a polymer.
) The photoreversible color-changing fabric described in ).