JP2012188796A - Method for manufacturing rugged color-changing fabric - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a rugged color-changing fabric in which a color thereof is changed and a decorative effect with specific beauty is exhibited due to a rugged shape formed therein, so that a specific color effect may be exhibited by the color-changing property and the rugged shape.SOLUTION: A method for manufacturing a rugged color-changing fabric comprises the steps of: adhering, onto a back face of a color-changing fabric 2, a fabric or a resin sheet 3 having higher heat shrinkability than the color-changing fabric with some adhered portions and some non-adhered portions; forming a rugged shape in the color-changing fabric by heating and contracting the color-changing fabric and the fabric or resin sheet; and peeling the fabric or resin sheet off.

Description

  The present invention relates to a method for producing an uneven color-changing fabric. More specifically, the present invention relates to a method for producing a color-changing fabric having an uneven surface.

Conventionally, some proposals are disclosed regarding a discolorable fabric (for example, refer patent documents 1 and 2).
The color-changing fabric is applied to doll costumes, toy fields, and the like, and even if a variety of color changes can be enjoyed by temperature changes, the color-changing fabric has a color (1) to color (2) However, the appearance before and after the color change was monotonous and did not sufficiently satisfy the taste and decoration.

JP-A-61-179371 JP-A-6-272178

  The present invention solves the problems of conventional discoloring fabrics, and not only changes the color of the fabric, but also satisfies a unique aesthetics and decoration effect, and is suitable for doll costumes, toys, decoration fields, etc. An object of the present invention is to provide a method for producing an uneven color-changing fabric.

In the present invention, a fabric or resin sheet having a heat shrinkability larger than that of the discolorable fabric is adhered to the back surface of the discolorable fabric so as to have a plurality of adhering locations and non-adhering locations, and heated. The manufacturing method of the uneven | corrugated color-change fabric which shrinks | contracts a fabric or a resin sheet | seat, forms an unevenness | corrugation in a discolorable cloth, and peels the said cloth or resin sheet | seat is required.
Further, the discolorable fabric is either a reversible thermochromic fabric provided with a reversible thermochromic layer on the fabric or a photochromic fabric provided with a photochromic layer on the fabric, and the reversible thermochromic with the fabric. It is required that a non-discoloring layer is provided between the layers or the photochromic layer, a transparent metallic luster layer is provided on the reversible thermochromic layer or the photochromic layer, and the like.

  The present invention relates to a method for producing a concavo-convex color-changing fabric in which the color of the fabric changes, the concavo-convex formed on the fabric has a unique aesthetics and decoration effect, and the color change and the concavo-convex combine to develop a unique color effect. Can be provided.

It is a longitudinal cross-sectional enlarged explanatory drawing which shows the state before the heating of one Example of the uneven | corrugated shaped discolorable fabric of this invention. It is a longitudinal cross-sectional enlarged explanatory view which shows the state after the uneven | corrugated shaped discolorable fabric of FIG. 1 is heated. It is a longitudinal cross-sectional enlarged explanatory view which shows the state which peeled the resin-made sheet | seat from the uneven | corrugated color-change fabric of FIG. It is a longitudinal cross-sectional enlarged explanatory view which shows the state before the heating of the other Example of the uneven | corrugated color-change fabric of this invention. It is a longitudinal cross-sectional enlarged explanatory view which shows the state after heating the uneven | corrugated shaped color-change fabric of FIG. FIG. 6 is an enlarged explanatory view of a longitudinal section showing a state where a heat-shrinkable fabric is peeled from the uneven color-changing fabric of FIG. 5.

The material of the fabric used for the discolorable fabric is not particularly limited, and examples thereof include polyester, nylon, acrylic, vinylon, polyurethane, polyvinylidene chloride, rayon, cupra, acetate, cotton, wool, silk, hemp and the like. .
Examples of the form of the fabric include forms such as a woven fabric, a knitted fabric, a braid, a nonwoven fabric, and a lace fabric.

As the cloth, printing means such as screen printing, offset printing, gravure printing, coater, transfer printing, and printing such as spray coating using an ink or paint in which a reversible thermochromic material is dispersed in a vehicle containing a binder resin. Or screen printing, offset printing, gravure printing, coater, transfer using a reversible thermochromic fabric formed by a coating means to form a reversible thermochromic fabric, ink or paint in which a photochromic compound is dispersed in a vehicle containing a binder resin Examples thereof include a photochromic fabric in which a photochromic layer is formed by printing means such as printing or printing or coating means such as spray coating.
Further, the cloth can be immersed in an ink or paint containing a reversible thermochromic material or a photochromic compound to obtain a color-changing cloth.
Furthermore, a discolorable fabric such as a knitted fabric, a woven fabric, or a non-woven fabric can be obtained using a reversible thermochromic material or a discolorable yarn containing a photochromic compound.

Examples of the reversible thermochromic material include inorganic materials such as Ag ₂ HgI ₄ and Cu ₂ HgI ₄ , liquid crystals, electron-donating color-forming organic compounds, electron-accepting compounds, and reversible color reactions of the two. A reversible thermochromic material of a heat decoloring type or a heat coloring type containing three components with the organic compound medium to be generated is used.
Among these, a reversible thermochromic material including an electron donating color-forming organic compound, an electron-accepting compound, and an organic compound medium that reversibly causes a color reaction of the two will be described.

The reversible thermochromic material comprises (a) an electron donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reversible thermochromic material comprising a reaction medium that determines the temperature at which the color reaction of both occurs. Examples include reversible thermochromic microcapsule pigments that change from colored to colorless in which the composition is encapsulated.
Examples of the reversible thermochromic composition include those described in Japanese Patent Publication No. 51-44706, Japanese Patent Publication No. 51-44707, Japanese Patent Publication No. 1-29398, etc., at a predetermined temperature (discoloration point). Discolored before and after, decolored state in the temperature range above the high temperature side discoloration point, color development state in the temperature range below the low temperature side discoloration point, only one specific state exists in the normal temperature range among the two states, The other state is maintained as long as the heat or cold required to develop the state is applied, but when the heat or cold is no longer applied, the hysteresis width returns to the state exhibited in the normal temperature range. A heat decoloring reversible thermochromic composition having relatively small characteristics (ΔH = 1 to 7 ° C.) can be applied (see FIG. 1).

In addition, large hysteresis characteristics (ΔH _B = 8 to 50 ° C.) described in JP- _B -4-17154, JP-A-7-179777, JP-A-7-33997, JP-A-8-39936, and the like. ), That is, when the shape of the curve plotting the change in the color density due to the temperature change is lowering the temperature from the lower temperature side than the color changing temperature range, as opposed to increasing the temperature from the lower temperature side. In the specific temperature range, the color changes in a low temperature range below the complete color development temperature (t ₁ ) or the color erase state in the high temperature range above the complete color erase temperature (t ₄ ). A heat decoloring reversible thermochromic composition having color memory in the [temperature range between t _{2 and} t ₃ (substantially two-phase holding temperature range)] can also be applied (see FIG. 2).

The hysteresis characteristic in the color density-temperature curve of the reversible thermochromic composition will be described.
In FIG. 2, the vertical axis represents color density and the horizontal axis represents temperature. The change in color density due to the temperature change proceeds along the arrow. Here, A is a point indicating a density at a temperature t ₄ (hereinafter referred to as a complete decoloring temperature) that reaches a completely decolored state, and B is a temperature t ₃ (hereinafter referred to as a decoloring start temperature). C is a point indicating a density at a temperature t ₂ at which color development starts (hereinafter referred to as a color development start temperature), and D is a temperature t ₁ at which a complete color development state is reached (hereinafter referred to as a complete color development state). This is a point indicating a density at a color development temperature).
Discoloration temperature region is a temperature range between the t ₁ and t _4, it is possible to exhibit any of the states of the colored state and the decolored state, between t ₂ and t ₃ is a region having a large difference in color density The temperature range is substantially the discoloration temperature range.
The length of the line segment EF is a scale indicating the discoloration contrast, and the length of the line segment HG passing through the midpoint of the line segment EF is a temperature width indicating the degree of hysteresis (hereinafter referred to as hysteresis width ΔH). If this ΔH value is small, only one specific state can exist in the normal temperature range among both states before and after the color change. Further, when the ΔH value is large, it is easy to maintain each state before and after the color change.

Examples of the compounds (a), (b), and (c) of the reversible thermochromic composition are shown below.
Examples of the electron donating color-forming organic compound as component (a) of the present invention include diphenylmethane phthalides, phenyl indolyl phthalides, indolyl phthalides, diphenyl methane azaphthalides, and phenyl indolyl azaphthalides. , Fluorans, stylinoquinolines, diazarhodamine lactones and the like.
Examples of these compounds are given below.
3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide,
3- (4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide,
3,3-bis (1-n-butyl-2-methylindol-3-yl) phthalide,
3,3-bis (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide,
3- [2-ethoxy-4- (N-ethylanilino) phenyl] -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide,
3,6-diphenylaminofluorane,
3,6-dimethoxyfluorane,
3,6-di-n-butoxyfluorane,
2-methyl-6- (N-ethyl-Np-tolylamino) fluorane,
3-chloro-6-cyclohexylaminofluorane,
2-methyl-6-cyclohexylaminofluorane,
2- (2-chloroamino) -6-dibutylaminofluorane,
2- (2-chloroanilino) -6-di-n-butylaminofluorane,
2- (3-trifluoromethylanilino) -6-diethylaminofluorane,
2- (N-methylanilino) -6- (N-ethyl-Np-tolylamino) fluorane,
1,3-dimethyl-6-diethylaminofluorane,
2-chloro-3-methyl-6-diethylaminofluorane,
2-anilino-3-methyl-6-diethylaminofluorane,
2-anilino-3-methyl-6-di-n-butylaminofluorane,
2-xylidino-3-methyl-6-diethylaminofluorane,
1,2-benz-6-diethylaminofluorane,
1,2-benz-6- (N-ethyl-N-isobutylamino) fluorane,
1,2-benz-6- (N-ethyl-N-isoamylamino) fluorane,
2- (3-methoxy-4-dodecoxystyryl) quinoline,
Spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5,1 '(3'H) isobenzofuran] -3'-one,
2- (diethylamino) -8- (diethylamino) -4-methyl-spiro [5H- (1) benzopyrano (2,3-g) pyrimidine-5,1 ′ (3′H) isobenzofuran] -3-one,
2- (Di-n-butylamino) -8- (di-n-butylamino) -4-methyl-spiro [5H- (1) benzopyrano (2,3-g) pyrimidine-5,1 '(3' H) Isobenzofuran] -3-one,
2- (Di-n-butylamino) -8- (diethylamino) -4-methyl-spiro [5H- (1) benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) isobenzofuran] -3-one,
2- (Di-n-butylamino) -8- (N-ethyl-Ni-amylamino) -4-methyl-spiro [5H- (1) benzopyrano (2,3-g) pyrimidine-5,1 ' (3′H) isobenzofuran] -3-one,
2- (Dibutylamino) -8- (dipentylamino) -4-methyl-spiro [5H- (1) benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran] -3 -On,
3- (2-methoxy-4-dimethylaminophenyl) -3- (1-butyl-2-methylindol-3-yl) -4,5,6,7-tetrachlorophthalide,
3- (2-ethoxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) -4,5,6,7-tetrachlorophthalide,
3- (2-ethoxy-4-diethylaminophenyl) -3- (1-pentyl-2-methylindol-3-yl) -4,5,6,7-tetrachlorophthalide,
4,5,6,7-Tetrachloro-3- [4- (dimethylamino) -2-methylphenyl] -3- (1-ethyl-2-methyl-1H-indol-3-yl) -1 (3H ) -Isobenzofuranone,
3 ', 6'-bis [phenyl (2-methylphenyl) amino] -spiro [isobenzofuran-1 (3H), 9'-[9H] xanthen] -3-one,
3 ', 6'-bis [phenyl (3-methylphenyl) amino] -spiro [isobenzofuran-1 (3H), 9'-[9H] xanthen] -3-one,
3 ', 6'-bis [phenyl (3-ethylphenyl) amino] -spiro [isobenzofuran-1 (3H), 9'-[9H] xanthen] -3-one,
4- [2,6-bis (2-ethoxyphenyl) -4-pyridinyl] -N, N-dimethylbenzenamine and the like can be mentioned.

As the electron-accepting compound of the component (b), a compound group having active protons, a pseudo-acidic compound group (a compound group that is not an acid but acts as an acid in the composition to cause the component (I) to develop color), There is a group of compounds having electron vacancies.
Examples of compounds having active protons include monophenols to polyphenols as compounds having phenolic hydroxyl groups, and alkyl groups, aryl groups, acyl groups, alkoxycarbonyl groups, carboxy groups and esters thereof as substituents. Alternatively, those having an amide group, a halogen group, etc., and bis-type and tris-type phenols, phenol-aldehyde condensation resins and the like can be mentioned. Moreover, the metal salt of the compound which has the said phenolic hydroxyl group may be sufficient.
Specific examples are given below.
Phenol, o-cresol, tertiary butylcatechol, nonylphenol, n-octylphenol, n-dodecylphenol, n-stearylphenol, p-chlorophenol, p-bromophenol, o-phenylphenol, n-butyl p-hydroxybenzoate N-octyl p-hydroxybenzoate, resorcin, dodecyl gallate, 2,2-bis (4-hydroxyphenyl) propane, 4,4-dihydroxydiphenylsulfone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) sulfide, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4 -Hydroxyphenyl) -3-methylbu 1,1-bis (4-hydroxyphenyl) -2-methylpropane, 1,1-bis (4-hydroxyphenyl) n-hexane, 1,1-bis (4-hydroxyphenyl) n-heptane, , 1-bis (4-hydroxyphenyl) n-octane, 1,1-bis (4-hydroxyphenyl) n-nonane, 1,1-bis (4-hydroxyphenyl) n-decane, 1,1-bis ( 4-hydroxyphenyl) n-dodecane, 1,1-bis (4-hydroxyphenyl) 2-ethylhexane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) ethyl Propionate, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,2 Bis (4-hydroxyphenyl) n- heptane, there is 2,2-bis (4-hydroxyphenyl) n- nonane.
The compound having a phenolic hydroxyl group can develop the most effective thermochromic property, but aromatic carboxylic acids and aliphatic carboxylic acids having 2 to 5 carbon atoms, carboxylic acid metal salts, acidic phosphate esters and their It may be a compound selected from metal salts, 1,2,3-triazole and derivatives thereof.

The component (c) of the reaction medium that causes the electron transfer reaction by the components (a) and (b) to occur reversibly in a specific temperature range will be described.
Examples of the component (c) include alcohols, esters, ketones, and ethers.
Examples of the (C) component, color density - relates temperature curve, the temperature _{T 4} is 20 to 35 ° C., preferably suitably used a compound in the range of 25 to 35 ° C..
The said compound is illustrated below.
Examples of alcohols include pentadecyl alcohol, hexadecyl alcohol, heptadecyl alcohol and the like.

  Esters include stearyl caprylate, cetyl myristate, neopentyl palmitate, nonyl palmitate, n-undecyl stearate, pentadecyl stearate, cyclohexylmethyl stearate, cetyl benzoate, stearyl p-tert-butylbenzoate, phthalate Dimyristyl acid, distearyl phthalate, dimyristyl oxalate, dicetyl oxalate, dicetyl malonate, dilauryl succinate, dilauryl glutarate, dilauryl azelate, di- (n-nonyl) sebacate, 1,18-octadecylmethylenedicarboxylic acid Dineopentyl, ethylene glycol dimyristate, propylene glycol dilaurate, propylene glycol distearate, hexylene glycol dipalmitate, 1,5-pentane di Distearate, 1,2,6-hexanetriol trimyristate, 1,4-cyclohexanediol didecyl, 1,4-cyclohexanedimethanol dimyristate, xylene glycol dicaprate, xylene glycol distearate, etc. Can be mentioned.

In addition, esters of saturated fatty acids and branched fatty alcohols, unsaturated fatty acids or branched or substituted saturated fatty acids and esters of fatty alcohols having 16 or more carbon atoms, cetyl butyrate, stearyl butyrate and Ester compounds selected from behenyl butyrate are also effective.
Specifically, 2-ethylhexyl butyrate, 2-ethylhexyl behenate, 1-ethylpropyl behenate, 2-methylbutyl behenate, 3-methylbutyl behenate, 1-methylheptyl stearate, 1-methylheptyl behenate, behen Examples include 2-methylhexyl acid, 3,7-dimethyloctyl behenate, and the like.

  Furthermore, the carboxylic acid ester compound disclosed in Japanese Patent Publication No. 4-17154, for example, a carboxylic acid ester containing a substituted aromatic ring in the molecule, a carboxylic acid containing an unsubstituted aromatic ring, and an aliphatic having 10 or more carbon atoms Esters of alcohol, carboxylic acid ester having a cyclohexyl group in the molecule, fatty acid having 6 or more carbon atoms and unsubstituted aromatic alcohol or phenol, fatty acid having 8 or more carbon atoms and branched aliphatic alcohol or ester, dicarboxylic acid and aromatic Esters of aliphatic or branched aliphatic alcohols, dibenzyl cinnamate, heptyl stearate, didecyl adipate, dilauryl adipate, dimyristyl adipate, dicetyl adipate, distearyl adipate, trilaurin, trimyristin, tristearin, dimyristin , Distearin And the like.

Fatty acid ester compound obtained from an odd aliphatic monohydric alcohol having 9 or more carbon atoms and an aliphatic carboxylic acid having an even carbon number, n-pentyl alcohol or n-heptyl alcohol and an even aliphatic carboxylic acid having 10 to 16 carbon atoms A fatty acid ester compound having a total carbon number of 17 to 23 obtained from an acid is also effective.
Specifically, n-nonyl caprylate, n-undecyl caprylate, n-tridecyl caprylate, n-pentadecyl caprylate, n-heptyl caprate, n-nonyl caprate, n-undecyl caprate, n-caprate Tridecyl, n-pentadecyl caprate, n-tridecyl laurate, n-pentadecyl laurate, n-tridecyl myristate, n-pentadecyl myristate, n-tridecyl palmitate, n-pentadecyl palmitate, n-undecyl stearate , N-tridecyl stearate, n-pentadecyl stearate, n-nonyl eicosanoate, n-undecy eicosanoate, n-tridecyl eicosanoate, n-pentadecyl eicosanoate, n-nonyl behenate, n-undecyl behenate, behenine Acid n Tridecyl, n- pentadecyl, and the like behenic acid.

Examples of ketones include 2-decanone, 3-decanone, 4-decanone, 2-undecanone, 3-undecanone, 4-undecanone, 5-undecanone, 2-dodecanone, 3-dodecanone, 4-dodecanone, 5-dodecanone, 2 -Tridecanone, 3-tridecanone, 2-tetradecanone, 2-pentadecanone, 8-pentadecanone, 2-hexadecanone, 3-hexadecanone, 9-heptadecanone, 2-pentadecanone, 2-octadecanone, 2-nonadecanone, 10-nonadecanone, 2-eicosanone 11-eicosanone, 2-heneicosanone, 2-docosanone, laurone, stearon and the like.
Further, arylalkyl ketones having a total carbon number of 12 to 24, such as n-octadecanophenone, n-heptadecanophenone, n-hexadecanophenone, n-pentadecanophenone, n-tetradecane. Nophenone, 4-n-dodecanacetophenone, n-tridecanophenone, 4-n-undecanoacetophenone, n-laurophenone, 4-n-decanoacetophenone, n-undecanophenone, 4-n-nonylacetophenone, n-decanophenone, 4-n-octylacetophenone, n-nonanophenone, 4-n-heptylacetophenone, n-octanophenone, 4-n-hexylacetophenone, 4-n-cyclohexylacetophenone, 4-tert-butylpropiophenone , N-heptaphenone, 4-n-pentylacetofu Non, cyclohexyl phenyl ketone, benzyl -n- butyl ketone, 4-n-butyl acetophenone, n- hexanophenone, 4-isobutyl acetophenone, 1-acetonaphthone, 2-acetonaphthone, cyclopentyl phenyl ketone.

  Further, as the electron-accepting compound, a specific alkoxyphenol compound having a linear or side chain alkyl group having 3 to 18 carbon atoms may be used (Japanese Patent Laid-Open Nos. 11-129623 and 11-5973), Heat-coloring reversible thermochromic composition using hydroxybenzoic acid ester (Japanese Patent Laid-Open No. 2001-105732) or gallic acid ester (Japanese Patent Publication No. 51-44706, Japanese Patent Laid-Open No. 2003-253149) It is also possible to apply a microcapsule pigment enclosing an object (see FIG. 3).

  The blending ratio of the components (a), (b), and (c) depends on the concentration, the color change temperature, the color change form, and the type of each component. In general, the component ratio at which a desired color change characteristic is obtained is as follows. (B) Component 1 is in the range of (b) Component 0.1-50, preferably 0.5-20, (c) Component 1-800, preferably 5-200. Part by mass).

Methods for microencapsulating the reversible thermochromic composition include interfacial polymerization, interfacial polycondensation, in situ polymerization, in-liquid curing coating, phase separation from aqueous solution, and phase separation from organic solvent. There are a melt dispersion cooling method, an air suspension coating method, a spray drying method, and the like, which are appropriately selected according to use. Further, a secondary resin film may be provided on the surface of the microcapsule according to the purpose to impart durability, or the surface characteristics may be modified for practical use.
Here, a non-thermochromic dye or pigment may be blended in the microcapsule pigment so as to exhibit a tautomatic color change from colored (1) to colored (2).
By encapsulating in the microcapsule, a chemically and physically stable pigment can be formed, and an average particle size of 0.1 to 50 μm, preferably 0.5 to 30 μm, more preferably 1 to 20 μm is practical. Meet.
The particle size and particle size distribution were measured using a laser diffraction / scattering particle size distribution measuring apparatus (manufactured by Horiba, Ltd .; LA-300), and the average particle size (median diameter) based on the numerical values. Is calculated.

The reversible thermochromic material is blended at a ratio of 20 to 400 parts by mass with respect to 100 parts by mass of the binder resin. If it is less than 20 parts by mass, no clear thermochromic property is exhibited. On the other hand, when it exceeds 400 parts by mass, a color residue at the time of decoloring tends to occur, and it is preferably applied within the range of 50 to 350 parts by mass.
By satisfying the blending ratio of the reversible thermochromic material and the binder resin, the durability of the reversible thermochromic layer is maintained and the hardness of the texture is prevented.

The binder resin may be either a water-soluble or oil-soluble resin, and can be appropriately selected and used according to the purpose.
Specifically, ionomer resin, isobutylene-maleic anhydride resin copolymer resin, acrylonitrile-acrylic styrene copolymer resin, acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, acrylonitrile chlorinated polyethylene-styrene copolymer. Resin, ethylene-vinyl chloride copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl acetate-vinyl chloride graft copolymer resin, vinylidene chloride resin, vinyl chloride resin, chlorinated vinyl chloride resin, vinyl chloride-vinylidene chloride Polymer resin, chlorinated polyethylene resin, chlorinated polypropylene resin, polyamide resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polycarbonate resin, polystyrene resin, high impact Styrene resin, polypropylene resin, polymethylstyrene resin, polyacrylate resin, polymethyl methacrylate resin, epoxy acrylate resin, alkylphenol resin, rosin modified phenol resin, rosin modified alkyd resin, phenol resin modified alkyd resin, epoxy resin modified alkyd resin , Styrene-modified alkyd resin, acrylic-modified alkyd resin, amino alkyd resin, vinyl chloride-vinyl acetate resin, styrene-butadiene resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polyurethane resin, alkyd resin, natural rubber, polyisobutylene , Butyl rubber, polyvinyl alkyl ether, rosin, rosin ester, rosin derivative, polyterpene resin, oil-soluble phenol resin, petroleum hydrocarbon resin, Shellac, cyclized rubber, vinyl acetate emulsion resin, styrene-butadiene emulsion resin, acrylate emulsion resin, aqueous silicone rubber emulsion resin, water soluble alkyd resin, water soluble melamine resin, water soluble urea resin, water soluble phenol Resin, water-soluble epoxy resin, water-soluble polybutadiene resin, cellulose acetate, cellulose nitrate, ethyl cellulose, etc. can be mentioned, and the reversible thermochromic material is dispersed by dissolving or dispersing in an appropriate solvent such as water or an organic solvent. Vehicle can be obtained.
Moreover, the said resin can use together 1 type, or 2 or more types.

As the photochromic compound, spirooxazine compounds, spiropyran compounds, diarylethene compounds and the like are effective.
The photochromic compound is preferably used by dissolving in a styrene-based oligomer, and the color density can be increased or the color change sensitivity can be adjusted.
The styrene oligomer has a weight average molecular weight of 250 to 4000, preferably 300 to 4000.
The weight average molecular weight is measured by GPC method (gel permeation chromatography).
Examples of the styrene oligomer include low molecular weight polystyrene, styrene-α-methylstyrene copolymer, α-methylstyrene polymer, α-methylstyrene and vinyltoluene copolymer, and the like.
The photochromic compound can also be used as a photochromic microcapsule pigment encapsulated in microcapsules.
As the binder resin used for forming the photochromic layer, the same binder resin as that of the reversible thermochromic layer is used.

In addition, a non-discoloring layer or a non-discoloring image can be provided between the fabric and the reversible thermochromic layer or the photochromic layer, or a non-discoloring image can be provided on the reversible thermochromic layer or the photochromic layer.
Examples of the non-color-change image include images selected from characters, symbols, alphanumeric characters, dots, lines, and designs.

A transparent metallic luster layer may be provided on the reversible thermochromic layer or photochromic layer.
The transparent metallic luster layer is a binder resin made of a transparent metallic luster pigment (for example, a pigment in which the surface of a transparent core material such as natural mica, synthetic mica, glass pieces, alumina, etc. is coated with a metal oxide such as titanium oxide). At the same time, it can be applied on a reversible thermochromic layer, or can be provided by attaching an iris sheet (film) or a hologram sheet (film).
As the iris sheet, a transparent metal compound having a refractive index difference of 0.05 or more from the base material surface (for example, titanium oxide, silicon oxide, zinc oxide, cadmium sulfide, magnesium fluoride, fluoride) A thin film layer of cerium, etc., and laminated with an uneven transparent resin layer having a refractive index difference of 0.05 or more in that order, and a multilayer of transparent plastic thin films with different refractive indexes. It can be illustrated.
As the hologram sheet, a light reflecting layer is provided by vapor-depositing a metal such as Al, Cr, Ni, Sn, Fe, Co, Cu, Pb, Sb, Mg, Cd, Bi on at least one surface of a fine uneven pattern. The thing can be illustrated.

On the back surface of the discolorable fabric, a fabric or a resin sheet having a heat shrinkability larger than that of the discolorable fabric is adhered so as to have a plurality of adhesion locations and non-adhesion locations. And after heating and shrinking a cloth or a resin-made sheet | seat and forming an unevenness | corrugation in a discolorable cloth, the said cloth or resin-made sheet | seat is peeled.
With the above-described configuration, a concavo-convex color-changing fabric having a unique aesthetic and decorative effect having irregularities (textures, folds, wrinkles, wrinkles) on the surface can be obtained.

  As the fabric or resin sheet having a larger heat shrinkability than the discolorable fabric, a woven fabric made of polyester fiber, acrylic fiber, polyolefin fiber, nylon fiber, etc., which has been given heat shrinkage by stretching, chemical treatment, resin composition, etc. Examples thereof include uniaxial or biaxially stretched films such as cloth, knitted fabric, non-woven fabric, heat-shrinkable polyester, polystyrene, polyethylene, polypropylene, polyvinylidene chloride, and polyvinyl chloride.

  The discolorable fabric includes stuffed toys, doll costumes, accessories for dolls such as shoes and bags, dresses, swimwear, clothes such as raincoats, footwear, handmade items such as handkerchiefs and furoshiki, indoor ornaments such as curtains, Used for rugs, shoes, hats, bags, cushions, cushions, pillows, mattresses, ribbons, artificial flowers, boxes, banners, flags, etc.

Examples are shown below, but the present invention is not limited thereto.
In addition, the part in an Example shows a mass part.
Example 1 (see FIGS. 1 to 3)
A microcapsule pigment in which a heat-decolorable reversible thermochromic composition having a color memory property that changes from pink to colorless is encapsulated on the surface of a taffeta fabric made of white nylon fibers having a basis weight of 60 g / m ² as the fabric 21 [ Average particle size 8μm, complete color development temperature 15 ° C, complete color erasing temperature 30 ° C] 30 parts, urethane emulsion resin 50 parts, thickener 2 parts, leveling agent 0.5 parts, antifoaming agent 0.5 parts, cross-linking Using a reversible thermochromic ink composed of 5 parts of the agent, solid printing was performed on a 120 mesh screen plate to form a reversible thermochromic layer 22 to obtain a color-changing fabric (reversible thermochromic fabric) 2.
Separately, on the resin sheet 3 made of a heat-shrinkable polyolefin film having a thickness of 0.01 mm, an adhesive made of an isocyanate-based resin is screen-printed at a 1 cm interval in a circular shape having a diameter of 2 mm, and the color change property The back surface of the fabric and the resin sheet on which the adhesive was printed were pressure-bonded and left at 40 ° C. for 30 minutes to completely cure the adhesive, and heat-treated at 80 ° C. for 5 minutes to shrink the resin sheet. .
Thereafter, the resin sheet was peeled off to obtain an uneven color-changing fabric 1.
When the uneven color-changing fabric is heated to 30 ° C. or higher, the entire surface becomes white, and this state is stored and held in a temperature range exceeding 15 ° C.
Next, when ice water was attached to the uneven color-changing fabric, it turned pink, and this state was stored and held in a temperature range of less than 30 ° C.
When the temperature was again raised to 30 ° C. or more, it turned white, and this change in appearance could be repeated.
Further, the unevenness formed on the uneven color-changing fabric made the fabric three-dimensional and had a unique aesthetics and decoration effect, and the unique color effect could be expressed by combining the thermochromic property and the unevenness.

Example 2
On the surface of a tricot knitted fabric made of white polyester fibers with a basis weight of 100 g / m ^{2 as} a fabric, 10 parts of yellow fluorescent pigment, 50 parts of urethane emulsion resin, 2 parts of thickener, 0.5 part of leveling agent, 0 defoaming agent A non-discoloring layer was formed by printing a polka dot pattern on a 180 mesh screen using a fluorescent ink comprising 5 parts and 5 parts of a crosslinking agent.
Next, 30 parts of a microcapsule pigment (average particle size 8 μm, color change temperature 28 ° C.) encapsulating a heat decolorable reversible thermochromic composition that changes color from black to colorless, 50 parts of urethane emulsion resin, thickener 2 The reversible thermochromic layer is formed on the 100-mesh screen using a reversible thermochromic ink consisting of 5 parts, leveling agent 0.5 part, defoaming agent 0.5 part, and cross-linking agent 5 part. Thus, a discolorable fabric (reversible thermochromic fabric) was obtained.
Separately, on the resin sheet made of a heat-shrinkable polystyrene / polyester composite film with a thickness of 30 μm, an adhesive made of an epoxy resin is screen-printed at 1.5 cm intervals in a circular shape with a diameter of 2 mm, The back surface of the discolorable fabric and the resin sheet on which the adhesive is printed are pressure-bonded, and left to stand at 50 ° C. for 30 minutes to completely cure the adhesive, and the heat treatment is performed at 100 ° C. for 5 minutes to back the discolorable fabric. The resin sheet partially adhered to was shrunk.
Thereafter, the resin sheet was peeled off to obtain an uneven color-changing fabric.
The uneven color-changing fabric was black in a room at 20 ° C., but changed to a yellow polka dot pattern on a white background outdoors at a temperature of 30 ° C. The uneven color-changing fabric turned black again in a room at 20 ° C., and the change in appearance could be repeatedly performed by changing the temperature.
Further, the unevenness formed on the uneven color-changing fabric made the fabric three-dimensional and had a unique aesthetics and decoration effect, and the unique color effect could be expressed by combining the thermochromic property and the unevenness.

Example 3 (see FIGS. 4 to 6)
A microcapsule in which a heat-erasable reversible thermochromic composition having color memory that changes from pink to colorless is encapsulated on the surface of a tricot knitted fabric made of white polyester fibers having a basis weight of 50 g / m ² as the fabric 21 30 parts of pigment (average particle size 8 μm, complete color development temperature 18 ° C., complete color erasing temperature 30 ° C.), blue coloring pigment 0.3 part, urethane emulsion resin 50 parts, thickener 2 parts, leveling agent 0.5 part Then, a reversible thermochromic layer 22 is formed on the entire surface of a 100-mesh screen using a reversible thermochromic ink comprising 0.5 parts of an antifoaming agent and 5 parts of a crosslinking agent, and the reversible heat discoloration layer 22 is further formed. A transparent iris multi-layer film IRIDESCENT FILM IF-8181R / G (BASF), in which an acrylic resin emulsion is coated on the discoloring layer and exhibits an iris due to a light interference phenomenon To obtain a discoloration resistant fabric (reversible thermochromic fabric) 2 by sticking Ltd.) provided with a transparent metallic luster layer 23.
Separately, on the cloth 3 made of heat-shrinkable polyester fiber with a basis weight of 60 g / m ² , an adhesive made of isocyanate resin is screen-printed at a 1 cm interval in a circular shape with a diameter of 2 mm, and the discolorable cloth The back surface of the fabric and the fabric on which the adhesive is printed are pressure-bonded and left at 40 ° C. for 30 minutes to completely cure the adhesive, and then heat-treated at 80 ° C. for 5 minutes to partially stick to the back surface of the discolorable fabric. The applied heat-shrinkable fabric was shrunk.
Thereafter, the fabric having heat shrinkability was peeled off to obtain an uneven color-changing fabric 1.
When the uneven color-changing fabric was heated to 30 ° C. or higher, the entire surface became blue with iris properties, and this state was stored and retained in a temperature range exceeding 18 ° C.
Next, when ice water was attached to the uneven color-changing fabric, the reversible thermochromic layer became purple, and gold and green iris colors appeared. This state was stored and held in a temperature range of less than 30 ° C.
When the temperature was again raised to 30 ° C. or higher, the color became blue with iris, and this aspect change could be repeated.
Further, the unevenness formed on the uneven color-changing fabric made the fabric three-dimensional and had a unique aesthetics and decoration effect, and the unique color effect could be expressed by combining the thermochromic property and the unevenness.

Example 4
As a fabric, a white T / C (65/35) broad fabric surface having a weight per unit area of 110 g / m ² and containing a heat-erasable reversible thermochromic composition having color memory that changes from black to colorless. 30 parts of capsule pigment (average particle size 8 μm, complete color developing temperature 15 ° C., complete color erasing temperature 30 ° C.), acrylic emulsion resin 50 parts, thickener 2 parts, leveling agent 0.5 part, antifoaming agent 0.5 A reversible thermochromic layer is formed by printing a plurality of heart patterns on a 100 mesh screen plate using a reversible thermochromic ink comprising 5 parts of a cross-linking agent and a reversible thermochromic layer. Acrylic resin emulsion is coated on the surface, and it consists of a thin film of polymethyl methacrylate resin and a thin film of polyethylene terephthalate resin. A transparent glittering film composed of 2 parts by weight of a rate resin (Skyrol Fancylite Film, manufactured by SKG Korea, thickness 22 μm, thin film is 100 layers or more) is pasted to provide a transparent metallic luster layer and discoloration Fabric (reversible thermochromic fabric) was obtained.
The transparent glittering film has a reflected light that varies depending on the angle even when the transmitted light is blue, and when the reversible thermochromic layer is dark, high-luminance gold or green is visible, and the reversible thermochromic layer disappears. If the color is white or light, blue or reddish purple with high luminance is visually recognized.
Separately, an adhesive made of an isocyanate resin is screen-printed in a circular shape with a diameter of 2 mm at intervals of 1 cm on a cloth made of heat-shrinkable polyester fiber having a basis weight of 80 g / m ² , and The back side and the fabric printed with the adhesive are pressure-bonded, left at 40 ° C. for 30 minutes to completely cure the adhesive, and heat-treated at 80 ° C. for 5 minutes to partially adhere to the back side of the discolorable fabric. The heat-shrinkable fabric made was shrunk.
Thereafter, the heat-shrinkable fabric was peeled off to obtain an uneven color-changing fabric.
When the uneven color-changing fabric was heated to 30 ° C. or higher, the entire surface became blue or reddish purple with high luminance, and this state was stored and held in a temperature range exceeding 15 ° C.
Next, when ice water is attached to the uneven color-changing fabric, the reversible thermochromic layer becomes black, and thus a bright gold or green heart pattern appears, and this state is stored in a temperature range below 30 ° C. It was done.
When the temperature was again raised to 30 ° C. or more, the entire surface became blue or reddish purple with high luminance, and this aspect change could be repeated.
In addition, the unevenness formed on the uneven color-changing fabric has a three-dimensional fabric that has a unique aesthetic and decorative effect, and a unique color that has glitter due to the change in angle due to thermal discoloration and unevenness. The effect could be expressed.

Example 5
As a support, a tricot knitted cloth surface comprising a white polyester fiber basis weight 40 g / m ^2, 10 parts of pink fluorescent pigment, 50 parts of urethane emulsion resin, 2 parts of a thickener, leveling agent 0.5 parts, vanishing A non-discoloring layer was formed by printing a plurality of heart patterns on a 180 mesh screen using a fluorescent ink comprising 0.5 parts of a foaming agent and 5 parts of a crosslinking agent.
Next, 30 parts of a microcapsule pigment (average particle diameter 8 μm, color change temperature 18 ° C., 30 ° C.) containing acrylic reversible thermochromic composition having a color erasability that changes color from black to colorless, acrylic emulsion Full surface solid printing with 100 mesh screen plate using reversible thermochromic ink consisting of 50 parts resin, 2 parts thickener, 0.5 part leveling agent, 0.5 part defoaming agent and 5 parts crosslinking agent. A reversible thermochromic layer is formed, and an acrylic resin emulsion is coated on the reversible thermochromic layer, and a transparent iris multi-layer film [IRIDESCENT FILM IF-8181R / G (BASF Corp. Product)] was pasted to obtain a discolorable fabric (reversible thermochromic fabric).
Separately, an adhesive made of an isocyanate resin is screen-printed in a circular shape with a diameter of 2 mm at intervals of 1 cm on a cloth made of heat-shrinkable polyester fiber having a basis weight of 80 g / m ² , and The back side and the fabric printed with the adhesive are pressure-bonded, left at 40 ° C. for 30 minutes to completely cure the adhesive, and heat-treated at 80 ° C. for 5 minutes to partially adhere to the back side of the discolorable fabric. The heat-shrinkable fabric made was shrunk.
Thereafter, the heat-shrinkable fabric was peeled off to obtain an uneven color-changing fabric.
When the uneven color-changing fabric was heated to 30 ° C. or higher, a pink heart pattern having iris properties appeared on a white background, and this state was stored and retained in a temperature range exceeding 18 ° C.
Next, when ice water was attached to the uneven color-changing fabric, the reversible thermochromic layer became black, and gold and green iris colors appeared. This state was stored and held in a temperature range of less than 30 ° C.
When the temperature was raised again to 30 ° C. or more, a pink heart pattern having irisiness appeared on a white background, and this change in appearance could be repeated.
Further, the unevenness formed on the uneven color-changing fabric made the fabric three-dimensional and had a unique aesthetics and decoration effect, and the unique color effect could be expressed by combining the thermochromic property and the unevenness.

Example 6
A microcapsule pigment in which a heat-erasable reversible thermochromic composition having a color memory property that changes color from pink to colorless is encapsulated on the surface of a taffeta fabric made of white polyester fibers having a basis weight of 50 g / m ² as the fabric 21 (Average particle diameter 8 μm, complete color development temperature 18 ° C., complete color erasing temperature 30 ° C.) 30 parts, blue coloring pigment 0.3 part, urethane emulsion resin 50 parts, thickener 2 parts, leveling agent 0.5 part, Using a reversible thermochromic ink composed of 0.5 parts of an antifoaming agent and 5 parts of a cross-linking agent, the entire surface is printed on a 100-mesh screen plate to form the reversible thermochromic layer 22, and the reversible thermochromic color further. A transparent iris multi-layer film IRIDESCENT FILM IF-8181R / G (manufactured by BASF Corp.) that applies an acrylic resin emulsion on the layer and exhibits iris properties due to the light interference phenomenon. Wearing a transparent metallic luster layer is provided to obtain a discoloration resistant fabric (reversible thermochromic fabric) 2.
Separately from this, an adhesive made of an isocyanate-based resin is formed in a circular shape having a diameter of 3 mm on a resin-made sheet made of a polystyrene-polyester composite film that is thermally shrunk only in the width direction (one direction) having a thickness of 30 μm. Screen printing is performed at intervals of 5 cm, the back side of the discolorable fabric and the resin sheet on which the adhesive is printed are pressure-bonded, and left at 50 ° C. for 30 minutes to completely cure the adhesive, and heated at 100 ° C. for 5 minutes. The resin sheet that was treated and partially adhered to the back surface of the discolorable fabric was shrunk.
Thereafter, the resin sheet having heat shrinkability was peeled off to obtain an uneven color-changing fabric.
When the uneven color-changing fabric was heated to 30 ° C. or higher, the entire surface became blue with iris properties, and this state was stored and retained in a temperature range exceeding 18 ° C.
Next, when ice water was attached to the uneven color-changing fabric, the reversible thermochromic layer became purple, and gold and green iris colors appeared. This state was stored and held in a temperature range of less than 30 ° C.
When the temperature was again raised to 30 ° C. or higher, the color became blue with iris, and this aspect change could be repeated.
Further, the unevenness formed on the uneven color-changing fabric made the fabric three-dimensional and had a unique aesthetics and decoration effect, and the unique color effect could be expressed by combining the thermochromic property and the unevenness.

Example 7
As a fabric, the surface of a tricot knitted fabric made of white polyester fiber having a basis weight of 50 g / m ² , and 1,3,3-trimethyl-6-trifluoromethyl-6 '-(1-piperidinyl) -spiroindoline naphtho as a photochromic compound 30 parts of microcapsule pigment encapsulating 1 part of oxazine and 50 parts of a styrene-α-methylstyrene copolymer (Rika Hercules Co., Ltd., trade name: Picolatic A5, weight average molecular weight 317), urethane emulsion resin 50 Light on a 100-mesh screen using a photochromic ink consisting of 2 parts, 2 parts thickener, 0.5 parts leveling agent, 0.5 parts defoaming agent and 5 parts crosslinker. A discoloration layer is formed, and further, an acrylic resin emulsion is applied on the photodiscoloration layer, and iris properties are obtained by a light interference phenomenon. To give a clear iris multilayer film IRIDESCENT FILM IF-8181R / G (manufactured by BASF Co.) attached to transparent metallic luster layer provided discoloration fabric (photochromic fabric).
Separately, an adhesive made of isocyanate resin is screen-printed at intervals of 1 cm in a circular shape with a diameter of 3 mm on a cloth made of heat-shrinkable polyester fiber having a basis weight of 60 g / m ² , The back side and the fabric printed with the adhesive are pressure-bonded, left at 40 ° C. for 30 minutes to completely cure the adhesive, and heat-treated at 80 ° C. for 5 minutes to partially adhere to the back side of the discolorable fabric. The heat-shrinkable fabric made was shrunk.
Thereafter, the heat-shrinkable fabric was peeled off to obtain an uneven color-changing fabric.
When the uneven color-changing fabric was irradiated with ultraviolet light with black light, the entire surface became purple with iris properties. Next, when UV irradiation was stopped, it was purple for about 3 minutes, but it gradually turned colorless. Thus, it became a state having iris on a white background, and this aspect change could be repeated.
Further, the unevenness formed on the uneven color-changing fabric made the fabric three-dimensional and had a unique aesthetics and decoration effect, and the unique color effect could be expressed by combining the photochromic property and the unevenness.

Example 8
As a fabric, on the surface of a tricot knitted fabric made of white polyester fiber having a basis weight of 50 g / m ² , 4 parts by weight of 1,3,3-trimethylindolino-6 ′-(1-piperidinyl) -spironaphthoxazine as a photochromic compound; Styrene-α-methylstyrene copolymer (Rika Hercules Co., Ltd., trade name: Picola stick A75, weight average molecular weight 917) 30 parts of microcapsule pigment encapsulating 40 parts by weight, urethane emulsion resin 50 parts, increase Using a photochromic ink consisting of 2 parts of a sticking agent, 0.5 part of a leveling agent, 0.5 part of an antifoaming agent, and 5 parts of a crosslinking agent, the entire surface is printed on a 100 mesh screen plate to form a photochromic layer A transparent rainbow formed by applying an acrylic resin emulsion on the photochromic layer and exhibiting iris properties by a light interference phenomenon. Sex multilayer film Iridescent FILM obtain IF-8181R / G a (BASF Co.) stuck to a transparent metal luster layer discoloration fabric by (photochromic fabric).
Separately from this, an adhesive made of an isocyanate-based resin is formed in a circular shape having a diameter of 3 mm on a resin-made sheet made of a polystyrene-polyester composite film that is thermally shrunk only in the width direction (one direction) having a thickness of 30 μm. Screen printing is performed at intervals of 5 cm, the back side of the discolorable fabric and the resin sheet on which the adhesive is printed are pressure-bonded, and left at 50 ° C. for 30 minutes to completely cure the adhesive, and heated at 100 ° C. for 5 minutes. The resin sheet that was treated and partially adhered to the back surface of the discolorable fabric was shrunk.
Thereafter, the resin sheet having heat shrinkability was peeled off to obtain an uneven color-changing fabric.
When the uneven color-changing fabric was irradiated with ultraviolet light with black light, the entire surface became blue with iris, and then when the ultraviolet irradiation was stopped, it showed blue for about 5 minutes, but gradually turned colorless. Thus, it became a state having iris on a white background, and this aspect change could be repeated.
Further, the unevenness formed on the uneven color-changing fabric made the fabric three-dimensional and had a unique aesthetics and decoration effect, and the unique color effect could be expressed by combining the photochromic property and the unevenness.

DESCRIPTION OF SYMBOLS 1 Convex-shaped discolorable fabric 2 Discolorable fabric 21 Fabric 22 Reversible thermochromic layer 23 Transparent metallic luster layer 3 Fabric or resin sheet

Claims (4)

  A fabric or resin sheet having a heat shrinkability greater than that of the discolorable fabric is adhered to the back surface of the discolorable fabric so as to have a plurality of adhering locations and non-adhering locations, and heated to be made of fabric or resin. The manufacturing method of the uneven | corrugated color-change fabric which shrinks | contracts a sheet | seat, forms an unevenness | corrugation in a discolorable fabric, and peels the said cloth or resin-made sheets.   The uneven color-changing fabric according to claim 1, wherein the color-changing fabric is either a reversible thermochromic fabric having a reversible thermochromic layer on the fabric or a photochromic fabric having a photochromic layer on the fabric. Production method.   The method for producing an uneven color-changing fabric according to claim 2, wherein a non-color-changing layer is provided between the fabric and the reversible thermochromic layer or photochromic layer.   The method for producing a concavo-convex color-changing fabric according to claim 2 or 3, wherein a transparent metallic luster layer is provided on the reversible thermochromic layer or photochromic layer.

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