JP6648982B2 - Cracked printed or painted material and method for producing the same - Google Patents

Description

  The present invention relates to a cracked printed or painted article and a method for producing the same. More specifically, the present invention relates to a printed or painted article having a cracked pattern and a method for producing the same.

BACKGROUND ART Conventionally, it has been disclosed that a nail material for forming a crack-patterned film and a crack-patterned film provided on the nail using the same (for example, see Patent Document 1).
Further, a method of providing a crack pattern for cracking an outer coating layer provided on the surface of a pattern-attached body, and a crack-pattern-attached body are disclosed (for example, see Patent Document 2).
Even if an irregular cracked pattern is formed on the surface of the nail polish and the cracked pattern-provided body, the irregular pattern alone has poor surprising properties, and its use may be limited depending on the application.

JP 2013-147440 A JP-A-2006-56000

  The present invention is intended to solve the problem of this type of cracked printing or painted material, and has an unexpected pattern provided with an irregular pattern and a cracked pattern along a concave portion of the support, and is rich in applications. An object of the present invention is to provide a cracked printed or painted article and a method for producing the same.

The present invention is made by providing a coating by printing or painting on a support having at least a recess, wherein the coating possess a cracked pattern along the recess, and irregular crack patterns, reversible color change in said film the Ruhibiware printing or coating, such containing sexual material and requirements.
Furthermore, prior Symbol reversible color change material can be selected from the thermochromic material or reversibly photochromic material, wherein the coating is a requirement, such as to have optical transparency.
Further, on a support having at least a concave portion, a coating is formed by printing or painting using a liquid composition comprising at least an inorganic pigment, a resin, and a solvent, and the coating is cracked to form a crack pattern along the concave portion. And a method for producing a cracked printed or painted article that forms an irregular cracked pattern.

  The present invention relates to a crack printed or coated article having irregular crack patterns and crack patterns along concave portions of a supporter, which has unexpected properties and is applicable to various uses, and a method for producing the same. Can be provided.

It is a front view of the reference example of a crack print or a coating. It is a front view of the solid施例cracks printing or coating of the present invention. FIG. 3 is a front view showing a state in which the reversible color-changing material of the cracked print or the painted object in FIG. 2 has disappeared. FIG. 3 is an explanatory longitudinal sectional view of the cracked printed or painted object of FIG. 2. FIG. 3 is an explanatory diagram showing the discoloration behavior of a microcapsule pigment containing a heat-decolorable reversible thermochromic composition. FIG. 3 is an explanatory view showing the color change behavior of a microcapsule pigment containing a heat-decolorable reversible thermochromic composition having color memory. FIG. 2 is an explanatory diagram showing the color change behavior of a microcapsule pigment containing a heat-colorable reversible thermochromic composition.

According to the present invention, a coating is provided on a support having a concave portion, and the coating is a crack-printed or painted article having a crack pattern along the concave portion and an irregular crack pattern.
The concave portion may be formed by forming a regular groove formed in a linear shape, a curved shape, or a combination thereof on the support to form a concave portion, or a convex portion may be formed on the support, and the periphery of the support and the convex portion may be formed. Can be a concave portion.
As a method of forming the concave portion on the support, it may be formed at the time of molding the support, or the support may be formed by cutting, melting, or the like, or formed by fixing the supports to each other. It can be formed by providing a coating film or the like.
It is preferable that the concave portions are regularly arranged on the support.
Examples of the support having the concave portion include paper, synthetic paper, knitted fabric, woven fabric, non-woven fabric, and the like, synthetic leather, natural leather, rubber, plastic, glass, ceramics, metal, wood, stone, and the like. The form may be a planar form or a three-dimensional form.
A colorant may be contained in the support, or a colored layer containing the colorant may be provided on the support.
The colored layer may be a colored image, such as a picture, a pattern, a pattern, a character, or a symbol.

A coating for forming a cracked pattern is provided on the support.
The coating is formed by printing or coating a liquid composition comprising at least an inorganic pigment and a solvent on a support, and cracking the coating when dried to form a cracked coating.

  The inorganic pigment is added in order to form a cracked film in the process of volatilization of the solvent, and includes silicon dioxide, titanium dioxide, zirconium dioxide, aluminum oxide, magnesium silicate, magnesium oxide, chromium oxide, and iron oxide. , Zinc oxide, calcium carbonate and the like are used.

  Examples of the solvent include toluene, xylene, chlorobenzene, mineral spirit, solvesso, heptane, cyclohexanone, acetone, tetrahydrofuran, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, isobutyl acetate, ethylene glycol dimethyl ether, methyl cellosolve acetate, butyl cellosolve And organic solvents such as ethanol, propanol and butanol, and water.

Further, if necessary, a resin can be added to the liquid composition.
The resin may be a water-soluble or oil-soluble resin, but an oil-soluble resin is preferably used.
Specific examples of the resin include an ionomer resin, an isobutylene-maleic anhydride resin copolymer resin, an acrylonitrile-acrylic styrene copolymer resin, an acrylonitrile-styrene copolymer resin, an acrylonitrile-butadiene-styrene copolymer resin, and an acrylonitrile chlorinated polyethylene resin. 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 copolymer resin, chlorinated polyethylene resin, chlorinated polypropylene resin, polyamide resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polycarbonate resin, polystyrene resin, c Impact polystyrene resin, polypropylene resin, polymethylstyrene resin, polyacrylate resin, polymethylmethacrylate resin, epoxy acrylate resin, alkylphenol resin, rosin-modified phenolic resin, rosin-modified alkyd resin, phenolic 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, poly Isobutylene, butyl rubber, polyvinyl alkyl ether, rosin, rosin ester, rosin derivative, polyterpene resin, oil-soluble phenol resin, petroleum Hydrogenated 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 and the like.
The resins may be used alone or in combination of two or more.

Further, a dye or a pigment can be contained in the liquid composition.
Examples of the dye include acid dyes, basic dyes, and direct dyes.Examples of pigments include carbon black, inorganic pigments such as ultramarine blue, phthalocyanine, azo, anthraquinone, diketopyrrolopyrrole, and quinacridone. Organic pigments such as isoindolinone type are exemplified.
As the fluorescent pigment, a fluorescent pigment in the form of fine particles of a synthetic resin in which various fluorescent dyes are made a solid solution in a resin matrix can be used.

Further, a reversible discolorable material may be contained in the liquid composition.
Examples of the reversible color-changing material include a reversible thermochromic material and a reversible photochromic material.
Examples of the reversible thermochromic material include inorganic materials such as Ag ₂ HgI ₄ and Cu ₂ HgI ₄ , liquid crystal, an electron-donating color-forming organic compound, an electron-accepting compound, and a reversible color reaction between the two. A heat-decolorable reversible thermochromic material containing three components with an organic compound medium generated on the other hand, or an electron-donating color-forming organic compound, an electron-accepting compound, and a reversible color reaction between the two. A heat-colorable reversible thermochromic material containing three components with an organic compound medium generated in the process is used.
Among them, 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 between 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 for determining the temperature at which the color reaction of the two occurs. A reversible thermochromic microcapsule pigment (reversible thermochromic pigment) containing a composition and changing color from color to colorless is exemplified.
The reversible thermochromic composition is described in JP-B-51-44706, JP-B-51-44707, JP-B-1-29398 and the like at a predetermined temperature (discoloration point). Discolored before and after, a decolored state in the temperature range above the high-temperature side discoloration point, presents a color-developed state in the temperature range below the low-temperature side discoloration point, and only one specific state exists in the normal temperature range of the two states, The other state is maintained while the heat or cold required to develop the state is applied, but returns to the state exhibited in the normal temperature range when the application of the heat or cold disappears, the hysteresis width is increased. A heat-decolorable reversible thermochromic composition (decolored by heating and colored by cooling) having relatively small properties (ΔH = 1 to 7 ° C.) can be applied (see FIG. 5).

Also, large hysteresis characteristics (ΔH _B = 8 to 50 ° C.) described in Japanese Patent Publication No. 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 coloring density due to the temperature change is such that the temperature rises from a temperature lower than the color change temperature range, and conversely, the temperature decreases from a temperature higher than the color change temperature range. The color changes in a low temperature range below the complete color development temperature (t ₁ ), or the decoloration state in a high temperature range above the complete decolorization temperature (t ₄ ). Heat-decoloring type (decolorizes by heating and develops color by cooling) reversible thermochromic composition having a color memory property in the [temperature range between t _{2 and} t ₃ (substantially two-phase holding temperature range)] (See FIG. 6).

The hysteresis characteristics of the reversible thermochromic composition in a color density-temperature curve will be described.
In FIG. 6, the vertical axis represents color density, and the horizontal axis represents temperature. The change in the 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) at which a complete decoloring state is reached, and B is a temperature t ₃ at which decoloring starts (hereinafter, a decoloring start temperature and a decoloring start temperature). C) is a point indicating the 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 (hereinafter, complete) at which a full color development state is reached. (Referred to as a coloring 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 Is a substantial discoloration temperature range.
Further, the length of the line segment EF is a scale indicating the contrast of discoloration, and the length of the line segment HG passing through the midpoint of the line segment EF is a temperature width (hereinafter, referred to as a hysteresis width ΔH) indicating a degree of hysteresis. If the ΔH value is small, only one specific state can exist in the normal temperature range between the two states before and after the color change. Further, when the ΔH value is large, it is easy to maintain each state before and after discoloration.

Hereinafter, the components (a), (b), and (c) of the reversible thermochromatic composition will be described.
Examples of the electron-donating color-forming organic compound (a) include diphenylmethanephthalide, phenylindolylphthalide, indolylphthalide, diphenylmethaneazaphthalide, phenylindolylazaphthalide, and fluoran. , Styrinoquinolines, diazarhodamine lactones, pyridines, quinazolines, bisquinazolines and the like.
Hereinafter, these compounds will be exemplified.
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-diphenylaminofluoran,
3,6-dimethoxyfluoran,
3,6-di-n-butoxyfluoran,
2-methyl-6- (N-ethyl-Np-tolylamino) fluoran,
3-chloro-6-cyclohexylaminofluoran,
2-methyl-6-cyclohexylaminofluoran,
2- (2-chloroamino) -6-dibutylaminofluoran,
2- (2-chloroanilino) -6-di-n-butylaminofluoran,
2- (3-trifluoromethylanilino) -6-diethylaminofluoran,
2- (N-methylanilino) -6- (N-ethyl-Np-tolylamino) fluoran,
1,3-dimethyl-6-diethylaminofluoran,
2-chloro-3-methyl-6-diethylaminofluoran,
2-anilino-3-methyl-6-diethylaminofluoran,
2-anilino-3-methoxy-6-diethylaminofluoran,
2-anilino-3-methyl-6-di-n-butylaminofluoran,
2-anilino-3-methoxy-6-di-n-butylaminofluoran,
2-xyridino-3-methyl-6-diethylaminofluoran,
1,2-benz-6-diethylaminofluoran,
1,2-benz-6- (N-ethyl-N-isobutylamino) fluoran,
1,2-benz-6- (N-ethyl-N-isoamylamino) fluoran,
2- (3-methoxy-4-dodecoxystyryl) quinoline,
Spiro [5H- (1) benzopyrano (2,3-d) pyrimidin-5,1 ′ (3′H) isobenzofuran] -3′-one,
2- (diethylamino) -8- (diethylamino) -4-methyl-spiro [5H- (1) benzopyrano (2,3-g) pyrimidin-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-dimethylbenzeneamine,
2- (4'-dimethylaminophenyl) -4-methoxy-quinazoline,
4,4 '-(ethylenedioxy) -bis [2- (4-diethylaminophenyl) quinazoline] and the like.
In addition, as the fluorans, in addition to the compounds having a substituent on a phenyl group forming a xanthene ring, a substituent is also present on a phenyl group having a substituent on a phenyl group forming a xanthene ring and also forming a lactone ring (for example, , An alkyl group such as a methyl group, and a halogen atom such as a chloro group).

As the electron accepting compound of the component (b), a compound group having an active proton, a pseudo-acid compound group (a compound group which is not an acid, but acts as an acid in the composition to form the component (a) to develop a color), There is a group of compounds having electron vacancies.
When the compound having an active proton is exemplified, the compound having a phenolic hydroxyl group includes monophenols to polyphenols, and further, as a substituent thereof, an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, a carboxy group and an ester thereof. Or phenol-aldehyde condensed resins such as bis- and tris-type phenols having an amide group, a halogen group and the like. Further, a metal salt of the compound having a phenolic hydroxyl group may be used.
Specific examples are described below.
Phenol, o-cresol, tert-butylcatechol, nonylphenol, n-octylphenol, n-dodecylphenol, n-stearylphenol, p-chlorophenol, p-bromophenol, o-phenylphenol, n-butyl p-hydroxybenzoate N-octyl p-hydroxybenzoate, resorcinol, dodecyl gallate, 4,4-dihydroxydiphenylsulfone, bis (4-hydroxyphenyl) sulfide, 1,1-bis (4-hydroxyphenyl) ethane, 1,1- Bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) n-butane, 1,1-bis (4-hydroxyphenyl) n-pentane, 1,1-bis (4-hydroxyphenyl) n-hexane, 1,1-bis (4- (Droxyphenyl) n-heptane, 1,1-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-methylpropane, 1,1-bis (4-hydroxyphenyl) -3-methylbutane 1,1-bis (4-hydroxyphenyl) -3-methylpentane, 1,1-bis (4-hydroxyphenyl) -2,3-dimethylpentane, 1,1-bis (4-hydroxyphenyl) -2 -Ethylbutane, 1,1-bis (4-hydroxyphenyl) -2-ethylhexane, 1,1-bis (4-hydroxyphenyl) -3,7-dimethyloctane, -Phenyl-1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) n-butane, 2,2-bis ( 4-hydroxyphenyl) n-pentane, 2,2-bis (4-hydroxyphenyl) n-hexane, 2,2-bis (4-hydroxyphenyl) n-peptane, 2,2-bis (4-hydroxyphenyl) n-octane, 2,2-bis (4-hydroxyphenyl) n-nonane, 2,2-bis (4-hydroxyphenyl) n-decane, 2,2-bis (4-hydroxyphenyl) n-dodecane, , 2-bis (4-hydroxyphenyl) ethyl propionate, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 2,2-bis (4-hydroxyphenyl) Enyl) -4-methylhexane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-hydroxy-3-methylphenyl) propane and the like.
Although the compound having a phenolic hydroxyl group can exhibit the most effective thermochromic properties, aromatic carboxylic acids and aliphatic carboxylic acids having 2 to 5 carbon atoms, carboxylic acid metal salts, acidic phosphoric acid esters and their salts It may be a compound selected from metal salts, 1,2,3-triazole and derivatives thereof, and the like.

The component (c) of the reaction medium that causes the electron transfer reaction by the components (a) and (b) to reversibly occur in a specific temperature range will be described.
Examples of the component (c) include alcohols, esters, ketones, and ethers.
The compounds are exemplified below.
As the alcohols, aliphatic monovalent saturated alcohols having 10 or more carbon atoms are effective. Specifically, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl Alcohol, heptadecyl alcohol, octadecyl alcohol, eicosyl alcohol, docosyl alcohol and the like.

As the esters, esters having 10 or more carbon atoms are effective, and any combination of a monovalent carboxylic acid having an aliphatic and alicyclic or aromatic ring and a monohydric alcohol having an aliphatic and alicyclic or aromatic ring , Aliphatic and alicyclic esters obtained from any combination of polyhydric carboxylic acids having aliphatic and alicyclic or aromatic rings and monohydric alcohols having aliphatic and alicyclic or aromatic rings Alternatively, esters obtained from an arbitrary combination of a monovalent carboxylic acid having an aromatic ring and a polyhydric alcohol having an aliphatic and alicyclic or aromatic ring, and specifically, ethyl caprylate, octyl caprylate, and caprylate Stearyl acid, myristyl caprate, docosyl caprate, 2-ethylhexyl laurate, n-decyl laurate, myris 3-methylbutyl phosphate, cetyl myristate, isopropyl palmitate, neopentyl palmitate, nonyl palmitate, cyclohexyl palmitate, n-butyl stearate, 2-methylbutyl stearate, 3,5,5-trimethylhexyl stearate, stearin N-undecyl acid, pentadecyl stearate, stearyl stearate, cyclohexylmethyl stearate, isopropyl behenate, hexyl behenate, lauryl behenate, behenyl behenate, cetyl benzoate, stearyl p-tert-butyl benzoate, dimyristyl phthalate , Distearyl phthalate, dimyristyl oxalate, dicetyl oxalate, dicetyl malonate, dilauryl succinate, dilauryl glutarate, diundecyl adipate, azelaic acid Lauryl, di- (n-nonyl) sebacate, dineopentyl 1,18-octadecylmethylenedicarboxylate, ethylene glycol dimyristate, propylene glycol dilaurate, propylene glycol distearate, hexylene glycol dipalmitate, 1,5-pentane Diol distearate, 1,2,6-hexanetrioltrimyristate, 1,4-cyclohexanedioldidecyl, 1,4-cyclohexanedimethanol dimyristate, xylene glycol dicaprinate, xylene glycol distearate, and the like. No.
Further, an ester of a saturated fatty acid and a branched aliphatic alcohol, an ester of an unsaturated fatty acid or a saturated fatty acid having a branch or a substituent or an aliphatic alcohol 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, 2-ethylhexyl myristate, 2-ethylhexyl caprate, 3,5,5-trimethylhexyl laurate, 3,5,5-trimethylhexyl palmitate, 3,5,5-trimethylhexyl stearate, 2-methylbutyl caproate, 2-methylbutyl caprylate, 2-methylbutyl caprate, 1-ethylpropyl palmitate, 1-ethylpropyl stearate, 1-ethylpropyl behenate, 1-ethylhexyl laurate, 1-ethylhexyl myristate, 1-ethylhexyl palmitate, 2-methylpentyl caproate, 2-methylpentyl caprylate, 2-methylpentyl caprate, 2-methylpentyl laurate, 2-methylstearate Met Butyl, 2-methylbutyl stearate, 3-methylbutyl stearate, 1-methylheptyl stearate, 2-methylbutyl behenate, 3-methylbutyl behenate, 1-methylheptyl stearate, 1-methylheptyl behenate, caproic acid 1 -Ethylpentyl, 1-ethylpentyl palmitate, 1-methylpropyl stearate, 1-methyloctyl stearate, 1-methylhexyl stearate, 1,1-dimethylpropyl laurate, 1-methylpentyl caprate, palmitic acid 2-methylhexyl, 2-methylhexyl stearate, 2-methylhexyl behenate, 3,7-dimethyloctyl laurate, 3,7-dimethyloctyl myristate, 3,7-dimethyloctyl palmitate, 3,3 stearic acid 7-Jim Ruoctyl, 3,7-dimethyloctyl behenate, stearyl oleate, behenyl oleate, stearyl linoleate, behenyl linoleate, 3,7-dimethyloctyl erucate, stearyl erucate, isostearyl erucate, cetyl isostearate, isostearin Stearyl acid, 2-methylpentyl 12-hydroxystearate, 2-ethylhexyl 18-bromostearate, isostearyl 2-ketomyristate, 2-ethylhexyl 2-fluoromyristate, cetyl butyrate, stearyl butyrate, behenyl butyrate and the like. Can be

  The component (c) for obtaining a reversible thermochromic composition having color memory properties is a carboxylic acid ester compound having a ΔT value (melting point−cloud point) of 5 ° C. or more and less than 50 ° C. A carboxylic acid ester containing a substituted aromatic ring, an ester of a carboxylic acid containing an unsubstituted aromatic ring and an aliphatic alcohol having 10 or more carbon atoms, a carboxylic acid ester containing a cyclohexyl group in a molecule, and a fatty acid having 6 or more carbon atoms. Unsubstituted aromatic alcohol or phenol ester, fatty acid having 8 or more carbon atoms and branched aliphatic alcohol or ester, dicarboxylic acid and aromatic alcohol or branched aliphatic alcohol ester, dibenzyl cinnamate, heptyl stearate, didecyl adipate , Dilauryl adipate, dimyristyl adipate, dicetyl adipate, disteary adipate , Trilaurin, trimyristin, tristearin, Dimyristate, distearate and the like are used.

A 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 fatty acid having 10 to 16 carbon atoms. Fatty acid ester compounds having a total of 17 to 23 carbon atoms obtained from aromatic carboxylic acids are also effective.
Specifically, n-pentadecyl acetate, n-tridecyl butyrate, n-pentadecyl butyrate, n-undecyl caproate, n-tridecyl caproate, n-pentadecyl caproate, n-nonyl caprylate, n-undecyl caprylate, N-tridecyl caprylate, n-pentadecyl caprylate, n-heptyl caprate, n-nonyl caprate, n-undecyl caprate, n-tridecyl caprate, n-pentadecyl caprate, n-pentyl laurate, lauric acid n-heptyl, n-nonyl laurate, n-undecyl laurate, n-tridecyl laurate, n-pentadecyl laurate, n-pentyl myristate, n-heptyl myristate, n-nonyl myristate, n-myristate Undecyl, n-tridecyl myristate, N-pentadecyl listate, n-pentyl palmitate, n-heptyl palmitate, n-nonyl palmitate, n-undecyl palmitate, n-tridecyl palmitate, n-pentadecyl palmitate, n-nonyl stearate, stearic acid n-undecyl, n-tridecyl stearate, n-pentadecyl stearate, n-nonyl eicosanoate, n-undecyl eicosanoate, n-tridecyl eicosanoate, n-pentadecyl eicosanoate, n-nonyl behenate, n-behenate Undecyl, n-tridecyl behenate, n-pentadecyl behenate and the like can be mentioned.

As ketones, aliphatic ketones having a total carbon number of 10 or more are effective, and 2-decanone, 3-decanone, 4-decanone, 2-undecanone, 3-undecanone, 4-undecanone, 5-undecanone, 5-undecanone, -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, lauron, stearone, and the like.
Further, arylalkyl ketones having a total carbon number of 12 to 24, for example, n-octadecanophenone, n-heptadecanophenone, n-hexadecanophenone, n-pentadecanophenone, n-tetradecano Phenone, 4-n-dodecaacetophenone, 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-pentylacetophene Emissions, cyclohexyl phenyl ketone, benzyl -n- butyl ketone, 4-n-butyl acetophenone, n- hexanophenone, 4-isobutyl acetophenone, 1-acetonaphthone, 2-acetonaphthone, may be mentioned cyclopentyl phenyl ketone.

  As ethers, aliphatic ethers having a total carbon number of 10 or more are effective, and dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, dinonyl ether, didecyl ether, diundecyl ether, didodecyl ether, ditriethyl ether Decyl ether, ditetradecyl ether, dipentadecyl ether, dihexadecyl ether, dioctadecyl ether, decanediol dimethyl ether, undecanediol dimethyl ether, dodecanediol dimethyl ether, tridecanediol dimethyl ether, decanediol diethylether, undecanediol diethylether, etc. Can be mentioned.

  Further, a specific alkoxyphenol compound having a linear or side chain alkyl group having 3 to 18 carbon atoms may be used as the electron accepting compound (JP-A-11-129623 and JP-A-11-5973), or Using a hydroxybenzoic acid ester (Japanese Patent Application Laid-Open No. 2001-105732) or using a gallic acid ester or the like (Japanese Patent Publication No. 51-44706, Japanese Patent Application Laid-Open No. 2003-253149) A reversible thermochromic microcapsule pigment (reversible thermochromic pigment) containing a reversible thermochromic composition (decolored by cooling) can also be applied (see FIG. 7).

  The mixing ratio of the components (A), (B) and (C) depends on the density, the discoloration temperature, the discoloration form, and the type of each component. Generally, the component ratio at which desired discoloration characteristics are obtained is as follows: Component (b) ranges from 0.1 to 50, preferably from 0.5 to 20, component (c) from 1 to 800, and preferably from 5 to 200, relative to component 1. Parts by weight).

Examples of the method for microencapsulating the reversible thermochromic composition include an interfacial polymerization method, an interfacial polycondensation method, an in situ polymerization method, a curing-in-liquid coating method, a phase separation method from an aqueous solution, and a phase separation method from an organic solvent. , A melt-dispersion cooling method, an air suspension coating method, a spray drying method and the like, which are appropriately selected according to the application.
Further, a secondary resin film may be further provided on the surface of the microcapsule according to the purpose to impart durability, or the surface properties may be modified for practical use.
Here, a non-thermochromic dye or pigment may be blended in the microcapsule to have a configuration that exhibits a tautomeric color change from colored (1) to colored (2).
By being encapsulated in the microcapsules, a chemically and physically stable pigment can be constituted, and the average particle diameter is in the range of 0.1 to 50 μm, preferably 0.5 to 30 μm, more preferably 1 to 20 μm. Meet.
The particle size was measured using a laser diffraction / scattering type particle size distribution measuring device (LA-300, manufactured by Horiba, Ltd.), and the average particle size (median size) was determined on a volume basis based on the numerical value. Is calculated by

As the reversible photochromic material, a photochromic compound, or a reversible photochromic microcapsule pigment in which a photochromic compound is encapsulated in microcapsules, a reversible photochromic resin in which a photochromic compound is dispersed in a thermoplastic or thermosetting resin. Examples include reversible photochromic pigments such as particles.
Examples of the method of microencapsulating the photochromic compound include the above-described methods, and can form a chemically and physically stable pigment, and have an average particle diameter of 0.1 to 50 μm, preferably 0.5 to 30 μm, and more preferably The range of 1 to 20 μm satisfies practicality.
Non-thermochromic dyes and pigments may be blended in the microcapsules to provide a structure that exhibits a tonal color change from colored (1) to colored (2).

Among the photochromic compounds, spirooxazine derivatives are shown below, but the present invention is not limited thereto.
As the indolinospirobenzoxazine-based compound,
1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine],
6'-chloro-5-fluoro-1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine],
3,3-dimethyl-1-ethylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine],
5,7-difluoro-1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine],
5-cyano-3,3-dimethyl-1- (methoxycarbonyl) methylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine],
1'-methyldispiro [cyclohexane-1,3 '-[3H] indole-2'(1'H), 3 "-[3H] pyrido [4,3-f] [1,4] benzoxazine],
1'-methyl-5'-nitrodispiro [cyclopentane-1,3 '-[3H] -indole-2'(1'H), 3 "-[3H] pyrido [4,3-f] [1,4 Benzoxazine],
1,3,3,5'-tetramethylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine],
6'-Fluoro-1'-methyldispiro [cyclohexane-1,3 '-[3H] indole-2'(1'H), 3 "-[3H] pyrido [4,3-f] [1,4] benzo Oxazine],
1-benzyl-6'-chloro-3,3-dimethylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine],
6'-methoxy-1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine],
5-chloro-1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine],
5-bromo-1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine],
5-iodo-1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine],
5-trifluoromethyl-1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine],
3,3-diethyl-1-methylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine],
1,3,3,6'-tetramethylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine],
6-chloro-1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine],
5'-fluoro-1'-methyldispiro [cyclohexane-1,3 '-[3H] indole-2'(1'H), 3 "-[3H] pyrido [4,3-f] [1,4] benzo Oxazine],
5-cyano-1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine],
5-ethoxycarbonyl-1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine],
4 ', 6'-difluoro-1'-methyldispiro [cyclohexane-1,3'-[3H] indole-2 '(1'H), 3 "-[3H] pyrido [4,3-f] [1, 4] benzoxazine],
3,3-dimethyl-1- (methoxycarbonyl) methylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine],
3,3-dimethyl-1-phenylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine],
5-methoxy-1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine],
1,3,3,5-tetramethylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine],
7'-chloro-1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine],
1,3,3,7'-tetramethylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine],
7'-methoxy-1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine],
1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] pyrido [2,3-f] [1,4] benzoxazine],
6'-chloro-5-fluoro-1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] pyrido [2,3-f] [1,4] benzoxazine],
5-chloro-1,3-dimethyl-3-ethyl-5'-methoxyspiro [2H-indole-2,3 '-[3H] pyrido [2,3-f] [1,4] benzoxazine],
3,3-diethyl-1-methyl-5-nitrospiro [2H-indole-2,3 '-[3H] pyrido [2,3-f] [1,4] benzoxazine],
1 ', 6'-dimethylspiro [cyclohexane-1,3'-[3H] indole-2 '(1'H), 3 "-[3H] pyrido [2,3-f] [1,4] benzoxazine ],
9 "-bromo-1'-methoxycarbonylmethyl-5'-trifluoromethyldispiro [cyclopentane-1,3 '-[3H] -indole-2'[1'H],3"-[3H] pyrido [2,3-f] [1,4] benzoxazine],
1-benzyl-3,3-di-nbutyl-7'-ethyl-5-methoxyspiro [2H-indole-1,3 '-[3H] pyrido [2,3-f] [1,4] benzoxazine ],
1'-n-butyl-6'-iododispiro [cycloheptane-1,3 '-[3H] -indole-2'(1'H), 3 "-[3H] pyrido [2,3-f] [1 , 4] benzoxazine],
3,3-dimethyl-9'-iodo-1-naphthylspiro [2H-indole-2,3 '-[3H] pyrido [2,3-f] [1,4] benzoxazine],
4'-cyano-1 '-(2- (methoxycarbonyl) ethyl) dispiro [cyclohexane-1,3'-[3H] indole-2 '(1'H), 3 "-[3H] pyrido [2,3 -F] [1,4] benzoxazine],
7-methoxycarbonyl-1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] pyrido [2,3-f] [1,4] benzoxazine],
4-bromo-3,3-diethyl-9'-ethoxy-1- (2-phenyl) ethylspiro [2H-indole-2,3 '-[2,3-f] [1,4] benzoxazine],
1'-methyldispiro [cyclohexane-1,3 '-[3H] -indole-2'(1'H), 3 "-[3H] pyrido [2,3-f] [1,4] benzoxazine],
6-fluoro-1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] pyrido [2,3-f] [1,4] benzoxazine],
5-ethyl-9-fluoro-1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] pyrido [2,3-f] [1,4] benzoxazine],
1'-benzyl-6 "-iododispiro [cyclopentane-1,3 '-[3H] -indole-2'(1'H),3"-[3H] pyrido [2,3-f] [1,4 Benzoxazine],
5-ethoxy-1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] pyrido [2,3-f] [1,4] benzoxazine],
1'-methyl-5'-trichloromethyldispiro [cyclohexane-1,3 '-[3H] -indole-2'(1'H), 3 "-[3H] pyrido [2,3-f] [1 , 4] benzoxazine],
1,3-diethyl-3-methylspiro [2H-indole-2,3 ′-[3H] pyrido [2,3-f] [1,4] benzoxazine],
1'-methoxycarbonylmethyldispiro [cyclohexane-1,3 '-[3H] -indole-2'(1'H)-[3H] pyrido [2,3-f] [1,4] benzoxazine] And halogenated, methyl, ethyl, methylene, ethylene, and hydroxyl groups of the indole and benzene rings of indolinospirobenzoxazine.

As the indolinospironaphthoxazine-based compound,
1,3,3-trimethyl-spiroindolinenaphthooxazine,
1,3,3-trimethyl-5-chloro-spiroindoline naphthooxazine,
1,3,3-trimethyl-5-bromo-spiroindolinenaphthooxazine,
1,3,3,5-tetramethyl-spiroindolinenaphthooxazine,
1,3,3-trimethyl-5-n-propyl-spiroindolinenaphthooxazine,
1,3,3-trimethyl-5-iso-butyl-spiroindolinenaphthooxazine,
1,3,3-trimethyl-5-methoxy-spiroindolinenaphthooxazine,
1,3,3-trimethyl-5-n-propoxy-spiroindolinenaphthooxazine,
1,3,3-trimethyl-5-cyano-spiroindoline naphthoxazine,
1-n-propyl-3,3-dimethyl-spiroindolinenaphthooxazine,
1-iso-butyl-3,3-dimethyl-spiroindolinenaphthooxazine,
1-n-octyl-3,3-dimethyl-spiroindolinenaphthooxazine,
1-n-octadecyl-3,3-dimethyl-spiroindolinenaphthooxazine,
Sodium 1,3,3-trimethyl-8'-sulfonate-spiroindolinenaphthooxazine,
1,3,3-trimethyl-9'-methoxyspiroindoline naphthooxazine,
1,3,3-trimethyl-8'-cyano-spirobenzoindoline naphthooxazine,
1,3,3-trimethyl-5-trifluoro-spiroindolinenaphthooxazine,
1- (4'-methylphenyl) -3,3-dimethyl-spiroindolinenaphthooxazine,
1,3,3-trimethyl-6 '-(2,3-dihydro-1-indolino) -spiroindolinenaphthooxazine,
1,3,3-trimethyl-6 '-(1-piperidinyl) -spiroindolinenaphthooxazine,
1,3,3-trimethyl-6 '-(1-morpholino) -spiroindolinenaphthooxazine,
1-ethyl-3,3-dimethyl-6-trifluoromethyl-6 '-(1-morpholino) -spiroindolinenaphthooxazine,
1,3,3-trimethyl-6-trifluoromethyl-6 ′-(1-piperidinyl) -spiroindolinenaphthoxazine,
1-benzyl-3,3-dimethyl-spiroindolinenaphthooxazine,
1- (4-methoxybenzyl) -3,3-dimethyl-spiroindolinenaphthooxazine,
1- (4-chlorobenzyl) -3,3-dimethyl-spiroindolinenaphthooxazine,
1-ethyl-3,3-dimethyl-spiroindolinenaphthooxazine,
1-isopropyl-3,3-dimethyl-spiroindolinenaphthooxazine,
1- (2-phenoxyethyl) -3,3-dimethyl-spiroindolinenaphthooxazine,
1,3-dimethyl-3-ethyl-spiroindolinenaphthooxazine,
1,3,3-trimethyl-9'-hydroxy-spiroindoline naphthoxazine,
1,3-dimethyl-3-ethyl-8'-hydroxy-spiroindoline naphthoxazine, 1,3,3,5-tetramethyl-9'-methoxy-spiroindoline naphthoxazine,
1,3,3,5,6-pentamethyl-9'-methoxy-spiroindolinenaphthooxazine,
1,3,3-trimethyl-4-trifluoromethyl-5'-methoxy-spiroindolinenaphthooxazine,
1,3,3-trimethyl-5'-methoxy-6'-trifluoromethyl-spiroindolinenaphthooxazine,
1,3,3-trimethyl-4-trifluoromethyl-9'-methoxy-spiroindolinenaphthooxazine,
1,3,5,6-tetramethyl-3-ethyl-spiroindolinenaphthooxazine,
1,3,3,5,6-pentamethyl-spiroindolinenaphthooxazine,
1-methyl-3,3-diphenyl-spiroindolinenaphthooxazine,
1- (4-methoxybenzyl) -3,3-dimethyl-spiroindolinenaphthooxazine,
1- (3,5-dimethylbenzyl) -3,3-dimethyl-spiroindolinenaphthoxazine,
1- (2-fluorobenzyl) -3,3-dimethyl-spiroindoline naphthoxazine and the like are substituted with indolino spironaphthoxazine, indole ring and benzene ring of halogen, methyl, ethyl, methylene, ethylene, hydroxyl group and other substituents. Examples can be given.

As naphthopyran compounds,
3,3,9,9-tetraphenyl-3H, 9H-naphtho [2,1-b: 6,5-b ']-dipyran,
3,3,10,10-tetraphenyl-3H, 10H-naphtho [2,1-b: 7,8-b '] dipyran,
3,3,9,9-tetraphenyl-3H, 10H-naphtho [4,3-b: 8,7-b] -dipyran,
3,3-diphenyl-9-methoxy-3H-naphtho [4,3-b] pyran,
3,3-diphenyl-10-methyl-3H-naphtho [2,1-b: 5,6-b] dipyran-8-one,
3,3,9,9-tetra (4'-methoxy-phenyl) -3H, 9H-naphtho [2,1-b: 6,5-b ']-dipyran;
3,3-diphenyl-8- (2- (4-dimethylamino) phenyl) ethene-3H-naphtho [4,3-b] pyran,
3,3-diphenyl-5-acetoxy-3H-naphtho [4,3-b] pyran,
3,3-Diphenyl-8- (1H-benzotriazol-1-yl) carbonyl-3H-naphtho [4,3-b] pyran can be exemplified.

  Examples of indolinospirophenanthrooxazine compounds include 1,3,3-trimethyl-spiroindoline phenanthrooxazine, 1,3,3-trimethyl-5-chloro-spiroindoline phenanthrooxazine, and the like. Examples of the substituents include halogen, methyl, ethyl, methylene, ethylene, and a hydroxyl group on the indole ring and the benzene ring of linospirophenanthrooxazine.

  Examples of the indolino spiroquinolinoxazine-based compound include 1,3,3-trimethyl-spiroindolinequinolinoxazine and the like, halogens of indole ring and benzene ring of indolino spiroquinolinoxazine, methyl, ethyl, methylene, ethylene, hydroxyl group and the like. Each substituent can be exemplified.

Among the photochromic compounds, spiropyran derivatives are shown below, but the present invention is not limited thereto.
1,3,3-trimethylindolinobenzopyrrolospirane, 1,3,3-trimethylindolino-6'-bromobenzopyrrolospirane, 1,3,3-trimethylindolino-8'-methoxybenzopyrrolos Examples thereof include pyran, 1,3,3-trimethylindolino-β-naphthopyrrospirane, 1,3,3-trimethylindolino-6′-nitrobenzopyrrospirane and the like.
Further, a photochromic compound such as a fulgide-based compound and a diarylethene-based compound having an optical memory property (color memory property and photochromic property) can also be used.

Using the liquid composition for forming a crack-patterned film, a crack-printed or painted product is obtained by the following production method.
A coating is formed on a support having a concave portion by printing or coating by a printing method such as screen printing, offset printing, gravure printing, a coater, or transfer printing, or a coating method such as spray coating.
The coating has irregular cracks in a portion having no concave portion when dried, and a portion having a concave portion, or a coating having a regular crack pattern along the concave portion in the vicinity of the portion having the concave portion. Formed, resulting in a cracked print or coating.

On the film, a protective layer having transparency may be provided to impart abrasion resistance, a light stabilizer layer may be provided, or a layer containing a transparent metallic gloss pigment may be provided.
Specifically, the light stabilizer layer is selected from an ultraviolet absorber, an antioxidant, an antioxidant, a singlet oxygen quencher, a superoxide anion quencher, an ozone decolorant, a visible light absorber, and an infrared absorber. This is a layer in which the light stabilizer is fixed in a dispersed state.
Examples of the transparent metallic luster pigment include natural mica, synthetic mica, glass flakes, alumina, and pigments in which the surface of a transparent film piece is coated with a metal oxide such as titanium oxide as a core substance.

When a reversible color-changing material is contained in the cracked film, the film may have light transmittance or light shielding, but preferably has light transmittance.
Due to the light transmission of the crack-patterned film, the color of the support is visually recognized in the state where the reversible color-changing material is decolored, and the crack pattern is hard to be visually recognized.In the state where the reversible color-changing material is colored, the crack pattern is formed. Can be provided with the unexpectedness of being visually recognized.

Further, a colored layer having a light transmitting property containing a coloring agent may be provided on the coating.
By providing the colored layer having the light transmitting property, the color of the colored layer is exhibited in a state where the reversible color-changing material is erased, and a color mixed with the color of the colored layer in a state where the reversible color-changing material is colored. Since the cracked pattern is visually recognized, it is possible to obtain a cracked print or a painted product that shows an unexpected color change.

  As the cracked printed or painted material, specifically, dolls or animal figurative toys, doll houses and furniture, accessories for dolls such as clothing, hats, bags, shoes, accessory toys, building blocks toys, block toys, tops, kites , Musical instrument toys, cooking toys, gun toys, capture toys, background toys, vehicles, animals, plants, buildings, toys that imitate food, etc., indoor decorations such as clothing, footwear, cloth personal belongings, frames, artificial flowers, and accessories , Stationery, cosmetics, cups, plates, chopsticks, spoons, forks, pots, pans and other kitchenware, calendars, labels, cards, recording materials, various printed materials for anti-counterfeiting, books such as picture books, gloves, ties, hats , Bags, packaging containers, sports equipment, fishing gear, toothbrushes, coasters, watches, glasses, lighting fixtures, heating and cooling appliances, musical instruments, cairo, regenerators, photo stands, wallets and other bags, umbrellas, furniture, vehicles, construction Things, can be exemplified training tool.

Examples are described below, but the present invention is not limited to these examples.
The parts in the examples are parts by mass.
Reference Example 1
Preparation of Liquid Composition 25 parts of hydrophilic fumed silica (trade name: AEROSIL 90G) was dispersed in 30 parts of a toluene solution (solid content: 45%) of an acrylic resin (trade name: Acridic A-180), and xylene and It was diluted with methyl isobutyl ketone to obtain a liquid composition.

Production of cracked printing or painted material (see Fig. 1)
Using the liquid composition, a spray gun is applied to a red ABS plate-like molded body provided with a lattice-shaped concave portion as a support 2 and dried at room temperature for 20 minutes to form a coating 3. In the process, a crack occurred in the coating, and a coating having a crack pattern was provided.
The cracked printed or coated article had a cracked pattern 4 along the concave portion and an irregular cracked pattern 5, and the red color of the support was visually recognized from the cracked portion, and had unexpectedness.

Reference example 2
Preparation of Liquid Composition 15 parts of hydrophobic fumed silica (trade name: AEROSIL R812) was diluted with xylene and methyl isobutyl ketone to obtain a liquid composition.

Cracked printing or preparation of a coated article Using the liquid composition, a spray gun was applied to a blue ABS minicar provided with concave portions around a hood, a door, and a light as a support, and dried at room temperature for 20 minutes. A coating was formed, and the coating was cracked in the course of drying to provide a coating with a cracked pattern, thereby obtaining a cracked printed or painted product.
The cracked printed or painted article had a cracked pattern along the concave portion and an irregular cracked pattern, and the blue color of the support was visually recognized from the cracked portion, and had unexpectedness.

Reference Example 3
Preparation of Liquid Composition 20 parts of hydrophilic fumed silica (trade name: AEROSIL 90G) and 5 parts of blue pigment were added to 30 parts of a toluene solution (solid content: 45%) of an acrylic resin (trade name: Acridic A-180). It was dispersed and diluted with xylene and methyl isobutyl ketone to obtain a liquid composition.

Cracked printing or preparation of a coated article Using the liquid composition described above, a white printing ink was used as a support to coat a white ABS plate-like molded body provided with corrugated concave portions with a spray gun, and the resulting composition was heated at room temperature for 20 minutes. The film was dried to form a film, and the film was cracked during the drying process to provide a film having a crack pattern, thereby obtaining a cracked print or a coated product.
The cracked printed or painted article had a cracked pattern along the concave portion and an irregular cracked pattern, and the white color of the support was visually recognized from the cracked portion, and had unexpectedness.

Example 1
Preparation of Liquid Composition 1 part of 3- (2-ethoxy-4-diethylaminophenyl) -3- (1-ethylindol-3-yl) -4-azaphthalide as the component (a) and 4,4 as the component (b) Reversible thermochromic microcapsule pigment (t ₁ ) in which a reversible thermochromic composition comprising 5 parts of '-(2-ethylhexylidene) bisphenol and 50 parts of myristyl myristate as a component (c) is encapsulated in a microcapsule wall film. : 31 ° C., t ₄ : 41 ° C., ΔH: 7 ° C., 5 parts of color change from blue to colorless) and 20 parts of hydrophilic fumed silica (trade name: AEROSIL 90G) with an acrylic resin (trade name: acrylic) Dick A-180) was dispersed in 30 parts of a toluene solution (solid content: 45%) and diluted with xylene and methyl isobutyl ketone to obtain a liquid composition.

Production of cracked printing or painted material (see Figs. 2 to 4)
Using the liquid composition described above, a coating 3 was formed by applying a spray gun on a white ABS plate-like molded body provided with three concave portions as a support 2 in the longitudinal direction and drying at room temperature for 20 minutes. In the course of drying, the coating was cracked to provide a cracked coating, and a cracked printed or coated article 1 was obtained.
At 25 ° C., the cracked printed or coated article had a cracked pattern 4 along the concave portion and an irregular cracked pattern 5, and the white color of the support was visually recognized from the cracked portion, and had unexpectedness (FIG. 2).
When the cracked printed or coated material was heated to 41 ° C. or higher, the blue cracked film became white, and the cracked pattern became invisible (FIG. 3).
When the temperature was lowered to 31 ° C. or lower, a blue cracked pattern and white color by the support were visually recognized from the cracked portion, and the appearance change could be repeatedly performed.

Example 2
Preparation of Liquid Composition 1 part of 3- (2-ethoxy-4-diethylaminophenyl) -3- (1-ethylindol-3-yl) -4-azaphthalide as the component (a) and 4,4 as the component (b) Reversible thermochromic microcapsule pigment (t ₁ ) in which a reversible thermochromic composition comprising 5 parts of '-(2-ethylhexylidene) bisphenol and 50 parts of myristyl myristate as a component (c) is encapsulated in a microcapsule wall film. _{: 31 ℃, t 4: 41} ℃, ΔH: 7 ℃, color change) 5 parts from blue to colorless, and hydrophobic fumed silica (trade name: AEROSIL R812) 10 parts, with xylene and methyl isobutyl ketone To obtain a liquid composition.

Cracked printing or preparation of a coated article Using the liquid composition, a spray gun was used to coat a pink polystyrene egg-shaped container provided with a spiral concave portion as a support, followed by drying at room temperature for 20 minutes to form a coating. The coating was formed and cracked in the process of drying to form a coating with a crack pattern, thereby obtaining a cracked printed or painted product.
The cracked printed or coated article had a crack pattern along the concave portion and an irregular crack pattern at 25 ° C., and the pink color of the support was visually recognized from the cracked portion, and had unexpectedness.
When the cracked print or the coated material is heated to 41 ° C. or more, the blue cracked pattern film becomes white, and the pink color of the support is visually recognized from the cracked portion.
When the temperature was lowered to 31 ° C. or lower, a blue crack pattern was observed again, and a pink color due to the support was visually recognized from the crack portion, and the appearance change could be repeatedly performed.

Example 3
Preparation of Liquid Composition 1 part of 3- (2-ethoxy-4-diethylaminophenyl) -3- (1-ethylindol-3-yl) -4-azaphthalide as the component (a) and 4,4 as the component (b) Reversible thermochromic microcapsule pigment (t ₁ ) in which a reversible thermochromic composition comprising 5 parts of '-(2-ethylhexylidene) bisphenol and 50 parts of myristyl myristate as a component (c) is encapsulated in a microcapsule wall film. _{: 31 ℃, t 4: 41} ℃, ΔH: 7 ℃, color change from blue to colorless), 5 parts of hydrophilic fumed silica (trade name: AEROSIL 90G) 20 parts, and the pink pigment, 1 part of acrylic Dispersed in 30 parts of a toluene solution (solid content: 45%) of a resin (trade name: Acridic A-180) and diluted with xylene and methyl isobutyl ketone to form a liquid composition Obtained.

Cracked printing or preparation of a painted product Using the liquid composition, a spray gun was applied to a white ABS minicar provided with concave portions around a hood, a door and a light as a support, and dried at room temperature for 20 minutes. A coating was formed, and the coating was cracked in the course of drying to provide a coating with a cracked pattern, thereby obtaining a cracked printed or painted product.
In the cracked printed or painted material, a cracked pattern along the concave portion and an irregular cracked pattern were visually recognized, and had unexpectedness.
At 25 ° C., the cracked printed or coated article has a purple cracked pattern and a white color due to the support from the cracked portion.
When the cracked print or the coated material is heated to 41 ° C. or higher, the purple cracked film becomes pink, and the white color of the support is visually recognized from the cracked portion.
When the temperature was lowered to 31 ° C. or lower, a purple crack pattern and white color by the support were visually recognized from the crack portion, and the appearance change could be repeatedly performed.

Example 4
Preparation of liquid composition 1 part of 3,3-diphenyl-9-methoxy-3H-naphtho [2,1-b] pyran, 10 parts of a styrene-α-methylstyrene copolymer (trade name: picolastic A-5) , Bis (1,2,2,6,6-pentamethyl-4-piperidyl sebacate) [trade name: SANOL LS-765] containing 0.2 parts of a reversible photochromic material in a microcapsule wall film. 10 parts of a backlight discoloring microcapsule pigment (color change to yellow in a light place and colorless in a dark place) and 20 parts of hydrophilic fumed silica (trade name: AEROSIL 90G) are mixed with an acrylic resin (trade name: Acridic A). -180) was dispersed in 30 parts of a toluene solution (solid content: 45%) and diluted with xylene and methyl isobutyl ketone to obtain a liquid composition.

Cracked printing or preparation of a painted product Using the liquid composition, a spray gun was applied to a white ABS minicar provided with concave portions around a hood, a door and a light as a support, and dried at room temperature for 20 minutes. A coating was formed, and the coating was cracked in the course of drying to provide a coating with a cracked pattern, thereby obtaining a cracked printed or painted product.
In the cracked printed or painted material, a cracked pattern along the concave portion and an irregular cracked pattern were visually recognized, and had unexpectedness.
When light is applied to the cracked print or the painted material, the cracked pattern film turns yellow, and white by the support is visually recognized from the cracked portion.
When the cracked print or the painted product was left in a dark place, the film of the cracked pattern became white, and the cracked pattern became invisible.
When the light was irradiated again, a yellow crack pattern and a white color due to the support were visually recognized from the crack portion, and the appearance change could be repeatedly performed.

1 crack printed or coated member 2 supports 3 coating 4 complete coloring temperature t ₂ heating microcapsule pigment enclosing a cracked pattern 5 irregular crack pattern t ₁ heating decolorizable reversible thermochromic composition along the recess decoloring starting temperature t ₄ heated decoloring type microcapsule pigment enclosing a coloring initiation temperature t ₃ heat-decolorizable reversible thermochromic composition of the microcapsule pigment enclosing a reversible thermochromic composition of the decolorizable Complete color erasing temperature of microcapsule pigment containing reversible thermochromic composition of formula (I) T ₁ Complete decoloring temperature of microcapsule pigment containing heat reversible thermochromic composition T ₂ coloring start temperature T ₄ heating-coloring type of soluble microcapsules pigments containing sex composition decoloring starting temperature T ₃ heat-coloring type reversible thermal discoloration composition of the microcapsule pigment enclosing Complete color development temperature ΔH hysteresis width of microcapsule pigment containing reverse thermochromic composition

Claims (4)

It is provided a coating by printing or painting on a support having at least a recess, wherein the coating possess a cracked pattern along the recess, and irregular crack pattern, it contains a reversible color change material in said coating Ruhibiware printing or coating, such was. The cracked print or painted article according to claim 1, wherein the reversible color-changing material is selected from a reversible thermochromic material or a reversible photochromic material. The cracked printed or painted article according to claim 1, wherein the coating has a light transmitting property. On a support having at least a concave portion, a coating is formed by printing or painting using a liquid composition comprising at least an inorganic pigment, a resin, and a solvent, and the coating is cracked to form a cracked pattern along the concave portion. A method for producing a cracked printed or painted article that forms a regular cracked pattern.

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