JP6709067B2 - Reversible color-changing printing or coating and method for producing the same - Google Patents

Description

The present invention relates to a reversible color-changing printing or coated article and a method for producing the same. More specifically, it relates to a reversible color-changing printing or coated article having a crack pattern and a method for producing the same.

Conventionally, a printed matter in which a thermochromic image containing a thermochromic material is provided on a support has been disclosed (for example, refer to Patent Document 1).
In the printed matter, even if the thermochromic material develops color due to a temperature change and the thermochromic image is visually recognized, the thermochromic image that appears is poor in surprise.

JP 2001-353950 A

The present invention is intended to solve the problems of this type of printed matter, and provides a reversible color-changeable printing or coated article and a method for producing the same, which imparts an unexpectedness to the image visually recognized when the color-changing material is colored. It is the one we are trying to provide.

The present invention is a printed or painted product having a crack-patterned coating on a support, in which the support is visible from the cracked portion, wherein an inorganic pigment and a reversible color-changing material are contained in the coating. Ri Na contained, and the reversible color-changing material requirements reversible thermochromic printing or painting was Ru is selected from thermochromic material or reversibly photochromic material.
Furthermore, before Symbol coating is required for the like having optical transparency.
Furthermore, a film is printed or coated on the support with a liquid composition comprising at least an inorganic pigment, a reversible color-changing material selected from a reversible thermochromic material or a reversible photochromic material, and a solvent. formed, let me cracked the coating to form a coating film cracking pattern during drying of the coating, is required for the manufacturing process of reversible color change printing or painting was that the support body is visible from cracked portions.

INDUSTRIAL APPLICABILITY The present invention can provide a reversible color-changing printing or coated article which is clearly visible in a crack pattern which is visually recognized when a color of the reversible color-changing material is developed, and a manufacturing method thereof, which is excellent in unexpectedness and design.

It is explanatory drawing which shows the discoloration behavior of the microcapsule pigment which encapsulated the reversible thermochromic composition of heat decolorization type. It is explanatory drawing which shows the discoloration behavior of the microcapsule pigment which encapsulated the heat-erasable type reversible thermochromic composition which has color memory. It is explanatory drawing which shows the discoloration behavior of the microcapsule pigment which encapsulated the reversible thermochromic composition of a heat-coloring type. FIG. 3 is a front view showing a state in which the reversible color-changing material of the present invention or the reversible color-changing material of a coated product has developed color. It is a front view which shows the state which the reversible color-change material of the reversible color-change printing or coating of FIG. FIG. 5 is a vertical cross-sectional explanatory view of the reversible color-changeable print or the coated article of FIG. 4.

The present invention is a reversible color-changing print or coated product, which comprises a support and a coating containing a reversible color-changing material having a crack pattern, and the support is visually recognized from a cracked portion.
Examples of the support include paper, synthetic paper, knitted cloth, woven cloth, non-woven cloth, synthetic leather, natural leather, rubber, plastic, glass, ceramics, metal, wood, stone, and the like. Further, the form may be a flat form or an uneven form.
A colorant may be contained in the support, or a color layer containing the colorant may be provided on the support.
The colored layer may be a colored image, and examples thereof include images of patterns, designs, patterns, characters, symbols and the like.

A coating containing a reversible discolorable material having a crack pattern is provided on the support.
The coating is formed by printing or coating a liquid composition containing at least an inorganic pigment, a reversible thermochromic material and a solvent on a support, and cracking the coating when dried to form a cracked coating.

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

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 crystals, an electron-donating color-developing organic compound, an electron-accepting compound, and a reversible color reaction between the two. Reversible thermochromic material of heat-decoloring type containing three components with an organic compound medium to be generated in, or an electron-donating color-developing organic compound, an electron-accepting compound, and the color reaction of both of them is reversible A reversible thermochromic material of a heat-coloring type is used, which contains three components with an organic compound medium to be generated.
Among them, a reversible thermochromic material including an electron-donating color-developing organic compound, an electron-accepting compound, and an organic compound medium that reversibly causes the color reaction of the both will be described.
The reversible thermochromic material comprises (a) an electron-donating color-developing organic compound, (b) an electron-accepting compound, and (c) a reaction medium that determines the temperature at which the color reaction between the two occurs. A reversible thermochromic microcapsule pigment (reversible thermochromic pigment) that changes the color from a colored color to a colorless color containing the composition is included.
The reversible thermochromic composition is 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 (color change point). Discolored before and after, a decolored state in a temperature range above the high-temperature side discoloration point, exhibiting a color-developed state in a temperature range below the low-temperature side discoloration point, and only one specific state exists in the room temperature range of the above two states, The other state is maintained while the heat or cold required to develop that state is applied, but returns to the state exhibited at room temperature if the heat or cold is no longer applied, and the hysteresis width is A reversible thermochromic composition of heat erasable type (decolored by heating and developed by cooling) having relatively small characteristics (ΔH=1 to 7° C.) can be applied (see FIG. 1).

Further, 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, the shape of the curve plotting the change in coloring density due to temperature change is such that the temperature rises from the lower temperature side than the discoloration temperature range, and conversely, the temperature decreases from the higher temperature side than the discoloration temperature range. The color changes in a specific temperature range when the color changes at a temperature below the complete color development temperature (t ₁ ) or in the high temperature range above the complete color removal temperature (t ₄ ). Reversible thermochromic composition of a heat erasable type (color erasable by heating, color develops by cooling) having a color memory property in a temperature range (substantially two-phase holding temperature range) between [t _{2 and} t ₃ ]. 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 change in temperature progresses along the arrow. Here, A is a point indicating the density at a temperature t ₄ (hereinafter, referred to as a complete erasing temperature) at which a complete erasing state is reached, and B is a temperature t _{3 at} which erasing is started (hereinafter referred to as an erasing starting temperature). C) is a point indicating the density at C, C is a point at the temperature t ₂ at which color development starts (hereinafter referred to as the color development start temperature), and D is a temperature t ₁ at which a fully colored state is reached (hereinafter referred to as complete color development). This is a point showing the density at the color development temperature).
The color change temperature range is a temperature range between the above t ₁ and t ₄ , and can be in any one of a colored state and a decolored state, and between t ₂ and t ₃ which is a region with a large difference in color density. The temperature range of is the substantial discoloration temperature range.
Further, the length of the line segment EF is a scale showing 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 hysteresis width ΔH) showing the degree of hysteresis. However, if this ΔH value is small, only one specific state can exist in the normal temperature region of both states before and after discoloration. Further, when the ΔH value is large, it becomes easy to maintain each state before and after the color change.

The components (a), (b) and (c) of the reversible thermochromic composition will be described below.
The electron-donating color-developing organic compound as the component (a) includes diphenylmethanephthalides, phenylindolylphthalides, indolylphthalides, diphenylmethaneazaphthalides, phenylindolylazaphthalides, and fluorane. Examples thereof include styrinoquinolines, diazarhodamine lactones, pyridines, quinazolines, and bisquinazolines.
Examples of these compounds are shown 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-N-p-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-methoxy-6-diethylaminofluorane,
2-anilino-3-methyl-6-di-n-butylaminofluorane,
2-anilino-3-methoxy-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)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-on,
2-(di-n-butylamino)-8-(N-ethyl-N-i-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,
2-(4'-dimethylaminophenyl)-4-methoxy-quinazoline,
4,4'-(ethylenedioxy)-bis[2-(4-diethylaminophenyl)quinazoline] and the like can be mentioned.
As the fluoranes, in addition to the compound having a substituent on the phenyl group forming a xanthene ring, a substituent on the phenyl group forming a xanthene ring and also a substituent on the phenyl group forming a lactone ring (for example, , An alkyl group such as a methyl group, or a halogen atom such as a chloro group), and a compound exhibiting a blue or black color.

Examples of the electron-accepting compound as the component (b) include a compound group having an active proton, a pseudo-acidic compound group (a compound group which is not an acid but acts as an acid in the composition to color the component (a)), There is a group of compounds having electron vacancies.
Examples of the compound having an active proton include compounds having a phenolic hydroxyl group, from 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. Alternatively, examples thereof include those having an amide group, a halogen group, and the like, and bis type and tris type phenols, and phenol-aldehyde condensation resins. Further, it may be a metal salt of the compound having a phenolic hydroxyl group.
Specific examples are given 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, resorcin, 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-hydroxyphenyl)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, 1-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, 2,2-bis(4-hydroxyphenyl)ethyl propionate, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 2,2-bis(4-hydroxyphenyl) Phenyl)-4-methylhexane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-hydroxy-3-methylphenyl)propane and the like.
The compound having a phenolic hydroxyl group can develop the most effective thermochromic properties, but aromatic carboxylic acids and aliphatic carboxylic acids having 2 to 5 carbon atoms, carboxylic acid metal salts, acidic phosphoric acid esters and those It may be a compound selected from metal salts, 1,2,3-triazole and its derivatives.

The component (c) of the reaction medium that reversibly causes the electron transfer reaction by the components (a) and (b) in a specific temperature range will be described.
Examples of the component (c) include alcohols, esters, ketones and ethers.
The said compound is illustrated below.
As the alcohol, an aliphatic monovalent saturated alcohol having 10 or more carbon atoms is effective, and specifically, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl. Examples thereof include 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, alicyclic or aromatic ring. , An aliphatic, alicyclic or aromatic polycyclic carboxylic acid and an ester, an aliphatic or alicyclic obtained from any combination of an aliphatic, alicyclic or aromatic monohydric alcohol Alternatively, there may be mentioned esters obtained from any combination of a monovalent carboxylic acid having an aromatic ring and a polyhydric alcohol having an aliphatic and alicyclic ring or an aromatic ring, specifically, ethyl caprylate, octyl caprylate, and capryl. Acid stearyl, myristyl caprate, docosyl caprate, 2-ethylhexyl laurate, n-decyl laurate, 3-methylbutyl myristate, cetyl myristate, isopropyl palmitate, neopentyl palmitate, nonyl palmitate, cyclohexyl palmitate, stearin Acid n-butyl stearate 2-methylbutyl stearate 3,5,5-trimethylhexyl stearate, n-undecyl stearate, pentadecyl stearate, stearyl stearate, cyclohexylmethyl stearate, isopropyl behenate, hexyl behenate, behen Lauryl acid, behenyl behenate, cetyl benzoate, stearyl p-tert-butyl benzoate, dimyristyl phthalate, distearyl phthalate, dimyristyl oxalate, dicetyl oxalate, dicetyl malonate, dilauryl succinate, dilauryl glutarate, adipine. Diundecyl acid, dilauryl azelate, di-(n-nonyl) sebacate, dineopentyl 1,18-octadecyl methylene dicarboxylate, ethylene glycol dimyristate, propylene glycol dilaurate, propylene glycol distearate, hexylene glycol dipalmitate, 1,5-pentanediol distearate, 1,2,6-hexanetriol trimyristate, 1,4-cyclohexanediol didecyl, 1,4-cyclohexanedimethanol dimyristate, xylene glycol dicaprinate, xylene glycol Examples thereof include distearate.
In addition, esters of saturated fatty acids and branched aliphatic alcohols, unsaturated fatty acids or esters of aliphatic alcohols that are branched or saturated with branched or substituted fatty acids or have 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-stearic acid stearate Methylbutyl, 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, stearic acid 3, 7-dimethyloctyl, 3,7-dimethyloctyl behenate, stearyl oleate, behenyl oleate, stearyl linoleate, behenyl linoleate, 3,7-dimethyloctyl erucate, stearyl erucate, isostearyl erucate, isostearic acid Cetyl, stearyl isostearate, 2-methylpentyl 12-hydroxystearate, 2-ethylhexyl 18-bromostearate, isostearyl 2-ketomyristate, 2-ethylhexyl 2-fluoromyristate, cetyl butyrate, stearyl butyrate, behenyl butyrate. Etc.

Further, as the component (c) for obtaining the reversible thermochromic composition having a color memory property, a carboxylic acid ester compound having a ΔT value (melting point-clouding point) of 5° C. or more and less than 50° C., for example, in the molecule 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 the 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, distearyl adipate, trilaurin, trimyristin, tristearin, dimyristine, distearin and the like are used.

In addition, a fatty acid ester compound obtained from an odd-numbered aliphatic monohydric alcohol having 9 or more carbon atoms and an aliphatic carboxylic acid having an even-numbered carbon number, n-pentyl alcohol or n-heptyl alcohol, and an even-numbered fat having 10 to 16 carbon atoms A fatty acid ester compound having a total carbon number of 17 to 23 obtained from a group carboxylic acid is 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 myristate, n-pentyl palmitate, n-heptyl palmitate, n-nonyl palmitate, n-undecyl palmitate, n-tridecyl palmitate, n-pentadecyl palmitate, N-Nonyl stearate, n-undecyl stearate, n-tridecyl stearate, n-pentadecyl stearate, n-nonyl eicosanoate, n-undecyl eicosane, n-tridecyl eicosane, n-pentadecyl eicosane, behenic acid Examples thereof include n-nonyl, n-undecyl behenate, n-tridecyl behenate, and n-pentadecyl behenate.

As the 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, 2 -Dodecanone, 3-dodecanone, 4-dodecanone, 5-dodecanone, 2-tridecanone, 3-tridecanone, 2-tetradecanone, 2-pentadecanone, 8-pentadecanone, 2-hexadecanone, 3-hexadecanone, 9-heptadecane, 2-pentadecanone , 2-octadecanone, 2-nonadecanone, 10-nonadecanone, 2-eicosanone, 11-eicosanone, 2-heneicosanone, 2-docosanone, laurone, stearone and the like.
Further, arylalkylketones 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-pentylacetophenone, cyclohexylphenylketone, benzyl-n-butylketone, 4-n-butylacetophenone, n-hexanophenone, 4-isobutylacetophenone, 1-acetonaphthone, 2-acetonaphthone, cyclopentylphenylketone Etc. can be mentioned.

As the 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, ditridecyl ether. Decyl ether, ditetradecyl ether, dipentadecyl ether, dihexadecyl ether, dioctadecyl ether, decanediol dimethyl ether, undecanediol dimethyl ether, dodecanediol dimethyl ether, tridecanediol dimethyl ether, decanediol diethyl ether, undecanediol diethyl ether, etc. Can be mentioned.

Further, as the electron-accepting compound, a specific alkoxyphenol compound having a linear or side chain alkyl group having 3 to 18 carbon atoms is used (Japanese Patent Application Laid-Open Nos. 11-129623 and 11-5973), or a specific Using a hydroxybenzoic acid ester (Japanese Patent Laid-Open No. 2001-105732), using a gallic acid ester or the like (Japanese Patent Publication No. 51-44706, Japanese Patent Laid-Open No. 2003-253149), a heat-coloring type (coloring by heating, It is also possible to apply a reversible thermochromic microcapsule pigment (reversible thermochromic pigment) containing a reversible thermochromic composition (which is erased by cooling) (see FIG. 3).

The blending ratios of the components (a), (b), and (c) depend on the concentration, the color change temperature, the color change form, and the type of each component, but generally, the component ratio for obtaining a desired color change characteristic is: The component (b) is in the range of 0.1 to 50, preferably 0.5 to 20, and the component (c) is in the range of 1 to 800, preferably 5 to 200 with respect to the component (a) (1). Parts by weight).

Examples of the method for microencapsulating the reversible thermochromic composition include interfacial polymerization method, interfacial polycondensation method, in situ polymerization method, submerged curing coating method, phase separation method from aqueous solution, and phase separation method 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 depending on the application.
Further, the surface of the microcapsules may be provided with a secondary resin film depending on 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 microcapsules so as to exhibit an alternating color change from colored (1) to colored (2).
By encapsulating in the microcapsules, 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 is measured using a laser diffraction/scattering particle size distribution measuring device [LA-300, manufactured by Horiba, Ltd.], and the average particle size (median size) is used as a volume standard based on the numerical values. Calculate with.

As the reversible photochromic material, a photochromic compound, or a reversible photochromic microcapsule pigment containing a photochromic compound 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 for microencapsulating the photochromic compound include the methods described above, which can form a chemically and physically stable pigment, and have an average particle size of 0.1 to 50 μm, preferably 0.5 to 30 μm, and more preferably Satisfies the practicability in the range of 1 to 20 μm.
A non-thermochromic dye or pigment may be blended in the microcapsules so as to exhibit an alternating 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 indinospirobenzoxazine-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'-methyldisspiro[cyclohexane-1,3'-[3H]indole-2'(1'H),3"-[3H]pyrido[4,3-f][1,4]benzoxazine],
1'-Methyl-5'-nitrodisspiro[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'-methyldisspiro[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'-methyldisspiro[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'-methyldisspiro[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'-trifluoromethyldisspiro[cyclopentane-1,3'-[3H]-indole-2'[1'H],3"-[3H]pyrido [2,3-f][1,4]benzoxazine],
1-benzyl-3,3-di-n-butyl-7'-ethyl-5-methoxyspiro[2H-indole-1,3'-[3H]pyrido[2,3-f][1,4]benzoxazine ],
1'-n-butyl-6'-iododisspiro[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)disspiro[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'-methyldisspiro[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"-iododisspiro[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'-trichloromethyldisspiro[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'-methoxycarbonylmethyl dispiro [cyclohexane-1,3'-[3H]-indole-2'(1'H)-[3H]pyrido[2,3-f][1,4]benzoxazine], etc. Examples thereof include halogen, methyl, ethyl, methylene, ethylene, and hydroxyl group substitution products of the indole ring and the benzene ring of indolinospyrobenzoxazine.

As the indinospironaphthooxazine-based compound,
1,3,3-trimethyl-spiroindoline naphthoxazine,
1,3,3-trimethyl-5-chloro-spiroindoline naphthoxazine,
1,3,3-trimethyl-5-bromo-spiroindoline naphthoxazine,
1,3,3,5-tetramethyl-spiroindoline naphthoxazine,
1,3,3-trimethyl-5-n-propyl-spiroindoline naphthoxazine,
1,3,3-trimethyl-5-iso-butyl-spiroindoline naphthoxazine,
1,3,3-trimethyl-5-methoxy-spiroindoline naphthoxazine,
1,3,3-trimethyl-5-n-propoxy-spiroindoline naphthoxazine,
1,3,3-trimethyl-5-cyano-spiroindoline naphthoxazine,
1-n-propyl-3,3-dimethyl-spiroindoline naphthoxazine,
1-iso-butyl-3,3-dimethyl-spiroindoline naphthoxazine,
1-n-octyl-3,3-dimethyl-spiroindoline naphthoxazine,
1-n-octadecyl-3,3-dimethyl-spiroindoline naphthoxazine,
Sodium 1,3,3-trimethyl-8'-sulfonate-spiroindoline naphthoxazine,
1,3,3-trimethyl-9'-methoxyspiroindoline naphthoxazine,
1,3,3-trimethyl-8'-cyano-spirobenzoindoline naphthoxazine,
1,3,3-trimethyl-5-trifluoro-spiroindoline naphthoxazine,
1-(4'-methylphenyl)-3,3-dimethyl-spiroindoline naphthoxazine,
1,3,3-trimethyl-6'-(2,3-dihydro-1-indolino)-spiroindoline naphthoxazine,
1,3,3-trimethyl-6'-(1-piperidinyl)-spiroindoline naphthoxazine,
1,3,3-trimethyl-6'-(1-morpholino)-spiroindoline naphthoxazine,
1-ethyl-3,3-dimethyl-6-trifluoromethyl-6'-(1-morpholino)-spiroindoline naphthoxazine,
1,3,3-trimethyl-6-trifluoromethyl-6'-(1-piperidinyl)-spiroindoline naphthoxazine,
1-benzyl-3,3-dimethyl-spiroindoline naphthoxazine,
1-(4-methoxybenzyl)-3,3-dimethyl-spiroindoline naphthoxazine,
1-(4-chlorobenzyl)-3,3-dimethyl-spiroindoline naphthoxazine,
1-ethyl-3,3-dimethyl-spiroindoline naphthoxazine,
1-isopropyl-3,3-dimethyl-spiroindoline naphthoxazine,
1-(2-phenoxyethyl)-3,3-dimethyl-spiroindoline naphthoxazine,
1,3-dimethyl-3-ethyl-spiroindoline naphthoxazine,
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-spiroindoline naphthoxazine,
1,3,3-trimethyl-4-trifluoromethyl-5'-methoxy-spiroindoline naphthoxazine,
1,3,3-trimethyl-5'-methoxy-6'-trifluoromethyl-spiroindoline naphthoxazine,
1,3,3-trimethyl-4-trifluoromethyl-9'-methoxy-spiroindoline naphthoxazine,
1,3,5,6-tetramethyl-3-ethyl-spiroindoline naphthoxazine,
1,3,3,5,6-pentamethyl-spiroindoline naphthoxazine,
1-methyl-3,3-diphenyl-spiroindoline naphthoxazine,
1-(4-methoxybenzyl)-3,3-dimethyl-spiroindoline naphthoxazine,
1-(3,5-dimethylbenzyl)-3,3-dimethyl-spiroindoline naphthoxazine,
1-(2-fluorobenzyl)-3,3-dimethyl-spiroindoline naphthoxazine, etc. It can be illustrated.

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,
An example is 3,3-diphenyl-8-(1H-benzotriazol-1-yl)carbonyl-3H-naphtho[4,3-b]pyran.

Examples of indolinospyrophenanthroxazine compounds include 1,3,3-trimethyl-spiroindolinephenanthroxazine, 1,3,3-trimethyl-5-chloro-spiroindolinephenanthroxazine, and the like. Examples thereof include halogen, methyl, ethyl, methylene, ethylene, and hydroxyl group-substituted substituents on the indole ring and benzene ring of linospirophenanthroxazine.

Examples of the indolinospiroquinolinooxazine-based compound include 1,3,3-trimethyl-spiroindoline quinolinooxazine and the like, halogens, methyl, ethyl, methylene, ethylene and hydroxyl groups of the indole ring and benzene ring of indolinospiroquinolinooxazine. Each substitution product can be illustrated.

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'-methoxybenzopyrriros Examples thereof include pyran, 1,3,3-trimethylindolino-β-naphthopyrilospiran, 1,3,3-trimethylindolino-6'-nitrobenzopyrrilospiran and the like.
Further, a photochromic compound such as a fulgide-based compound or a diarylethene-based compound having an optical memory property (color memory-based photochromic property) can also be used.

Examples of the solvent include toluene, xylene, chlorobenzene, mineral spirits, 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. , Organic solvents such as ethanol, propanol and butanol, and water.

Further, a resin can be added if necessary.
The resin may be either water-soluble or oil-soluble resin, but oil-soluble resin is preferably used.
Specific examples of the resin include an 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 copolymer resin, chlorinated polyethylene resin, chlorinated polypropylene resin, polyamide resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polycarbonate resin, polystyrene resin, high impact polystyrene resin, polypropylene resin, polymethylstyrene resin, polyacrylic acid Ester resin, polymethylmethacrylate 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, acrylic ester emulsion resin, water-based silicone rubber emulsion resin, water-soluble alkyd Examples thereof include resins, water-soluble melamine resins, water-soluble urea resins, water-soluble phenol resins, water-soluble epoxy resins, water-soluble polybutadiene resins, cellulose acetate, cellulose nitrate, and ethyl cellulose.
Moreover, the said resin can use 1 type(s) or 2 or more types together.

The liquid composition obtained as described above may be mixed with a non-thermochromic dye or pigment so as to exhibit an alternating color change from colored (1) to colored (2). it can.
As the non-discoloring colored colorant, a general colored dye or pigment is used.
Examples of the dyes include acid dyes, basic dyes, and direct dyes.As pigments, carbon black, inorganic pigments such as ultramarine, phthalocyanine-based, azo-based, anthraquinone-based, diketopyrrolopyrrole-based, quinacridone-based, Examples include organic pigments such as isoindolinone.
As the fluorescent pigment, synthetic resin fine particle fluorescent pigments obtained by solidifying various fluorescent dyes in a resin matrix can be used.
Further, in the liquid composition, an ultraviolet absorber, an infrared absorber, an antioxidant, a singlet oxygen quencher, an antiaging agent, an antistatic agent, a polarity imparting agent, a thixotropic agent, a defoaming agent, a stabilizer, a plasticizer. If necessary, additives such as agents, flame retardants, extender pigments, lubricants, foaming agents, surface conditioners and the like can be added.

Using the liquid composition for forming a crack-patterned film, a reversible discoloration printing or coated product can be obtained by the following production method.
A film is formed on the support by printing or painting by a printing method such as screen printing, offset printing, gravure printing, coater or transfer printing, or a coating method such as spray painting.
When the coating film is dried, cracks are formed to form a coating film having a cracked pattern, and a reversible discoloration printing or a coated article in which the support is visually recognized from the cracked portion can be obtained.

The cracked coating may have a light-transmitting property or a light-shielding property, but preferably has a light-transmitting property.
Due to the light-transmitting property of the crack-patterned film, the color of the support is visually recognizable when the reversible color-changing material is in a decolored state, and the crack pattern is hard to be visually recognized. It is possible to impart the unexpectedness of being visually recognized.

A protective layer having transparency may be provided on the film to impart scratch resistance, a light stabilizer layer may be provided, and a layer containing a transparent metallic luster 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 quencher, a visible light absorber, and an infrared absorber. It is a layer in which a light stabilizer is fixed in a dispersed state.
Examples of the transparent metallic luster pigment include natural mica, synthetic mica, glass pieces, alumina, and transparent film pieces as the core material, the surface of which is coated with a metal oxide such as titanium oxide.

Further, a light-transmitting colored layer containing a coloring agent may be provided on the coating film.
By providing the light-transmitting colored layer, the color of the colored layer is exhibited when the reversible color-changing material is decolored, and the color of the color mixture layer is mixed with the color of the colored layer when the reversible color-changing material is colored. Since the cracked pattern is visually recognized, it is possible to obtain a reversible color-changeable print or a coated article which exhibits an unexpected color change.

Specific examples of the reversible discoloration printing or painting include doll or animal figure toys, doll houses and furniture, doll accessories such as clothing, hats, bags, shoes, accessory toys, building block toys, block toys, and spinning tops. , Kites, musical instrument toys, cooking toys, gun toys, capture toys, background toys, vehicles, animals, plants, buildings, toys imitating food, clothes, footwear, cloth accessories, picture frames, indoor ornaments such as artificial flowers , Accessories, stationery, cosmetics, cups, kitchen utensils such as plates, chopsticks, spoons, forks, pots, pans, calendars, labels, cards, recording materials, various anti-counterfeit printed materials, books such as picture books, gloves, ties. , Hats, bags, packaging containers, exercise equipment, fishing gear, toothbrushes, coasters, watches, glasses, lighting equipment, air conditioners, musical instruments, cairo, cold storage agents, photo frames, bags such as wallets, umbrellas, furniture, vehicles, Examples include buildings and teaching tools.

Examples will be described below, but the present invention is not limited to these examples.
The parts in the examples are parts by mass.
Example 1
Preparation of liquid composition 3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethylindol-3-yl)-4-azaphthalide as component (a) 1 part, component (b) 4,4 Reversible thermochromic microcapsule pigment (t ₁ containing a reversible thermochromic composition comprising 5 parts of'-(2-ethylhexylidene)bisphenol and 50 parts of myristyl myristate as the component (c) in a microcapsule wall film. : 31° C., t ₄ : 41° C., ΔH: 7° C., 5 parts by color change from blue to colorless, and 20 parts of hydrophilic fumed silica (trade name: AEROSIL 90G), 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.

Reversible discoloration printing or production of painted objects (see Figures 4 to 6)
Using the liquid composition, a white ABS plate-shaped molded body as a support 2 was coated with a spray gun and dried at room temperature for 20 minutes to form a film, and cracks were formed in the film during the drying process. A coating 3 having a cracked pattern was provided to obtain a reversible color-changeable printing or coated article 1.
At 25° C., the reversible discoloration-printed or coated article has a blue crack pattern and a white color due to the support is visually recognized from the cracked portion (FIG. 4).
When the reversible discoloration-printed or coated article was heated to 41° C. or higher, the blue cracked coating became white, and the cracked pattern was no longer visible (FIG. 5).
At 31° C. or lower, a blue crack pattern and a white color due to the support were visually recognized from the crack portion, and the appearance change could be repeated.

Example 2
Preparation of liquid composition 3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethylindol-3-yl)-4-azaphthalide as component (a) 1 part, component (b) 4,4 A reversible thermochromic microcapsule pigment (t ₁ containing a reversible thermochromic composition comprising 5 parts of ′-(2-ethylhexylidene)bisphenol and 50 parts of myristyl myristate as the component (c) in a microcapsule wall film. : 31° C., t ₄ : 41° C., ΔH: 7° C., 5 parts by color change from blue to colorless, and 10 parts of hydrophobic fumed silica (trade name: AEROSIL R812) using xylene and methyl isobutyl ketone. And diluted to obtain a liquid composition.

Reversible Discoloration Printing or Preparation of Painted Product Using the liquid composition, a pink polystyrene egg-shaped container as a support was coated with a spray gun and dried at room temperature for 20 minutes to form a film. During the process, cracks were formed in the coating and a coating with a crack pattern was provided.
Then, using an oil-based resin solution for spraying consisting of 30 parts of acrylic resin/xylene, 30 parts of methyl isobutyl ketone, 30 parts of cyclohexanone, and 10 parts of a polyisocyanate-based curing agent, spray coating is performed on a cracked pattern film, and at 70° C. After heating for 1 hour, a protective layer was provided to obtain a reversible color-changeable printing or coated article.
At 25° C., the reversible discoloration-printed or coated article has a blue crack pattern and a pink color due to the support is visually recognized from the crack portion.
When the reversible discoloration printing or coating is heated to 41° C. or higher, the blue cracked coating becomes white, and the pink color due to the support is visually recognized from the cracked portion.
At 31° C. or lower, a blue crack pattern and a pink color due to the support were visually recognized from the cracked portion, and the appearance change could be repeated.

Example 3
Preparation of liquid composition 3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethylindol-3-yl)-4-azaphthalide as component (a) 1 part, component (b) 4,4 Reversible thermochromic microcapsule pigment (t ₁ containing a reversible thermochromic composition comprising 5 parts of'-(2-ethylhexylidene)bisphenol and 50 parts of myristyl myristate as the component (c) in a microcapsule wall film. : 31° C., t ₄ : 41° C., ΔH: 7° C., 5 parts by color change from blue to colorless), 20 parts of hydrophilic fumed silica (trade name: AEROSIL 90G), and 1 part of pink pigment, acrylic A resin composition (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.

Reversible Discoloration Printing or Preparation of Painted Product Using the above liquid composition, a white ABS minicar as a support is coated with a spray gun and dried at room temperature for 20 minutes to form a film. A coating film having a crack pattern was formed on the surface and a reversible color-changing printing or coating (reversible thermo-color-changing minicar) was obtained.
At 25° C., the reversible discoloration-printed or coated product has a purple cracked pattern and white from the cracked portion due to the support.
When the reversible discoloration printing or coating is heated to 41° C. or higher, the purple cracked coating turns pink and the cracked portion allows white to be visually recognized by the support.
At 31° C. or lower, a purple crack pattern and white color from the support were visually recognized from the crack portion, and the appearance change could be repeated.

Example 4
1 part of an orange pigment was dispersed in 10 parts of an acrylic resin and further diluted with methyl isobutyl ketone to obtain a paint.
Using the above paint, a polyvinyl chloride resin doll was coated with a spray gun to provide a colored layer to obtain a doll (support).

Preparation of liquid composition 3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethylindol-3-yl)-4-azaphthalide as component (a) 1 part, component (b) 4,4 Reversible thermochromic microcapsule pigment (t ₁ containing a reversible thermochromic composition comprising 5 parts of'-(2-ethylhexylidene)bisphenol and 50 parts of myristyl myristate as the component (c) in a microcapsule wall film. : 31° C., t ₄ : 41° C., ΔH: 7° C., 5 parts by color change from blue to colorless, 10 parts of fumed metal oxide (trade name: AEROSIL Alu C), 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.

Reversible Discoloration Printing or Preparation of Painted Product Using the liquid composition, a doll (support) is painted with a spray gun and dried at room temperature for 20 minutes to form a film, which is cracked during the drying process. Then, a coating film having a crack pattern was formed to obtain a reversible color-changing print or a coated article (reversible thermo-color-changing doll).
At 25° C., the reversible discoloration-printed or coated article has a black crack pattern and an orange color due to the support is visually recognized from the cracked portion.
When the reversible discoloration-printed or coated article was heated to 41° C. or higher, the black cracked coating became white having a light-transmitting property, and the cracked pattern was not visible.
At 31°C or lower, a black crack pattern and an orange color due to the support were visually recognized from the cracked portion, and such a phase change could be repeated.

Example 5
Preparation of liquid composition 3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethylindol-3-yl)-4-azaphthalide as component (a) 1 part, component (b) 4,4 Reversible thermochromic microcapsule pigment (t ₁ containing a reversible thermochromic composition comprising 5 parts of'-(2-ethylhexylidene)bisphenol and 50 parts of myristyl myristate as the component (c) in a microcapsule wall film. : 31° C., t ₄ : 41° C., ΔH: 7° C., 5 parts by color change from blue to colorless, and 20 parts of hydrophilic fumed silica (trade name: AEROSIL 90G), 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.

Reversible Discoloration Printing or Preparation of Painted Material Using the above liquid composition, printing is performed on a white ABS plate-shaped molded article as a support, dried at room temperature for 20 minutes to form a film, and the film is formed in the process of drying. A crack was formed and a coating having a crack pattern was provided.
Then, 1 part of a pink pigment is dispersed in 10 parts of an acrylic resin, and a printing ink diluted with methyl isobutyl ketone is further used to print on the cracked coating and the support to provide a colored layer, which is reversible. A discolored print or a coated product was obtained.
At 25° C., the reversible discoloration-printed or coated article has a purple cracked pattern and a pink color due to the colored layer is visually recognized from the cracked portion.
When the reversible discoloration printing or the coated article was heated to 41° C. or higher, the purple cracked coating became pink, and the cracked pattern was not visible.
At 31° C. or lower, a purple cracked pattern and a pink color due to the colored layer were visually recognized from the cracked portion, and the appearance change could be repeated.

Example 6
Preparation of Liquid Composition 1 part of 3,3-diphenyl-9-methoxy-3H-naphtho[2,1-b]pyran, styrene-α-methylstyrene copolymer (trade name: picolastic A-5) 10 parts , Bis(1,2,2,6,6-pentamethyl-4-piperidyl sebacate) [trade name: SANOL LS-765] 0.2 parts of a reversible photochromic material can be included in the microcapsule wall film. Reverse photochromic microcapsule pigment (yellow in bright place, colorless in dark place), 10 parts, and hydrophilic fumed silica (trade name: AEROSIL 90G) 20 parts, 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.

Reversible Discoloration Printing or Preparation of Painted Product Using the above liquid composition, a white ABS minicar as a support is coated with a spray gun and dried at room temperature for 20 minutes to form a film. A reversible discoloration-printing or coated article having a cracked coating film on which cracks were formed was obtained.
When the reversible discoloration printing or coating is irradiated with light, the cracked coating becomes yellow, and white from the crack is visually recognized by the support.
When the reversible discoloration printing or the coated article was left in a dark place, the cracked coating became white, so that the cracked pattern was not visible.
When light was irradiated again, a yellow cracked pattern and a white color due to the support were visually recognized from the cracked portion, and the appearance change could be repeated.

Example 7
Preparation of liquid composition 3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethylindol-3-yl)-4-azaphthalide 1 part as component (a), 4,4 as component (b) Reversible thermochromic microcapsule pigment (t ₁ containing a reversible thermochromic composition comprising 5 parts of'-(2-ethylhexylidene)bisphenol and 50 parts of myristyl myristate as the component (c) in a microcapsule wall film. : 31° C., t ₄ : 41° C., ΔH: 7° C., color change from blue to colorless) 5 parts, antifoaming agent 1 part, and hydrophobic fumed silica (trade name: AEROSIL R812) 20 parts, acrylic A resin composition (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.

Reversible Discoloration Printing or Preparation of Painted Material Using the above liquid composition, screen printing is performed on a transparent PET film as a support and dried at room temperature for 20 minutes to form a film, and the film is cracked during the drying process. A coating having a cracking pattern was formed and a reversible discoloration printing or coating was obtained.
In the reversible discoloration-printing or coated product obtained by the above-mentioned production method, at 25° C., a blue crack pattern and transparency due to the support are visually recognized from the crack portion.
When the reversible discoloration printing or the coated article was heated to 41° C. or higher, the blue cracked coating became colorless and transparent, and the cracked pattern was no longer visible.
At 31° C. or lower, a blue crack pattern and transparency due to the support were visually recognized from the cracked portion, and the appearance change could be repeated.

Example 8
Preparation of Liquid Composition 1 part of 3,3-diphenyl-9-methoxy-3H-naphtho[2,1-b]pyran, styrene-α-methylstyrene copolymer (trade name: picolastic A-5) 10 parts , Bis(1,2,2,6,6-pentamethyl-4-piperidyl sebacate) [trade name: SANOL LS-765] 0.2 parts of a reversible photochromic material can be included in the microcapsule wall film. Reverse photochromic microcapsule pigment (yellow in the light, colorless in the dark) and 10 parts of hydrophobic fumed silica (trade name: AEROSIL R812), 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.

Reversible Discoloration Printing or Preparation of Painted Material Using the above liquid composition, spray coating on a light blue ABS brooch as a support and drying at 70° C. for 5 minutes to form a film, and the film is cracked during the drying process. A coating having a cracking pattern was formed and a reversible discoloration printing or coating was obtained.
When the reversible color-changing printing or coated product obtained by the above-mentioned production method is irradiated with light, the cracked coating film becomes green, and the light blue due to the support is visually recognized from the cracked portion.
When the reversible discoloration printing or the coated article was left in a dark place, the cracked coating became light blue, and the cracked pattern was no longer visible.
When light was irradiated again, a green crack pattern and a light blue color due to the support were visually recognized from the cracked portion, and such a phase change could be repeated.

t ₁ Full color development temperature of microcapsule pigment containing heat-erasable reversible thermochromic composition t ₂ Color development start temperature of microcapsule pigment containing heat-erasable reversible thermochromic composition t ₃ Heat disappearance Decolorization initiation temperature of the microcapsule pigment containing the color-type reversible thermochromic composition t ₄ Complete erasing temperature of the microcapsule pigment containing the heat-decolorable reversible thermochromic composition T ₁ Complete Decoloring Temperature of Microcapsule Pigment Encapsulating Reversible Thermochromic Composition T ₂ Decolorization Starting Temperature of Microcapsule Pigment Encapsulating Reversible Thermochromic Composition T ₃ Heating Reversible Thermochromic Property Color development start temperature of the microcapsule pigment containing the composition T ₄ Full color development temperature of the microcapsule pigment containing the heat-developing reversible thermochromic composition ΔH Hysteresis width 1 Reversible color-changing printing or coating 2 Support 3 Cracks Pattern coating

Claims (3)

A printed or painted product having a crack-patterned coating on a support, and the support being visually recognized from the cracked portion, wherein the coating contains an inorganic pigment and a reversible color-changing material. Ri, the reversible color change material is reversibly variable color printing or painting was Ru is selected from thermochromic material or reversibly photochromic material. The reversible color-changeable printing or coated article according to claim 1, wherein the coating has a light-transmitting property. On the support, an inorganic pigment, a reversible color-changing material selected from a reversible thermochromic material or a reversible photochromic material, and a liquid composition comprising at least a solvent to form a film by printing or painting, 3. The method for producing reversible color-changing printing or a coated article according to claim 1, wherein the coating film is cracked when the coating film is dried to form a cracked coating film, and the support is visually recognized from the cracked portion.

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