Luminescent, reversible thermochromic laminate

Abstract

This invention provides a phosphorescent, reversible, thermochromic laminate that offers a wide variety of color changes in bright light, exhibits appearance changes associated with color changes, and allows for clear and rapid visualization of appearance changes accompanied by luminescence in dark places, thereby improving convenience. [Solution] A phosphorescent reversible thermochromic laminate 1 is formed by laminating a phosphorescent layer 3, on which phosphorescent pigments are dispersed and fixed in a binder, and a reversible thermochromic layer 4 is laminated on which microcapsule pigments that change color from colored to colorless are dispersed and fixed in a binder, each containing a reversible thermochromic composition comprising (a) an electron-donating color-developing organic compound, (b) an electron-accepting compound, and (c) a reaction medium that reversibly causes an electron transfer reaction by components (a) and (b) in a specific temperature range, and the reversible thermochromic layer develops into a color other than black.

Description

Technical Field

[0001] The present invention relates to a phosphorescent reversible thermochromic laminate. More specifically, the present invention relates to a phosphorescent reversible thermochromic laminate that allows clear visual recognition of the appearance change accompanying color change in a bright place and the appearance change accompanied by light emission in a dark place.

Background Art

[0002] Conventionally, rewritable cards and rewritable labels each formed by laminating a reversible thermosensitive recording film on a phosphorescent layer have been disclosed (for example, refer to Patent Document 1). The cards and labels are cards and labels that allow the display content in a bright place to be visually recognized similarly even in a dark place.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of Invention

Problems to be Solved by the Invention

[0004] The present invention provides a phosphorescent reversible thermochromic laminate that has abundant variations in color change in a bright place of a laminate provided with a reversible thermochromic layer on a phosphorescent layer of this type, has an accompanying appearance change, and allows the appearance change accompanied by light emission in a dark place to be clearly and quickly visually recognized.

Means for Solving the Problems

[0005] The present invention requires a phosphorescent reversible thermochromic laminate formed by laminating a reversible thermochromic layer containing a reversible thermochromic material that changes color from colored to colorless on a phosphorescent layer containing a phosphorescent material, wherein the reversible thermochromic layer develops a color excluding black. Furthermore, the absorbance of the minimum absorption wavelength (A) at wavelengths of 400 nm to 700 nm during the color development of the reversible thermochromic layer is in the range of 400 nm to less than 510 nm, the absorbance of the maximum absorption wavelength (B) is in the range of more than 510 nm and less than or equal to 700 nm, and B / A is 1.4 or more, and the absorbance of the maximum absorption wavelength (B) at wavelengths of 400 nm to 700 nm during the color development of the reversible thermochromic layer is in the range of more than 520 nm and less than or equal to 700 nm. The requirements are that the reversible thermochromic layer is a layer in which microcapsule pigments containing a reversible thermochromic composition comprising (a) an electron-donating color-changing organic compound, (b) an electron-accepting compound, and (c) a reaction medium that reversibly causes an electron transfer reaction by components (a) and (b) in a specific temperature range are dispersed and fixed in a binder, and the phosphorescent layer is a layer in which phosphorescent pigments are dispersed and fixed in a binder. [Effects of the Invention]

[0006] The present invention provides a phosphorescent, reversible, thermochromic laminate that offers a wide variety of color changes in bright light, exhibits appearance changes associated with color changes, and allows for clear and rapid visualization of appearance changes accompanied by luminescence in dark places, thereby improving convenience. [Brief explanation of the drawing]

[0007] [Figure 1] This graph illustrates the hysteresis characteristics in the color density-temperature curve of a reversible thermochromic composition that decolorizes upon heating. [Figure 2] This graph illustrates the hysteresis characteristics in the color density-temperature curve of a reversible thermochromic composition that has color memory properties and heat-decolorizing properties. [Figure 3] This graph illustrates the hysteresis characteristics in the color density-temperature curve of a heat-activated, reversible thermochromic composition. [Figure 4] This is a longitudinal cross-sectional diagram illustrating one embodiment of the phosphorescent, reversible, thermochromic laminate of the present invention. [Modes for carrying out the invention]

[0008] The phosphorescent material contained in the phosphorescent layer can be any general-purpose material that has the property of absorbing and storing light rays from the sun or electric lights, and gradually emitting light in the dark (this is called afterglow). Phosphorescent pigments such as CaS / Bi, CaSrS / Bi, ZnS / Cu, ZnCdS / Cu, and SrAl2O4 / rare earth metal systems can be used. The phosphorescent pigment is dispersed in a medium containing a binder to prepare a liquid composition such as a paint or printing ink, and is applied to the surface of a support (substrate) as a phosphorescent layer by known methods, such as printing means such as screen printing, offset printing, gravure printing, coater, pad printing, and transfer, or by means such as brush coating, spray coating, electrostatic coating, electrodeposition coating, pour coating, roller coating, and dipping coating. The phosphorescent layer is formed by the evaporation of the solvent in the liquid composition and the formation of other compounds, and the phosphorescent pigment is fixed in a dispersed state in the binder. Examples of materials for the support include paper, synthetic paper, yarn, fabric, flocked or napped fabric, nonwoven fabric, synthetic leather, leather, plastic, glass, ceramics, wood, stone, and metal. Furthermore, a molded product formed using a molding resin composition in which the phosphorescent pigment is blended into a thermoplastic resin or thermosetting resin may be used as a phosphorescent layer, or the phosphorescent layer may be attached to a support.

[0009] The aforementioned reversible thermochromic layer is laminated over or partially on the phosphorescent layer, and its appearance changes in accordance with the color change due to temperature changes. The reversible thermochromic layer contains a reversible thermochromic material that changes color from colored to colorless, and as the material, a reversible thermochromic composition containing three components—an electron-donating colored organic compound, an electron-accepting compound, and a reaction medium that reversibly causes a color reaction—is preferably used. Examples of the reversible thermochromic composition include a heat-decolorizing type (which decolorizes upon heating and develops color upon cooling) that comprises at least three essential components of a reaction medium that determines the temperature at which the color reaction of components (a) and (b) occurs. As the aforementioned reversible thermochromic composition, a reversible thermochromic composition of the heat-decolorizing type (decolorizes when heated and develops color when cooled) can be used, as described in Japanese Patent Publication No. 51-44706, Japanese Patent Publication No. 51-44707, Japanese Patent Publication No. 1-29398, etc., which changes color before and after a predetermined temperature (color change point), exhibits a decolorized state in the temperature range above the high-temperature color change point and a colored state in the temperature range below the low-temperature color change point, and of the two states, only one specific state exists in the room temperature range, and the other state is maintained as long as the heat or cold required to bring about that state is applied, but returns to the state exhibited in the room temperature range when the application of such heat or cold is stopped, and has the characteristic of having a relatively small hysteresis width (ΔH) of 1 to 7°C (see Figure 1).

[0010] Furthermore, the hysteresis width (Δ) described in Japanese Patent Publication No. 4-17154, Japanese Patent Publication No. 7-179777, Japanese Patent Publication No. 7-33997, Japanese Patent Publication No. 8-39936, Japanese Patent Publication No. 2006-137880, Japanese Patent Publication No. 2008-280523, International Publication No. 2010 / 131684, International Publication No. 2010 / 131684, International Publication No. 2012 / 046837, International Publication No. 2014 / 200053, International Publication No. 2015 / 119161, International Publication No. 2016 / 027664, International Publication No. 2017 / 022471, International Publication No. 2018 / 155583, etc. H) exhibits a relatively large characteristic of 8°C to 80°C, meaning that the shape of the curve plotting the change in color density due to temperature changes follows a significantly different path when the temperature is increased from a temperature below the color change temperature range compared to when it is decreased from a temperature above the color change temperature range. Therefore, a reversible thermochromic composition that exhibits color memory in a specific temperature range [temperature range between t2 and t3 (effectively a two-phase retention temperature range)], where the colored state in the low temperature range below the complete color development temperature (t1) or the decolorized state in the high temperature range above the complete decolorization temperature (t4), can also be applied (see Figure 2). The hysteresis characteristics in the color density-temperature curve of the aforementioned reversible thermochromic composition will be described. In Figure 2, the vertical axis represents color density and the horizontal axis represents temperature. The change in color density due to temperature changes progresses along the arrows. Here, A represents the density at the temperature t4 (hereinafter referred to as the complete decolorization temperature) where complete decolorization is reached, B represents the density at the temperature t3 (hereinafter referred to as the decolorization start temperature) where decolorization begins, C represents the density at the temperature t2 (hereinafter referred to as the color development start temperature) where color development begins, and D represents the density at the temperature t1 (hereinafter referred to as the complete color development temperature) where complete color development is reached. The discoloration temperature range is the temperature range between t1 and t4, and can exhibit either a colored state or a decolorized state. The temperature range between t2 and t3, which is the region with a large difference in color density, is the effective discoloration temperature range. Furthermore, the length of line segment EF is a measure of the contrast of the discoloration, and the length of line segment HG passing through the midpoint of line segment EF is the temperature range indicating the degree of hysteresis (hereinafter referred to as the hysteresis range ΔH). If this ΔH value is small, only one of the two states before and after discoloration can exist in the room temperature range. Conversely, if the ΔH value is large, it becomes easier to maintain both the before and after discoloration states.

[0011] The following provides a detailed explanation of each component (a), (b), and (c). (a) Component, i.e., the electron-donating chromogenic organic compound, is the component that determines the color and is a compound that produces color by donating electrons to component (b), which is the color developer. Examples of the aforementioned electron-donating colorimetric organic compounds include phthalide compounds, fluorane compounds, styrinoquinoline compounds, diazalodamine lactone compounds, pyridine compounds, quinazoline compounds, and bisquinazoline compounds, among which phthalide compounds and fluorane compounds are preferred. Examples of the phthalide compounds include diphenylmethanephthalide compounds, phenylindolylphthalide compounds, indolylphthalide compounds, diphenylmethaneazaphthalide compounds, phenylindolylazaphthalide compounds, and their derivatives. Among these, phenylindolylazaphthalide compounds and their derivatives are preferred. Further, examples of the fluoran compound include aminofluoran compounds, alkoxyfluoran compounds, and derivatives thereof. These compounds are exemplified 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-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3-(2-hexyloxy-4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3-[2-ethoxy-4-(N-ethylanilino)phenyl]-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3-(2-acetamido-4-diethylaminophenyl)-3-(1-propylindol-3-yl)-4-azaphthalide, 3,6-bis(diphenylamino)fluoran, 3,6-dimethoxyfluoran, 3,6-di-n-butoxyfluoran, 2-methyl-6-(N-ethyl-N-p-tolylamino)fluoran, 3-chloro-6-cyclohexylaminofluoran, 2-methyl-6-cyclohexylaminofluoran, 2-(2-chloroanilino)-6-dibutylaminofluoran, 2-(2-chloroanilino)-6-di-n-butylaminofluoran, 2-(3-trifluoromethylanilino)-6-diethylaminofluoran, 2-(3-trifluoromethylanilino)-6-dipentylaminofluoran, 2-(dibenzylamino)-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, 2-anilino-3-methyl-6-(N-ethyl-Np-tolylamino)fluorane, 1,2-Benz-6-diethylaminofluorane, 1,2-Benz-6-(N-ethyl-N-isobutylamino)fluorane, 1,2-Benz-6-(N-ethyl-N-isoamylamino)fluorane, 2-(3-methoxy-4-dodecoxystyryl)quinoline, Spiro[5H-(1)benzopyrano(2,3-d)pyrimidine-5,1′(3′H)isobenzofuran]-3′-one,2-(diethylamino)-8-(diethylamino)-4-methyl, Spiro[5H-(1)benzopyrano(2,3-d)pyrimidine-5,1′(3′H)isobenzofuran]-3′-one,2-(di-n-butylamino)-8-(di-n-butylamino)-4-methyl, Spiro[5H-(1)benzopyrano(2,3-d)pyrimidine-5,1′(3′H)isobenzofuran]-3′-one,2-(di-n-butylamino)-8-(diethylamino)-4-methyl, Spiro[5H-(1)benzopyrano(2,3-d)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-d)pyrimidine-5,1′(3′H)isobenzofuran]-3′-one,2-(dibutylamino)-8-(dipentylamino)-4-methyl, 4,5,6,7-Tetrachloro-3-[4-(dimethylamino)-2-methoxyphenyl]-3-(1-butyl-2-methyl-1H-indole-3-yl)-1(3H)-isobenzofuranone, 4,5,6,7-Tetrachloro-3-[4-(diethylamino)-2-ethoxyphenyl]-3-(1-ethyl-2-methyl-1H-indole-3-yl)-1(3H)-isobenzofuranone, 4,5,6,7-Tetrachloro-3-[4-(diethylamino)-2-ethoxyphenyl]-3-(1-pentyl-2-methyl-1H-indole-3-yl)-1(3H)-isobenzofuranone, 4,5,6,7-tetrachloro-3-[4-(diethylamino)-2-methylphenyl]-3-(1-ethyl-2-methyl-1H-indole-3-yl)-1(3H)-isobenzofuranone, 3′,6′-bis[phenyl(2-methylphenyl)amino]-spiro[isobenzofuran-1(3H),9′-[9H]xanthene]-3-one, 3′,6′-bis[phenyl(3-methylphenyl)amino]-spiro[isobenzofuran-1(3H),9′-[9H]xanthene]-3-one, 3′,6′-bis[phenyl(3-ethylphenyl)amino]-spiro[isobenzofuran-1(3H),9′-[9H]xanthene]-3-one, 2,6-bis(2′-ethyloxyphenyl)-4-(4′-dimethylaminophenyl)pyridine, 2,6-Bis(2′,4′-diethyloxyphenyl)-4-(4′-dimethylaminophenyl)pyridine, 2-(4′-dimethylaminophenyl)-4-methoxyquinazoline, 4,4′-(ethylenedioxy)-bis[2-(4-diethylaminophenyl)quinazoline] Examples include: In addition to the aforementioned compounds having substituents on the phenyl group forming the xanthene ring, fluoranes may also be compounds exhibiting blue or black coloration, having substituents on the phenyl group forming the xanthene ring and also substituents (for example, alkyl groups such as methyl groups, halogen atoms such as chloro groups) on the phenyl group forming the lactone ring.

[0012] The aforementioned component (b), i.e., the electron-accepting compound, is a compound that accepts electrons from component (a) and functions as a color developer for component (a). The electron-accepting compounds include compounds selected from the group of compounds having active protons and their derivatives, the group of pseudoacidic compounds (compounds that are not acids but act as acids in the composition to cause component (a) to develop color), and the group of compounds having electron vacancies. Among these, compounds selected from the group of compounds having active protons are preferred. Examples of compounds having active protons and their derivatives include compounds having phenolic hydroxyl groups and their metal salts, carboxylic acids and their metal salts, preferably aromatic carboxylic acids, aliphatic carboxylic acids having 2 to 5 carbon atoms and their metal salts, acidic phosphate esters and their metal salts, as well as azol compounds and their derivatives, 1,2,3-triazoles and their derivatives. Among these, compounds having phenolic hydroxyl groups are preferred because they can exhibit effective thermal color change properties. The aforementioned compounds having phenolic hydroxyl groups broadly include monophenol compounds to polyphenol compounds, and further include bis-type and tris-type phenols, as well as phenol-aldehyde condensation resins. Among the compounds having phenolic hydroxyl groups, those having at least two benzene rings are preferred. These compounds may also have substituents, and examples of substituents include alkyl groups, aryl groups, acyl groups, alkoxycarbonyl groups, carboxyl groups and their esters or amide groups, halogen groups, and the like. Examples of metals included in the metal salt of the compound having the active proton include sodium, potassium, calcium, zinc, zirconium, aluminum, magnesium, nickel, cobalt, tin, copper, iron, vanadium, titanium, lead, and molybdenum.

[0013] 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, resorcinol, dodecyl gallate, 4,4-dihydroxydiphenylsulfone, bis(4-hydroxyphenyl)sulfide, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)propane, 1 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) Phenyl)-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, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1-phenyl-1,1-bis(4-hydroxyphenyl) 2,2-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-heptane, 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,Examples include 2-bis(4-hydroxyphenyl)ethylpropionate, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 2,2-bis(4-hydroxyphenyl)-4-methylhexane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,1-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, bis(2-hydroxyphenyl)methane, 1,1,1-tris(4-hydroxyphenyl)ethane, and 3,3-bis(3-methyl-4-hydroxyphenyl)butane. The compound having the phenolic hydroxyl group exhibits the most effective thermal color change properties, but compounds selected from aromatic carboxylic acids and aliphatic carboxylic acids having 2 to 5 carbon atoms, carboxylic acid metal salts, acidic phosphate esters and their metal salts, 1,2,3-triazoles and their derivatives may also be used.

[0014] The component (c) of the reaction medium that causes the electron transfer reaction by the components (a) and (b) described above to occur reversibly in a specific temperature range will now be explained. Examples of component (c) include alcohols, esters, ketones, ethers, and acid amides. When using the aforementioned component (c) for microencapsulation and secondary processing described later, low molecular weight compounds tend to evaporate outside the capsule when subjected to high heat treatment. Therefore, compounds with 10 or more carbon atoms are preferably used to stably retain them inside the capsule. Effective alcohols include monohydric aliphatic saturated alcohols with 10 or more carbon atoms, specifically decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, heptadecyl alcohol, octadecyl alcohol, eicosyl alcohol, and docosyl alcohol.

[0015] As for esters, esters with 10 or more carbon atoms are effective, and esters obtained from any combination of a monohydric carboxylic acid having an aliphatic and alicyclic or aromatic ring and a monohydric alcohol having an aliphatic and alicyclic or aromatic ring, esters obtained from any combination of a polyhydric carboxylic acid having an aliphatic and alicyclic or aromatic ring and a monohydric alcohol having an aliphatic and alicyclic or aromatic ring, or any combination of a monohydric carboxylic acid having an aliphatic and alicyclic or aromatic ring and a polyhydric alcohol having an aliphatic and alicyclic or aromatic ring Examples of esters obtained from these include, specifically, ethyl caprylate, octyl caprylate, stearyl caprylate, myristyl caprate, docosyl caprate, 2-ethylhexyl laurate, n-decyl laurate, 3-methylbutyl myristate, myristyl myristate, cetyl myristate, isopropyl palmitate, neopentyl palmitate, nonyl palmitate, cyclohexyl palmitate, n-butyl stearate, 2-methylbutyl stearate, and 3,5,5-trimethylhexyl stearate. n-undecyl stearate, pentadecyl stearate, stearyl stearate, cyclohexylmethyl stearate, isopropyl behenate, hexyl behenate, lauryl behenate, behenyl behenate, cetyl benzoate, p-tert-butyl stearyl benzoate, dimyristyl phthalate, distearyl phthalate, dimyristyl oxalate, dicetyl oxalate, dicetyl malonate, dilauryl succinate, dilauryl glutarate, diundecyl adipate, dilauryl azelaate, di-(n-nonyl) sebacate Examples include 1,18-octadecylmethylenedicarboxylic acid dineopentyl, 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 distearate, etc.

[0016] Furthermore, ester compounds selected from saturated fatty acids and branched aliphatic alcohols, unsaturated fatty acids or branched or substituted saturated fatty acids and branched or aliphatic alcohols with 16 or more carbon atoms, cetyl butyrate, stearyl butyrate, and 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 Xyl, 1-ethylhexyl myristate, 1-ethylhexyl palmitate, 2-methylpentyl caproate, 2-methylpentyl caprylate, 2-methylpentyl caprate, 2-methylpentyl laurate, 2-methylbutyl stearate, 2-methylbutyl stearate, 3-methylbutyl stearate, 1-methylheptyl stearate, 2-methylbutyl behenate, 3-methylbutyl behenate, 1-methylheptyl stearate, 1-methylheptyl behenate, 1-ethylpentyl caproate, 1-Ethylpentyl palmitate, 1-Methylpropyl stearate, 1-Methyloctyl stearate, 1-Methylhexyl stearate, 1,1-Dimethylpropyl laurate, 1-Methylpentyl caprate, 2-Methylhexyl palmitate, 2-Methylhexyl stearate, 2-Methylhexyl behenate, 3,7-Dimethyloctyl laurate, 3,7-Dimethyloctyl myristate, 3,7-Dimethyloctyl palmitate, 3,7-Dimethyloctyl stearate, 3,7-Dimethyloctyl behenate Examples include thiooctyl oleate, stearyl oleate, behenyl oleate, stearyl linoleate, behenyl linoleate, 3,7-dimethyloctyl erucate, stearyl erucate, isostearyl erucate, cetyl isostearate, stearyl isostearate, 2-methylpentyl 12-hydroxystearate, 2-ethylhexyl 18-bromostearate, isostearyl 2-ketomyristate, 2-ethylhexyl 2-fluoromyristate, cetyl butyrate, stearyl butyrate, and behenyl butyrate.

[0017] Furthermore, in order to exhibit large hysteresis characteristics with respect to the color density-temperature curve and change color, thereby providing color memory depending on temperature changes, carboxylic acid ester compounds exhibiting a ΔT value (melting point-cloud point) of 5°C or higher and less than 50°C as described in Japanese Patent Publication No. 4-17154, such as carboxylic acid esters containing a substituted aromatic ring in the molecule, esters of carboxylic acids containing an unsubstituted aromatic ring and aliphatic alcohols having 10 or more carbon atoms, carboxylic acid esters containing a cyclohexyl group in the molecule, esters of fatty acids having 6 or more carbon atoms and unsubstituted aromatic alcohols or phenols, esters of fatty acids having 8 or more carbon atoms and branched aliphatic alcohols, esters of dicarboxylic acids and aromatic alcohols or branched aliphatic alcohols, dibenzyl cinnamate, heptyl stearate, didecyl adipate, dilauryl adipate, dimyristyl adipate, dicetyl adipate, distearyl adipate, trilaurin, trimiristine, tristearin, dimyristine, distearin, etc. are mentioned.

[0018] Fatty acid ester compounds obtained from an odd-numbered aliphatic monohydric alcohol with 9 or more carbon atoms and an even-numbered aliphatic carboxylic acid, and fatty acid ester compounds with a total of 17 to 23 carbon atoms obtained from n-pentyl alcohol or n-heptyl alcohol and an even-numbered aliphatic carboxylic acid with 10 to 16 carbon atoms 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, n-heptyl laurate, n-nonyl laurate, n-undecyl laurate, n-tridecyl laurate, n-pentadecyl laurate, n-pentyl myristate, n-heptyl myristate, myristic acid Examples include n-nonyl palmitate, n-undecyl myristate, 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-undersi eicosanoate, n-tridecyl eicosanoate, n-pentadecyl eicosanoate, n-nonyl behenate, n-undecyl behenate, n-tridecyl behenate, and n-pentadecyl behenate.

[0019] Effective ketones include aliphatic ketones with a total carbon number of 10 or more, such as 2-decanone, 3-decanone, 4-decanone, 2-undecanone, 3-undecanone, 4-undecanone, 5-undecanone, 2-dodecanone, 3-dodecanone, 4-dodecanone, 5-dodecanone, 2-tridecanone, 3-tridecanone, 2-tetradecanone, 2-pentadecanone, 8-pentadecanone, 2-hexadecanone, 3-hexadecanone, 9-heptadecanone, 2-pentadecanone, 2-octadecanone, 2-nonadecanone, 10-nonadecanone, 2-eicosanone, 11-eicosanone, 2-heneicosanone, 2-docosanone, laurone, and stearone. Furthermore, arylalkyl ketones with a total carbon number of 12 to 24, such as n-octadecanophenone, n-heptadecanophenone, n-hexadecanophenone, n-pentadecanophenone, n-tetradecanophenone, 4-n-dodecacetophenone, n-tridecanophenone, 4-n-undecanoacetophenone, n-laurophenone, 4-n-decanoacetophenone, n-undecanophenone, 4-n-nonylacetophenone, n-decanophenone, 4-n-octylacetophenone, n-nonylacetophenone Examples include nophenone, 4-n-heptylacetophenone, n-octanophenone, 4-n-hexylacetophenone, 4-n-cyclohexylacetophenone, 4-tert-butylpropiophenone, n-heptaphenone, 4-n-pentylacetophenone, cyclohexylphenyl ketone, benzyl-n-butyl ketone, 4-n-butylacetophenone, n-hexanophenone, 4-isobutylacetophenone, 1-acetonaphthone, 2-acetonaphthone, and cyclopentylphenyl ketone.

[0020] As for ethers, aliphatic ethers with a total of 10 or more carbon atoms are effective, and examples include dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, dinonyl ether, didecyl ether, diundecyl ether, didodecyl ether, ditridecyl ether, ditetradecyl ether, dipentadecyl ether, dihexadecyl ether, dioctadecyl ether, decanediol dimethyl ether, undecanediol dimethyl ether, dodecanediol dimethyl ether, tridecanediol dimethyl ether, decanediol diethyl ether, and undecanediol diethyl ether.

[0021] Acid amides include acetamide, propionic acid amide, butyrate amide, caproic acid amide, caprylic acid amide, capric acid amide, lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, oleic acid amide, erucic acid amide, benzamide, caproic acid anilide, caprylic acid anilide, capric acid anilide, lauric acid anilide, myristic acid anilide, palmitic acid anilide, stearic acid anilide, behenic acid anilide, oleic acid anilide, erucic acid anilide, caproic acid N-methylamide, Caprylic acid N-methylamide, capric acid N-methylamide, lauric acid N-methylamide, myristate acid N-methylamide, palmitic acid N-methylamide, stearate N-methylamide, behenic acid N-methylamide, oleic acid N-methylamide, erucate N-methylamide, laurate N-ethylamide, myristate acid N-ethylamide, palmitic acid N-ethylamide, stearate N-ethylamide, oleic acid N-ethylamide, laurate N-butylamide, myristate acid N-butylamide, palmitic acid N-butylamide, stear N-butylamide phosphate, N-butylamide oleate, N-octylamide laurate, N-octylamide myristate, N-octylamide palmitate, N-octylamide stearate, N-octylamide oleate, N-dodecylamide laurate, N-dodecylamide myristate, N-dodecylamide palmitate, N-dodecylamide stearate, N-dodecylamide oleate, dilaurate, dimyristateamide, dipalmitamide, distearate, dioleamide, trilaurate, tri Myristic acid amide, tripalmitic acid amide, tristearic acid amide, trioleic acid amide, succinic acid amide, adipic acid amide, glutaric acid amide, malonic acid amide, azelaic acid amide, maleic acid amide, succinic acid N-methylamide, adipic acid N-methylamide, glutaric acid N-methylamide, malonic acid N-methylamide, azelaic acid N-methylamide, succinic acid N-ethylamide, adipic acid N-ethylamide, glutaric acid N-ethylamide, malonic acid N-ethylamide, azelaic acid N-ethylamide, succinic acid N-butylamide,Examples include N-butylamide adipic acid, N-butylamide glutarate, N-butylamide malonate, N-octylamide adipic acid, and N-dodecylamide adipic acid.

[0022] Furthermore, the compound represented by the following general formula (1) can also be used as component (c) above. [ka] [In the formula, R1 represents a hydrogen atom or a methyl group, m represents an integer from 0 to 2, and either X1 or X2 is -(CH2)] n OCOR2 or -(CH2) n COOR2, the other side represents a hydrogen atom, n is an integer from 0 to 2, R2 represents an alkyl group or alkenyl group with 4 or more carbon atoms, Y1 and Y2 represent a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, a methoxy group, or a halogen, and r and p are integers from 1 to 3. Among the compounds represented by formula (1) above, the case where R1 is a hydrogen atom is preferred because it yields a reversible thermochromic composition with a wider hysteresis width, and the case where R1 is a hydrogen atom and m is 0 is even more preferred. Furthermore, among the compounds represented by formula (1), the compound represented by the following general formula (2) is more preferably used. [ka] In the formula, R represents an alkyl or alkenyl group having 8 or more carbon atoms, preferably an alkyl group having 10 to 24 carbon atoms, and more preferably an alkyl group having 12 to 22 carbon atoms. Specific examples of the aforementioned compounds include 4-benzyloxyphenylethyl octanoate, 4-benzyloxyphenylethyl nonanoate, 4-benzyloxyphenylethyl decanoate, 4-benzyloxyphenylethyl undecanoate, 4-benzyloxyphenylethyl dodecanoate, 4-benzyloxyphenylethyl tridecanoate, 4-benzyloxyphenylethyl tetradecanoate, 4-benzyloxyphenylethyl pentadecanoate, 4-benzyloxyphenylethyl hexadecanoate, 4-benzyloxyphenylethyl heptadecanoate, and 4-benzyloxyphenylethyl octadecanoate.

[0023] Furthermore, as component (c) above, a compound represented by the following general formula (3) can also be used. [ka] (In the formula, R represents an alkyl or alkenyl group having 8 or more carbon atoms, m and n each represent an integer from 1 to 3, and X and Y represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen, respectively.) Specific examples of the aforementioned compounds include 1,1-diphenylmethyl octanoate, 1,1-diphenylmethyl nonanoate, 1,1-diphenylmethyl decanoate, 1,1-diphenylmethyl undecanoate, 1,1-diphenylmethyl dodecanoate, 1,1-diphenylmethyl tridecanoate, 1,1-diphenylmethyl tetradecanoate, 1,1-diphenylmethyl pentadecanoate, 1,1-diphenylmethyl hexadecanoate, 1,1-diphenylmethyl heptadecanoate, and 1,1-diphenylmethyl octadecanoate.

[0024] Furthermore, the compound represented by the following general formula (4) can also be used as component (c). [ka] (In the formula, X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, or a halogen atom; m represents an integer from 1 to 3; and n represents an integer from 1 to 20.) The aforementioned compounds include diesters of malonic acid and 2-[4-(4-chlorobenzyloxy)phenyl)]ethanol, succinic acid and 2-(4-benzyloxyphenyl)ethanol, succinic acid and 2-[4-(3-methylbenzyloxy)phenyl)]ethanol, glutaric acid and 2-(4-benzyloxyphenyl)ethanol, glutaric acid and 2-[4-(4-chlorobenzyloxy)phenyl)]ethanol, adipic acid and 2-(4-benzyloxyphenyl)ethanol, pimelic acid and 2-(4-benzyloxyphenyl)ethanol, suberic acid and 2-(4-benzyloxyphenyl)ethanol, and suberic acid and 2-[4-(3-methylbenzyloxy) Examples include diesters of 2-(4-(4-chlorobenzyloxy)phenyl)) ethanol, diesters of suberic acid and 2-(4-(2,4-dichlorobenzyloxy)phenyl)) ethanol, diesters of suberic acid and 2-(4-dichlorobenzyloxy)phenyl)) ethanol, diesters of azelaic acid and 2-(4-benzyloxyphenyl) ethanol, diesters of sebacic acid and 2-(4-benzyloxyphenyl) ethanol, diesters of 1,10-decanedicarboxylic acid and 2-(4-benzyloxyphenyl) ethanol, diesters of 1,18-octadecanedicarboxylic acid and 2-(4-benzyloxyphenyl) ethanol, and diesters of 1,18-octadecanedicarboxylic acid and 2-(4-methylbenzyloxy)phenyl)) ethanol.

[0025] Furthermore, the compound represented by the following general formula (5) can also be used as component (c). [ka] (In the formula, R represents an alkyl or alkenyl group having 1 to 21 carbon atoms, and n represents an integer from 1 to 3.) The aforementioned compounds include diesters of 1,3-bis(2-hydroxyethoxy)benzene and capric acid, diesters of 1,3-bis(2-hydroxyethoxy)benzene and undecanoic acid, diesters of 1,3-bis(2-hydroxyethoxy)benzene and lauric acid, diesters of 1,3-bis(2-hydroxyethoxy)benzene and myristic acid, diesters of 1,4-bis(hydroxymethoxy)benzene and butyric acid, diesters of 1,4-bis(hydroxymethoxy)benzene and isovaleric acid, diesters of 1,4-bis(2-hydroxyethoxy)benzene and acetic acid, Examples include diesters of 4-bis(2-hydroxyethoxy)benzene with propionic acid, 1,4-bis(2-hydroxyethoxy)benzene with valeric acid, 1,4-bis(2-hydroxyethoxy)benzene with caproic acid, 1,4-bis(2-hydroxyethoxy)benzene with caprylic acid, 1,4-bis(2-hydroxyethoxy)benzene with capric acid, 1,4-bis(2-hydroxyethoxy)benzene with lauric acid, and 1,4-bis(2-hydroxyethoxy)benzene with myristic acid.

[0026] Furthermore, the compound represented by the following general formula (6) can also be used as component (c). [ka] (In the formula, X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom; m represents an integer from 1 to 3; and n represents an integer from 1 to 20.) Examples of the aforementioned compounds include diesters of succinic acid and 2-phenoxyethanol, diesters of suberic acid and 2-phenoxyethanol, diesters of sebacic acid and 2-phenoxyethanol, diesters of 1,10-decanedicarboxylic acid and 2-phenoxyethanol, and diesters of 1,18-octadecanedicarboxylic acid and 2-phenoxyethanol.

[0027] Furthermore, the compound represented by the following general formula (7) can also be used as component (c). [ka] (In the formula, R represents any of a C4 to C22 alkyl group, a cycloalkylalkyl group, a cycloalkyl group, or a C4 to C22 alkenyl group; X represents any of a hydrogen atom, a C1 to C4 alkyl group, a C1 to C4 alkoxy group, or a halogen atom; and n represents 0 or 1.) Examples of the aforementioned compounds include decyl 4-phenylbenzoate, lauryl 4-phenylbenzoate, myristyl 4-phenylbenzoate, cyclohexylethyl 4-phenylbenzoate, octyl 4-biphenylacetate, nonyl 4-biphenylacetate, decyl 4-biphenylacetate, lauryl 4-biphenylacetate, myristyl 4-biphenylacetate, tridecyl 4-biphenylacetate, pentadecyl 4-biphenylacetate, cetyl 4-biphenylacetate, cyclopentyl 4-biphenylacetate, cyclohexylmethyl 4-biphenylacetate, hexyl 4-biphenylacetate, and cyclohexylmethyl 4-biphenylacetate.

[0028] Furthermore, the compound represented by the following general formula (8) can also be used as component (c). [ka] (In the formula, R represents any of an alkyl group having 3 to 18 carbon atoms or an aliphatic acyl group having 3 to 18 carbon atoms; X represents any of a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 or 2 carbon atoms, or a halogen atom; Y represents any of a hydrogen atom or a methyl group; and Z represents any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 or 2 carbon atoms, or a halogen atom.) Examples of the aforementioned compounds include phenoxyethyl 4-butoxybenzoate, phenoxyethyl 4-pentyloxybenzoate, phenoxyethyl 4-tetradecyloxybenzoate, esters of phenoxyethyl 4-hydroxybenzoate and dodecanoic acid, and dodecyl ether of phenoxyethyl vanillate.

[0029] Furthermore, the compound represented by the following general formula (9) can also be used as component (c). [ka] (In the formula, R represents any of the following: an alkyl group having 4 to 22 carbon atoms, an alkenyl group having 4 to 22 carbon atoms, a cycloalkylalkyl group, or a cycloalkyl group; X represents any of the following: a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom; Y represents any of the following: a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom; and n represents 0 or 1.) Examples of the aforementioned compounds include benzoic acid esters of octyl p-hydroxybenzoate, decyl p-hydroxybenzoate, p-methoxybenzoic acid ester of heptyl p-hydroxybenzoate, o-methoxybenzoic acid ester of dodecyl p-hydroxybenzoate, and benzoic acid ester of cyclohexylmethyl p-hydroxybenzoate.

[0030] Furthermore, the compound represented by the following general formula (10) can also be used as component (c). [ka] (In the formula, R represents any of the following: an alkyl group having 3 to 18 carbon atoms, a cycloalkylalkyl group having 6 to 11 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, or an alkenyl group having 3 to 18 carbon atoms; X represents any of the following: a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a halogen atom; and Y represents any of the following: a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, an ethoxy group, or a halogen atom.) Examples of the aforementioned compounds include phenoxyethyl ether of nonyl p-hydroxybenzoate, phenoxyethyl ether of decyl p-hydroxybenzoate, phenoxyethyl ether of undecyl p-hydroxybenzoate, and phenoxyethyl ether of dodecyl vanillate.

[0031] Furthermore, the compound represented by the following general formula (11) can also be used as component (c). [ka] (In the formula, R represents a cycloalkyl group having 3 to 8 carbon atoms or a cycloalkylalkyl group having 4 to 9 carbon atoms, and n represents an integer from 1 to 3.) Examples of the aforementioned compounds include diesters of 1,3-bis(2-hydroxyethoxy)benzene and cyclohexanecarboxylic acid, diesters of 1,4-bis(2-hydroxyethoxy)benzene and cyclohexanepropionic acid, and diesters of 1,3-bis(2-hydroxyethoxy)benzene and cyclohexanepropionic acid.

[0032] Furthermore, the compound represented by the following general formula (12) can also be used as component (c). [ka] (In the formula, R represents an alkyl group having 3 to 17 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a cycloalkylalkyl group having 5 to 8 carbon atoms; X represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a methoxy group, an ethoxy group, or a halogen atom; and n represents an integer from 1 to 3.) Examples of the aforementioned compounds include diesters of 4-phenylphenol ethylene glycol ether and cyclohexanecarboxylic acid, diesters of 4-phenylphenol diethylene glycol ether and lauric acid, diesters of 4-phenylphenol triethylene glycol ether and cyclohexanecarboxylic acid, diesters of 4-phenylphenol ethylene glycol ether and octanoic acid, diesters of 4-phenylphenol ethylene glycol ether and nonanoic acid, diesters of 4-phenylphenol ethylene glycol ether and decanoic acid, and diesters of 4-phenylphenol ethylene glycol ether and myristic acid.

[0033] Furthermore, specific alkoxyphenol compounds having a linear or side-chain alkyl group with 3 to 18 carbon atoms can be used as electron-accepting compounds (Japanese Patent Publication No. 11-129623, Japanese Patent Publication No. 11-5973), specific hydroxybenzoic acid esters can be used (Japanese Patent Publication No. 2001-105732), gallic acid esters can be used, etc. (Japanese Patent Publication No. 51-44706, Japanese Patent Publication No. 2003-253149), or a reversible thermochromic composition of the heat-developing type (develops color when heated and disappears when cooled) can be applied (see Figure 3).

[0034] The reversible thermochromic composition is a compatible mixture comprising the above-mentioned components (a), (b), and (c) as essential components. The proportion of each component depends on the concentration, discoloration temperature, discoloration form, and type of each component, but generally, the component ratios that yield the desired properties are in the range of 1 part of component (a) to 0.1 to 100 parts of component (b), preferably 0.1 to 50 parts, more preferably 0.5 to 20 parts, and 1 to 800 parts of component (c), preferably 5 to 200 parts, more preferably 5 to 100 parts, and even more preferably 10 to 100 parts (all of the above proportions are in parts by mass). By having the mass ratio of component (a), component (b), and component (c) within the above range, it becomes easier to create a reversible thermochromic composition that exhibits high concentration in the colored state and low residual color in the decolorized state, that is, a composition with even better contrast between the colored state and the decolorized state.

[0035] Furthermore, various light stabilizers can be added as needed. The light stabilizer is included to prevent photodegradation of the reversible thermochromic composition consisting of components (a), (b), and (c), and is included in a proportion of 0.3 to 24% by mass, preferably 0.3 to 16% by mass, per 1% by mass of component (a). Among the aforementioned light stabilizers, ultraviolet absorbers can effectively cut ultraviolet rays contained in sunlight, etc., and prevent photodegradation caused by the excitation state due to the photoreaction of component (a), while antioxidants, singlet oxygen quenchers, superoxide anion quenchers, ozone quenchers, etc., can suppress oxidation reactions caused by light. The light stabilizers may be used alone or in combination of two or more types. Furthermore, by incorporating a non-coloring coloring agent such as a general dye or pigment into the reversible thermochromic composition, it is possible to make it exhibit a color change behavior from colored (1) to colored (2).

[0036] The reversible thermochromic composition according to the present invention is effective when applied as is, but it can also be encapsulated in microcapsules to form reversible thermochromic microcapsule pigments (hereinafter sometimes referred to as "microcapsule pigments"), or dispersed in a thermoplastic resin or thermosetting resin to form reversible thermochromic resin particles (hereinafter sometimes referred to as "resin particles"). The aforementioned reversible thermochromic composition is preferably encapsulated in microcapsules to form a reversible thermochromic microcapsule pigment. This is because encapsulation in microcapsules allows for the formation of a chemically or physically stable pigment, and furthermore, the reversible thermochromic composition maintains the same composition and exerts the same effects under various usage conditions. Microencapsulation can be achieved using conventionally known methods such as isocyanate-based interfacial polymerization, melamine-formaldehyde-based in situ polymerization, liquid curing coating, phase separation from aqueous solutions, phase separation from organic solvents, melt-dispersion-cooling, air suspension coating, and spray drying, and is selected appropriately depending on the application. Furthermore, depending on the purpose, a secondary resin coating can be applied to the surface of the microcapsules to provide durability or modify the surface properties for practical use. The microcapsule pigment preferably has a mass ratio of encapsulated material to wall film of 7:1 to 1:1. By having the mass ratio of encapsulated material to wall film within this range, a decrease in color density and vividness during color development is prevented. More preferably, the mass ratio of encapsulated material to wall film is 6:1 to 1:1.

[0037] The average particle size of the reversible thermochromic microcapsule pigment or resin particles is preferably in the range of 0.01 to 50 μm, more preferably 0.1 to 30 μm, and even more preferably 0.5 to 20 μm. If the average particle size of the microcapsule pigment or resin particles exceeds 50 μm, it will lack dispersion stability and processability when blended into inks, paints, or resins. On the other hand, if the average particle size of the microcapsule pigment or resin particles is less than 0.01 μm, it will be difficult to achieve high-concentration color development. The average particle diameter was measured by determining the particle area using image analysis particle size distribution measurement software [Mountec Co., Ltd., product name: MacView], calculating the projected area circle equivalent diameter (Heywood diameter) from the area of ​​the particle area, and then measuring the average particle diameter of particles equivalent to an equivolute sphere based on that value. Furthermore, if the particle size of all or most of the particles exceeds 0.2 μm, it is also possible to measure the average particle size of particles equivalent to equivolute spheres using the Coulter method with a particle size distribution analyzer [Beckman Coulter, Ltd., product name: Multisizer 4e]. Furthermore, volume-based particle diameter and average particle diameter may be measured using a laser diffraction / scattering particle size distribution analyzer (manufactured by Horiba, Ltd., product name: LA-960V2) that has been calibrated based on the values ​​measured using the aforementioned software or a measuring device using the Coulter method.

[0038] The reversible thermochromic material is dispersed in a medium containing a binder to prepare a liquid composition such as a paint or printing ink, and is applied to the surface of a phosphorescent layer by known methods, such as printing methods like screen printing, offset printing, gravure printing, coater, pad printing, and transfer, or by means of brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, and dipping coating, and is applied as a reversible thermochromic layer. The reversible thermochromic layer is formed by the evaporation of the solvent in the liquid composition and the formation of other compounds, and the reversible thermochromic material is fixed in a dispersed state in the binder. Furthermore, a molded product formed using a molding resin composition in which the reversible thermochromic material is blended into a thermoplastic resin or thermosetting resin can be used as a reversible thermochromic layer, and a laminate may be formed by attaching the reversible thermochromic layer to a phosphorescent layer. By incorporating non-coloring colorants such as general dyes or pigments into the aforementioned reversible thermochromic layer, it is also possible to make it exhibit a color change behavior from colored (1) to colored (2).

[0039] The phosphorescent, reversible thermochromic laminate of the present invention comprises a phosphorescent layer on which a reversible thermochromic layer containing a reversible thermochromic material that changes color from colored to colorless is laminated. The reversible thermochromic layer is colored except black when the reversible thermochromic material is colored, and changes color to colorless or a different color when the reversible thermochromic material is decolorized. In bright light, the reversible thermochromic layer exhibits a rich variety of color changes. Furthermore, when light is shone on the reversible thermochromic material after it has developed color in bright light, the phosphorescent layer located beneath the reversible thermochromic layer absorbs (excites) light in the 200-450 nm range and emits light. Therefore, by partially decolorizing or changing the color of the reversible thermochromic layer in bright light, a colorful change in appearance can be observed. Additionally, because the phosphorescent layer emits light in the areas where the reversible thermochromic layer has decolorized or changed color, the luminescence from the phosphorescent layer can be observed in the dark, allowing for clear and rapid observation of the change in appearance in the dark. Furthermore, by irradiating the reversible thermochromic material contained in the reversible thermochromic layer with light while it has developed color in a bright place, and then partially decolorizing or changing the color of the reversible thermochromic layer in a dark place, the luminescence from the phosphorescent layer can be seen in the areas where the reversible thermochromic layer has decolorized or changed color, allowing for clear and rapid visualization of the change in appearance in the dark. Furthermore, when a reversible thermochromic layer containing a reversible thermochromic material that turns black is placed on a phosphorescent layer and irradiated with light, the phosphorescent layer located beneath the reversible thermochromic layer is less easily excited by the black-colored reversible thermochromic material. As a result, in the dark, it becomes difficult to see the luminescence from the phosphorescent layer in areas where the reversible thermochromic layer has faded or changed color, and the change in appearance in the dark is minimal. Furthermore, the reversible thermochromic layer exhibits a wide range of color variations, ranging from purple to red (purple, blue, green, red), due to the reversible thermochromic material having an absorbance of 400 to less than 510 nm at the minimum absorption wavelength (A) between 400 nm and 700 nm during color development, and an absorbance of 510 nm to 700 nm at the maximum absorption wavelength (B) with a B / A ratio of 1.4 or higher. In addition, the appearance changes caused by partially decolorizing or changing the color of the reversible thermochromic layer in bright light, and the luminescence and appearance changes caused by the phosphorescent layer in dark light, can be clearly and quickly observed. Furthermore, the B / A ratio is preferably 1.6 or higher, and more preferably 1.8 or higher. Furthermore, the reversible thermochromic layer exhibits a wide range of color variations due to the color change of the reversible thermochromic layer, which develops from purple to green (purple, blue, green). This is achieved when the reversible thermochromic material has an absorbance of 400 to less than 510 nm at the minimum absorption wavelength (A) between 400 nm and 700 nm, and an absorbance of 520 to 700 nm at the maximum absorption wavelength (B), with a B / A ratio of 1.4 or higher. In addition, the appearance change caused by partially decolorizing or changing the color of the reversible thermochromic layer in bright light, and the luminescence and appearance change caused by the phosphorescent layer in dark light, can be clearly and quickly observed. Such variability is possible because the phosphorescent material contained in the phosphorescent layer can effectively impart purple, blue, and green colors with excellent luminescence intensity. Therefore, the reversible thermochromic layer preferably has an absorbance of the maximum absorption wavelength (B) at a wavelength of 400 nm to 700 nm when the reversible thermochromic material develops color in the range of over 530 and under 700 nm, and more preferably in the range of over 540 and under 700 nm. Furthermore, the reversible thermochromic layer has the same color when the reversible thermochromic material is colored and the same color when the phosphorescent layer is emitted. This allows the color of the reversible thermochromic layer in bright light to match the color of the areas where the reversible thermochromic layer has faded in dark light, thus providing a unique change that makes it appear as if the areas that are colored (emitted) in bright light and dark light have been swapped.

[0040] Specific examples of products using the phosphorescent, reversible, thermochromic laminate obtained as described above include the following: (1)Toys Dolls and animal-shaped toys, hair for dolls and animal-shaped toys, dollhouses and furniture, clothing, hats, bags, shoes and other doll accessories, accessory toys, stuffed animals, drawing toys, picture books for toys, puzzle toys such as jigsaw puzzles, building blocks, block toys, spinning tops, kites, musical instrument toys, cooking toys, toy guns, capture toys, background toys, toys that imitate vehicles, animals, plants, buildings, food, etc. (2) Clothing Clothing such as T-shirts, sweatshirts, blouses, dresses, swimwear, raincoats, and ski wear; footwear such as shoes and shoelaces; cloth personal items such as handkerchiefs, towels, and furoshiki (wrapping cloths); gloves, ties, hats, scarves, mufflers, etc. (3) Indoor decorations Carpets, curtains, curtain cords, tablecloths, rugs, cushions, carpets, rugs, upholstery fabrics, seats, mats, picture frames, artificial flowers, photo frames, etc. (4) Furniture Bedding such as futons, pillows, and mattresses, lighting fixtures, heating and cooling appliances, etc. (5) Ornaments Rings, bracelets, tiaras, earrings, hair clips, false nails, ribbons, scarves, watches, glasses, etc. (6) Stationery Writing instruments, stamps, erasers, underlays, rulers, notebooks, adhesive tape, etc. (7) Kitchenware Cups, plates, chopsticks, spoons, forks, pots, frying pans, etc. (8) Others Calendars, labels, cards, recording materials, various anti-counterfeiting printed materials, books such as picture books, bags, packaging containers, embroidery thread, sports equipment, fishing gear, coasters, musical instruments, hand warmers, cooling packs, bags such as wallets, umbrellas, vehicles, buildings, temperature sensing indicators, training equipment, etc. [Examples]

[0041] Examples are shown below. In the examples, "parts" refer to parts by mass. Example 1 (see Figure 4) Fabrication of phosphorescent, reversible thermochromic laminates A phosphorescent oil-based spray paint was obtained by mixing 20 parts of green phosphorescent pigment (product name: N Luminova G-300M, manufactured by Nemoto Special Chemicals Co., Ltd.), 50 parts of acrylic resin / xylene solution, 60 parts of xylene, and 10 parts of isocyanate-based curing agent as phosphorescent materials. The phosphorescent oil-based spray paint was spray-painted onto the surface of a white ABS resin support 2, and then dried to form a phosphorescent layer 3. Next, on the upper surface of the phosphorescent layer 3, a reversible thermal transformation is applied, consisting of (a) 1 part of 2-(dibutylamino)-8-(dipentylamino)-4-methylspiro[5H-[1]benzopyrano[2,3-d]pyrimidine-5,1′(3H′)-isobenzofuran]-3′-one as component (a), 5 parts of 4,4′-(2-ethylhexylidene)bisphenol and 2 parts of 4,4′-(1-phenylethylidene)bisphenol as component (b), and 50 parts of neopentyl stearate as component (c). A reversible thermochromic oil-based spray paint was prepared by mixing and stirring 5 parts of a reversible thermochromic microcapsule pigment (complete decolorization temperature 30°C, complete color development temperature 15°C, pink-colorless) coated with an epoxy resin film, 2 parts of blue pigment, 20 parts of acrylic resin xylene solution (50% solids), 50 parts of acrylic resin / xylene solution, 60 parts of xylene, and 10 parts of isocyanate-based curing agent. The paint was then applied and dried to form a reversible thermochromic layer 4, obtaining a phosphorescent reversible thermochromic laminate 1. Furthermore, the absorbance at the minimum absorption wavelength (A) between 400 nm and 700 nm during the color development of the reversible thermochromic layer was 0.54 (428 nm), the absorbance at the maximum absorption wavelength (B) was 1.52 (546 nm), and the B / A ratio was 2.8.

[0042] The phosphorescent, reversible thermochromic laminate exhibited a purple color in its reversible thermochromic layer at temperatures below 15°C in bright light. At temperatures above 30°C, it changed from purple to blue, maintaining this state at room temperature. When the temperature was reduced again to below 15°C, it changed back to purple, maintaining this state at room temperature. Next, when a laminate that exhibits purple in bright light was irradiated with UV light, and then the reversible thermochromic layer was partially discolored with a dark color, the green emission from the phosphorescent pigment of the phosphorescent layer could be clearly seen in the areas where the reversible thermochromic layer had discolored. Furthermore, when a laminate that appears purple in bright light is irradiated with UV light, the reversible thermochromic layer partially changes color. Then, when the laminate is viewed in the dark, the green light emitted by the phosphorescent pigment in the phosphorescent layer can be clearly seen in the areas where the reversible thermochromic layer has changed color.

[0043] Example 2 Fabrication of phosphorescent, reversible thermochromic laminates A phosphorescent oil-based spray paint was obtained by mixing 20 parts of green phosphorescent pigment (product name: N Luminova G-300M, manufactured by Nemoto Special Chemicals Co., Ltd.), 50 parts of acrylic resin / xylene solution, 60 parts of xylene, and 10 parts of isocyanate-based curing agent as phosphorescent materials. The aforementioned phosphorescent oil-based spray paint was spray-coated onto the surface of a white ABS resin support, and then dried to form a phosphorescent layer. Next, on the upper surface of the phosphorescent layer, (a) 1.5 parts of 7-[2-ethoxy-4-(N-ethyl-N-phenylamino)phenyl]-7-(1-ethyl-2-methyl-1H-indole-3-yl)fl[3,4-b]pyridine-5(7H)-one as component (b), 5 parts of 4,4′-(2-ethylhexylidene)bisphenol and 2 parts of 4,4′-(1-phenylethylidene)bisphenol as component (c) 50 parts of neopentyl stearate as component A reversible thermochromic oil-based spray paint was obtained by mixing and stirring 5 parts of a reversible thermochromic microcapsule pigment (complete decolorization temperature 30°C, complete color development temperature 15°C, blue-colorless), which is a reversible thermochromic composition coated with an epoxy resin film, 20 parts of an acrylic resin xylene solution (50% solids), 50 parts of an acrylic resin / xylene solution, 60 parts of xylene, and 10 parts of an isocyanate-based curing agent, and then painting with this paint and drying to form a reversible thermochromic layer, thereby obtaining a phosphorescent reversible thermochromic laminate. Furthermore, the absorbance at the minimum absorption wavelength (A) between 400 nm and 700 nm during the color development of the reversible thermochromic layer was 0.49 (476 nm), the absorbance at the maximum absorption wavelength (B) was 1.57 (601 nm), and the B / A ratio was 3.2.

[0044] The aforementioned phosphorescent, reversible thermochromic laminate exhibited a blue color in its reversible thermochromic layer at temperatures below 15°C in bright light. At temperatures above 30°C, it changed from blue to colorless, becoming white due to the support material, and maintained this state at room temperature. Next, when the temperature was reduced to below 15°C again, it changed back to blue, and maintained this state at room temperature. Next, when the laminate, which exhibits a blue color in bright light, was irradiated with UV light, and then the reversible thermochromic layer was partially decolorized with a dark color, the green emission from the phosphorescent pigment of the phosphorescent layer could be clearly seen in the areas where the reversible thermochromic layer had been decolorized. Furthermore, when a laminate that exhibits blue color in bright light is irradiated with UV light, the reversible thermochromic layer is partially decolorized. Subsequently, when the laminate is viewed in the dark, the green emission from the phosphorescent pigment of the phosphorescent layer can be clearly seen in the areas where the reversible thermochromic layer has been decolorized.

[0045] Example 3 Fabrication of phosphorescent, reversible thermochromic laminates A phosphorescent printing ink was obtained consisting of 20 parts of green phosphorescent pigment (product name: N Luminova G-300M, manufactured by Nemoto Special Chemicals Co., Ltd.) as the phosphorescent material, 50 parts of acrylic resin emulsion (solid content 45%), 1 part of viscosity modifier, 0.2 parts of defoamer, and 28.8 parts of water. Using the aforementioned phosphorescent printing ink, screen printing was performed on the surface of a white synthetic paper support, and the surface was dried to form a phosphorescent layer. Next, screen printing was performed on the upper surface of the phosphorescent layer using a reversible thermochromic microcapsule pigment (color change temperature 30°C, red-to-colorless) coated with an epoxy resin film, the pigment being a reversible thermochromic composition consisting of (a) 3 parts 6'-(cyclohexylamino)-2'-methyl-spiro[isobenzofuran-1(3H),9'-xanthene]-3-one and 2 parts 3-diethylamino-7,8-benzofluorane, (b) 6 parts 4,4'-(2-methylpropane-1,1-diyl)diphenol and (c) n-hexadecanol and stearyl caprate, 50 parts acrylic resin emulsion (solids content 45%), 1 part viscosity modifier, 0.2 parts defoamer, and 18.8 parts water. The ink was then dried to form a reversible thermochromic layer and obtain a phosphorescent reversible thermochromic laminate. Furthermore, the absorbance at the minimum absorption wavelength (A) between 400 nm and 700 nm during the color development of the reversible thermochromic layer was 0.86 (427 nm), the absorbance at the maximum absorption wavelength (B) was 1.25 (515 nm), and the B / A ratio was 1.5.

[0046] In the aforementioned phosphorescent, reversible thermochromic laminate, the reversible thermochromic layer exhibits a red color in the room temperature (25°C) in bright light. Above 30°C, it changes from red to colorless, becoming white due to the support material, and then changes back to red when left at room temperature. Next, when the laminate, which exhibits a red color in bright light, was irradiated with UV light, and then the reversible thermochromic layer was partially decolorized with a dark color, green luminescence from the phosphorescent pigment of the phosphorescent layer could be observed in the areas where the reversible thermochromic layer had been decolorized. Furthermore, when a laminate that exhibits redness in bright light is irradiated with UV light, the reversible thermochromic layer is partially decolorized. Subsequently, when the laminate is viewed in the dark, the green emission from the phosphorescent pigment of the phosphorescent layer can be seen in the areas where the reversible thermochromic layer has been decolorized.

[0047] Example 4 Fabrication of phosphorescent, reversible thermochromic laminates A phosphorescent oil-based spray paint was obtained by mixing 20 parts of green phosphorescent pigment (product name: N Luminova G-300M, manufactured by Nemoto Special Chemicals Co., Ltd.), 50 parts of acrylic resin / xylene solution, 60 parts of xylene, and 10 parts of isocyanate-based curing agent as phosphorescent materials. The aforementioned phosphorescent oil-based spray paint was spray-coated onto the surface of a white ABS resin support, and then dried to form a phosphorescent layer. Next, on the upper surface of the phosphorescent layer, a reversible thermochromic solution consisting of (a) 1.5 parts of 7-[2-ethoxy-4-(N-ethyl-N-phenylamino)phenyl]-7-(1-ethyl-2-methyl-1H-indole-3-yl)fl[3,4-b]pyridine-5(7H)-one, (b) 5 parts of 4,4′-(2-ethylhexylidene)bisphenol and 2 parts of 4,4′-(1-phenylethylidene)bisphenol, and (c) 50 parts of neopentyl stearate is added. A reversible thermochromic oil-based spray paint was prepared by mixing and stirring 5 parts of a reversible thermochromic microcapsule pigment (complete decolorization temperature 30°C, complete color development temperature 15°C, blue-colorless) coated with an epoxy resin film, 0.3 parts of blue pigment, 0.2 parts of yellow pigment, 20 parts of acrylic resin xylene solution (50% solids), 50 parts of acrylic resin / xylene solution, 60 parts of xylene, and 10 parts of isocyanate-based curing agent. The paint was then applied and dried to form a reversible thermochromic layer, obtaining a phosphorescent reversible thermochromic laminate. Furthermore, the absorbance at the minimum absorption wavelength (A) between 400 nm and 700 nm during the color development of the reversible thermochromic layer was 0.57 (485 nm), the absorbance at the maximum absorption wavelength (B) was 1.47 (612 nm), and the B / A ratio was 2.6.

[0048] The aforementioned phosphorescent, reversible thermochromic laminate exhibited a blue color in its reversible thermochromic layer at temperatures below 15°C in bright light. At temperatures above 30°C, it changed from blue to green, maintaining this state at room temperature. Subsequently, when the temperature was reduced back below 15°C, it changed back to blue, maintaining this state at room temperature. Next, when a laminate that exhibits blue color in bright light was irradiated with UV light, and then the reversible thermochromic layer was partially discolored with a dark color, the green emission from the phosphorescent pigment of the phosphorescent layer could be clearly seen in the areas where the reversible thermochromic layer had discolored. Furthermore, when a laminate that appears blue in bright light is irradiated with UV light, the reversible thermochromic layer partially changes color, and then when the laminate is viewed in the dark, the green emission from the phosphorescent pigment of the phosphorescent layer can be clearly seen in the areas where the reversible thermochromic layer has changed color.

[0049] Example 5 Fabrication of phosphorescent, reversible thermochromic laminates A phosphorescent oil-based spray paint was obtained by mixing 20 parts of green phosphorescent pigment (product name: N Luminova G-300M, manufactured by Nemoto Special Chemicals Co., Ltd.), 50 parts of acrylic resin / xylene solution, 60 parts of xylene, and 10 parts of isocyanate-based curing agent as phosphorescent materials. The aforementioned phosphorescent oil-based spray paint was spray-coated onto the surface of a white ABS resin support, and then dried to form a phosphorescent layer. Next, on the upper surface of the phosphorescent layer, a solution consisting of (a) 1.5 parts of 7-[2-ethoxy-4-(N-ethyl-N-phenylamino)phenyl]-7-(1-ethyl-2-methyl-1H-indole-3-yl)fl[3,4-b]pyridine-5(7H)-one, (b) 5 parts of 4,4′-(2-ethylhexylidene)bisphenol and 2 parts of 4,4′-(1-phenylethylidene)bisphenol, and (c) 50 parts of neopentyl stearate is added. A reversible thermochromic oil-based spray paint was prepared by mixing and stirring 5 parts of a reversible thermochromic microcapsule pigment (complete decolorization temperature 30°C, complete color development temperature 15°C, blue-colorless) coated with an epoxy resin film, 1 part of a pink pigment, 20 parts of an acrylic resin xylene solution (50% solids), 50 parts of an acrylic resin / xylene solution, 60 parts of xylene, and 10 parts of an isocyanate-based curing agent. The paint was then applied and dried to form a reversible thermochromic layer, obtaining a phosphorescent reversible thermochromic laminate. Furthermore, the absorbance at the minimum absorption wavelength (A) between 400 nm and 700 nm during the color development of the reversible thermochromic layer was 0.52 (473 nm), and the absorbance at the maximum absorption wavelength (B) was 1.55 (609 nm), resulting in a B / A ratio of 3.0.

[0050] The aforementioned phosphorescent, reversible thermochromic laminate exhibited a blue color in its reversible thermochromic layer at temperatures below 15°C in bright light. At temperatures above 30°C, it changed from blue to pink, maintaining this state at room temperature. Subsequently, when the temperature was reduced back below 15°C, it changed back to blue, maintaining this state at room temperature. Next, when a laminate that exhibits blue color in bright light was irradiated with UV light, and then the reversible thermochromic layer was partially decolorized with a dark color, the green emission from the phosphorescent pigment of the phosphorescent layer could be clearly seen in the areas where the reversible thermochromic layer had changed color. Furthermore, when a laminate that appears blue in bright light is irradiated with UV light, the reversible thermochromic layer partially changes color, and then when the laminate is viewed in the dark, the green emission from the phosphorescent pigment of the phosphorescent layer can be clearly seen in the areas where the reversible thermochromic layer has changed color.

[0051] Example 6 Fabrication of phosphorescent, reversible thermochromic laminates A phosphorescent oil-based spray paint was obtained by mixing 20 parts of green phosphorescent pigment (product name: N Luminova G-300M, manufactured by Nemoto Special Chemicals Co., Ltd.), 50 parts of acrylic resin / xylene solution, 60 parts of xylene, and 10 parts of isocyanate-based curing agent as phosphorescent materials. The aforementioned phosphorescent oil-based spray paint was spray-coated onto the surface of a white ABS resin support, and then dried to form a phosphorescent layer. Next, on the upper surface of the phosphorescent layer, the following components are added: (a) 1.5 parts of 7-[2-ethoxy-4-(N-ethyl-N-phenylamino)phenyl]-7-(1-ethyl-2-methyl-1H-indole-3-yl)fl[3,4-b]pyridine-5(7H)-one as component (a), 5 parts of 4,4′-(2-ethylhexylidene)bisphenol and 2 parts of 4,4′-(1-phenylethylidene)bisphenol as component (b), and 50 parts of neopentyl stearate as component (c). A reversible thermochromic oil-based spray paint was prepared by mixing and stirring 5 parts of a reversible thermochromic microcapsule pigment (complete decolorization temperature 30°C, complete color development temperature 15°C, blue-colorless), 2 parts of yellow pigment, 20 parts of acrylic resin xylene solution (50% solids), 50 parts of acrylic resin / xylene solution, 60 parts of xylene, and 10 parts of isocyanate-based curing agent, and then painting with this paint and drying to form a reversible thermochromic layer, thereby obtaining a phosphorescent reversible thermochromic laminate. Furthermore, the absorbance at the minimum absorption wavelength (A) between 400 nm and 700 nm during the color development of the reversible thermochromic layer was 0.52 (485 nm), the absorbance at the maximum absorption wavelength (B) was 1.43 (601 nm), and the B / A ratio was 2.8.

[0052] The phosphorescent, reversible thermochromic laminate exhibited a green reversible thermochromic layer in bright light at temperatures below 15°C, changed from green to yellow at temperatures above 30°C, and maintained this state at room temperature. Next, when the temperature was reduced back to below 15°C, it changed back to green and maintained this state at room temperature. Next, when a laminate that exhibits green in bright light was irradiated with UV light, and then the reversible thermochromic layer was partially discolored with a dark color, the green emission from the phosphorescent pigment of the phosphorescent layer could be clearly seen in the areas where the reversible thermochromic layer had discolored. Furthermore, when a laminate that appears green in bright light is irradiated with UV light, the reversible thermochromic layer partially changes color, and then when the laminate is viewed in the dark, the green light emitted by the phosphorescent pigment in the phosphorescent layer can be clearly seen in the areas where the reversible thermochromic layer has changed color.

[0053] Example 7 Fabrication of phosphorescent, reversible thermochromic laminates A phosphorescent printing ink was obtained consisting of 20 parts of green phosphorescent pigment (product name: N Luminova G-300M, manufactured by Nemoto Special Chemicals Co., Ltd.) as the phosphorescent material, 50 parts of acrylic resin emulsion (solid content 45%), 1 part of viscosity modifier, 0.2 parts of defoamer, and 28.8 parts of water. Using the aforementioned phosphorescent printing ink, screen printing was performed on the surface of a white synthetic paper support, and the surface was dried to form a phosphorescent layer. Next, on the upper surface of the phosphorescent layer, 15 parts of a reversible thermochromic microcapsule pigment (complete decolorization temperature 30°C, complete color development temperature 15°C, blue-colorless) is coated with an epoxy resin film, comprising (a) 1.5 parts of 7-[2-ethoxy-4-(N-ethyl-N-phenylamino)phenyl]-7-(1-ethyl-2-methyl-1H-indole-3-yl)fl[3,4-b]pyridine-5(7H)-one as component (a), 5 parts of 4,4′-(2-ethylhexylidene)bisphenol and 2 parts of 4,4′-(1-phenylethylidene)bisphenol as component (b), and 50 parts of neopentyl stearate as component (c), and (a) 15 parts of a reversible thermochromic microcapsule pigment (complete decolorization temperature 30°C, complete color development temperature 15°C, blue-colorless) as component (a), and 2-(dibutylamino)-8-(dipentylamino)-4-methylspiro[5H-[1 A reversible thermochromic printing ink consisting of 1 part of benzopyrano[2,3-d]pyrimidine-5,1′(3H′)-isobenzofuran]-3′-one, (b) 5 parts of 4,4′-(2-ethylhexylidene)bisphenol and 2 parts of 4,4′-(1-phenylethylidene)bisphenol as component (c), and 50 parts of neopentyl stearate as component (c) was coated with an epoxy resin film to form a reversible thermochromic microcapsule pigment (complete decolorization temperature 30°C, complete color development temperature 15°C, pink-colorless), 50 parts of acrylic resin emulsion (solids content 45%), 1 part of viscosity modifier, 0.2 parts of defoamer, and 18.8 parts of water was used for screen printing, and the ink was dried to form a reversible thermochromic layer, thereby obtaining a phosphorescent reversible thermochromic laminate. Furthermore, the absorbance at the minimum absorption wavelength (A) between 400 nm and 700 nm during the color development of the reversible thermochromic layer was 0.57 (445 nm), the absorbance at the maximum absorption wavelength (B) was 1.27 (570 nm), and the B / A ratio was 2.2.

[0054] The aforementioned phosphorescent, reversible thermochromic laminate exhibited a purple color in its reversible thermochromic layer at temperatures below 15°C in bright light. At temperatures above 30°C, it changed from purple to colorless, becoming white due to the support material, and maintained this state at room temperature. Next, when the temperature was reduced to below 15°C again, it changed back to purple, and maintained this state at room temperature. Next, when the laminate, which exhibits a blue color in bright light, was irradiated with UV light, and then the reversible thermochromic layer was partially decolorized with a dark color, the green emission from the phosphorescent pigment of the phosphorescent layer could be clearly seen in the areas where the reversible thermochromic layer had been decolorized. Furthermore, when a laminate that exhibits blue color in bright light is irradiated with UV light, the reversible thermochromic layer is partially decolorized. Subsequently, when the laminate is viewed in the dark, the green emission from the phosphorescent pigment of the phosphorescent layer can be clearly seen in the areas where the reversible thermochromic layer has been decolorized.

[0055] Comparative Example 1 Fabrication of phosphorescent, reversible thermochromic laminates A phosphorescent oil-based spray paint was obtained by mixing 20 parts of green phosphorescent pigment (product name: N Luminova G-300M, manufactured by Nemoto Special Chemicals Co., Ltd.), 50 parts of acrylic resin / xylene solution, 60 parts of xylene, and 10 parts of isocyanate-based curing agent as phosphorescent materials. The aforementioned phosphorescent oil-based spray paint was spray-coated onto the surface of a white ABS resin support, and then dried to form a phosphorescent layer. Next, the upper surface of the phosphorescent layer was coated with a reversible thermochromic oil-based spray paint obtained by mixing and stirring a reversible thermochromic composition consisting of 3 parts 2-anilino-3-methyl-6-dibutylaminofluorane, 6 parts 4,4′-(2-methyl-propylene)bisphenol, and 50 parts neopentyl stearate, coated with an epoxy resin film, and containing 5 parts of a reversible thermochromic microcapsule pigment (complete decolorization temperature 32°C, complete color development temperature 15°C, black-colorless), 20 parts of acrylic resin xylene solution (50% solids), 50 parts of acrylic resin / xylene solution, 60 parts of xylene, and 10 parts of an isocyanate-based curing agent. The paint was then dried to form a reversible thermochromic layer, obtaining a phosphorescent reversible thermochromic laminate. Furthermore, the absorbance at the minimum absorption wavelength (A) between 400 nm and 700 nm during the color development of the reversible thermochromic layer was 1.23 (400 nm), the absorbance at the maximum absorption wavelength (B) was 1.35 (576 nm), and the B / A ratio was 1.1.

[0056] The phosphorescent, reversible thermochromic laminate exhibited a black reversible thermochromic layer in bright light at temperatures below 15°C. At temperatures above 32°C, it changed from black to colorless, becoming white due to the support material, and this state was maintained at room temperature. Next, when the temperature was reduced to below 15°C again, it changed back to black, and this state was maintained at room temperature. Next, when a laminate that appears black in bright light was illuminated with UV light, and the reversible thermochromic layer was partially decolorized in a dark color, the green emission from the phosphorescent pigment of the phosphorescent layer could not be seen in the areas where the reversible thermochromic layer had been decolorized.

[0057] Comparative Example 2 Fabrication of phosphorescent, reversible thermochromic laminates A phosphorescent printing ink was obtained consisting of 20 parts of green phosphorescent pigment (product name: N Luminova G-300M, manufactured by Nemoto Special Chemicals Co., Ltd.) as the phosphorescent material, 1 part of viscosity modifier, 0.2 parts of defoamer, and 28.8 parts of water. Using the aforementioned phosphorescent printing ink, screen printing was performed on the surface of a white synthetic paper support, and the surface was dried to form a phosphorescent layer. Next, screen printing was performed on the upper surface of the phosphorescent layer using a reversible thermochromic printing ink consisting of 30 parts of a reversible thermochromic microcapsule pigment (complete decolorization temperature 32°C, complete color development temperature 15°C, black-colorless), 50 parts of an acrylic resin emulsion (solid content 45%), 1 part of a viscosity modifier, 0.2 parts of an antifoaming agent, and 18.8 parts of water, which was coated with an epoxy resin film containing a reversible thermochromic composition consisting of 3 parts of 2-anilino-3-methyl-6-dibutylaminofluorane, 6 parts of 4,4′-(2-methyl-propylene)bisphenol, and 50 parts of neopentyl stearate, 50 parts of an acrylic resin emulsion (solid content 45%), 1 part of a viscosity modifier, 0.2 parts of an antifoaming agent, and 18.8 parts of water. The ink was then dried to form a reversible thermochromic layer, obtaining a phosphorescent reversible thermochromic laminate. Furthermore, the absorbance at the minimum absorption wavelength (A) between 400 nm and 700 nm during the color development of the reversible thermochromic layer was 0.94 (505 nm), the absorbance at the maximum absorption wavelength (B) was 1.2 (581 nm), and the B / A ratio was 1.3.

[0058] The phosphorescent, reversible thermochromic laminate exhibited a black reversible thermochromic layer in bright light at temperatures below 15°C. At temperatures above 32°C, it changed from black to colorless, becoming white due to the support material, and this state was maintained at room temperature. Next, when the temperature was reduced to below 15°C again, it changed back to black, and this state was maintained at room temperature. Next, when a laminate that appears black in bright light was illuminated with UV light, and the reversible thermochromic layer was partially decolorized in a dark color, the green emission from the phosphorescent pigment of the phosphorescent layer could not be seen in the areas where the reversible thermochromic layer had been decolorized.

[0059] Application Example 1 Making a phosphorescent, reversible, thermochromic miniature car The phosphorescent oil-based spray paint prepared in Example 1 was spray-painted onto the surface of a miniature car and allowed to dry to form a phosphorescent layer. Next, the upper surface of the phosphorescent layer was painted with the reversible thermochromic oil-based spray paint prepared in Example 1, and dried to form a reversible thermochromic layer, thereby obtaining a phosphorescent, reversible thermochromic miniature car.

[0060] The aforementioned phosphorescent, reversible, thermochromic miniature car was purple in bright light below 15°C, changed from purple to blue above 30°C, and maintained this state at room temperature. Next, when the temperature was reduced to below 15°C again, it changed back to purple and maintained this state at room temperature. Next, after shining sunlight on a purple miniature car in a bright place, the reversible heat-changeable layer on the hood was partially discolored with a dark color. The green light emitted by the phosphorescent pigment in the phosphorescent layer was clearly visible in the areas where the reversible heat-changeable layer had discolored. Furthermore, after shining sunlight on a purple miniature car in a bright place, the reversible color-changing layer on the hood changed color. Then, when the miniature car was viewed in a dark place, the green luminescence from the phosphorescent pigment in the phosphorescent layer on the hood was clearly visible.

[0061] Application Example 2 Making a phosphorescent, reversible, thermochromic miniature car Using the phosphorescent oil-based spray paint prepared in Example 2, a white miniature car surface was spray-painted and dried to form a phosphorescent layer. Next, the upper surface of the phosphorescent layer was painted with the reversible thermochromic oil-based spray paint prepared in Example 2, and dried to form a reversible thermochromic layer, thereby obtaining a phosphorescent, reversible thermochromic miniature car.

[0062] The aforementioned phosphorescent, reversible, thermochromic miniature car was blue in bright light at temperatures below 15°C, changed from blue to white at temperatures above 30°C, and maintained this state at room temperature. Next, when the temperature was reduced to below 15°C again, it changed back to blue and maintained this state at room temperature. Next, after irradiating a blue miniature car with UV light in a bright place, the reversible heat-changeable layer on the hood was decolorized with a dark color, and the green luminescence from the phosphorescent pigment in the phosphorescent layer was clearly visible. Furthermore, after irradiating a miniature car with UV light in a bright place, the reversible color-changing layer on the hood was decolorized. Then, when the miniature car was viewed in a dark place, the green luminescence from the phosphorescent pigment in the phosphorescent layer on the hood was clearly visible. [Explanation of Symbols]

[0063] t1 Complete color development temperature of a heat-decolorizing, reversible thermochromic composition t2: Color development start temperature of a heat-decolorizing, reversible thermochromic composition t3 Decolorization start temperature of reversible thermochromic composition that decolorizes by heating Complete decolorization temperature of t4 heat-decolorizing type reversible thermochromic composition Complete decolorization temperature of T1 heat-activated, reversible thermochromic composition Decolorization onset temperature of T2 heat-activated reversible thermochromic composition T3 Heat-Developing Reversible Thermochromic Composition: Color Development Initiation Temperature Complete color development temperature of T4 heat-activated reversible thermochromic composition ΔH Hysteresis width 1. Luminescent, reversible thermochromic laminate 2 Support 3. Luminous layer 4. Reversible thermal discoloration layer

Claims

1. A phosphorescent reversible thermochromic laminate comprising a phosphorescent layer containing a phosphorescent material, and a reversible thermochromic layer containing a reversible thermochromic material that changes color from colored to colorless, wherein the reversible thermochromic layer develops color in any color except black.

2. The phosphorescent reversible thermochromic laminate according to claim 1, wherein the absorbance of the minimum absorption wavelength (A) at a wavelength of 400 nm to 700 nm during the color development of the reversible thermochromic layer is in the range of 400 nm to less than 510 nm, the absorbance of the maximum absorption wavelength (B) is in the range of more than 510 nm and less than or equal to 700 nm, and B / A is 1.4 or more.

3. The phosphorescent reversible thermochromic laminate according to claim 2, wherein the absorbance of the absorption maximum wavelength (B) at a wavelength of 400 nm to 700 nm during the color development of the reversible thermochromic layer is in the range of over 520 and under 700 nm.

4. The reversible thermochromic layer is a layer in which microcapsule pigments containing a reversible thermochromic composition comprising (a) an electron-donating color-changing organic compound, (b) an electron-accepting compound, and (c) a reaction medium that reversibly causes an electron transfer reaction by components (a) and (b) in a specific temperature range are dispersed and fixed in a binder, and the phosphorescent layer is a layer in which phosphorescent pigments are dispersed and fixed in a binder, according to any one of claims 1 to 3.

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