Metallic luster thermal-discoloring toy

Abstract

To provide a metallic luster thermal-discoloring toy capable of visually recognizing a metallic luster color of high brightness as a metallic luster color of high brightness of different colors by moving a point of view and visually recognizing various phase changes together with color changes due to a change of temperature.SOLUTION: A metallic luster thermal-discoloring toy 1 is composed of a reversibly thermal-discoloring layer 3 and a metallic luster layer 4 containing a brilliant pigment and a coloring pigment. The brilliant pigment is a brilliant pigment covering the surface of a flat aluminum with iron oxide or a brilliant pigment covering the surface of a flat silicon dioxide with iron oxide, a mass of an iron element in the brilliant pigment is 5 to 400 pts.mass relative to an aluminum element or silicon element 100 pts.mass.SELECTED DRAWING: Figure 5

Description

[Technical field]

[0001] The present invention relates to a thermochromic toy with metallic luster. More specifically, the present invention relates to a thermochromic toy with metallic luster that changes its brilliant metallic luster color depending on the viewing angle and also changes color depending on the temperature, allowing the user to see the various aspects of the combination of these two. [Background technology]

[0002] Conventionally, proposals by the present applicant regarding thermochromic toys with metallic luster have already been disclosed (see, for example, Patent Documents 1 to 4). The above proposal is a toy in which, when the viewpoint is moved while the metallic luster color is visible, the metallic luster changes to a different color, and the toy also shows a more diverse range of appearance changes due to the color change of the reversible thermochromic composition. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2003-127293 A [Patent Document 2] JP 2004-230580 A [Patent Document 3] JP 2008-207510 A [Patent Document 4] JP 2012-166440 A Summary of the Invention [Problem to be solved by the invention]

[0004] The inventors have further explored the visual effects of this type of metallic luster thermochromic toy, and intend to provide a metallic luster thermochromic toy that can present different, highly luminous metallic luster colors by moving the viewpoint while a highly luminous metallic luster color is being viewed, and that can also present a wider variety of color changes due to the discoloration of the reversible thermochromic composition. [Means for solving the problem]

[0005] The present invention relates to a metallic luster thermochromic toy comprising a reversible thermochromic layer including a reversible thermochromic composition comprising an electron-donating organic color-forming compound, an electron-accepting compound, and an organic compound medium that reversibly induces a color-changing reaction between the two, and a metallic luster layer including a glittering pigment and a coloring pigment, the glittering pigment being a glittering pigment in which the surface of flat aluminum is coated with iron oxide, or a glittering pigment in which the surface of flat silicon dioxide is coated with iron oxide, and the mass of the iron element in the glittering pigment is 5 to 400 parts by mass per 100 parts by mass of the aluminum element or the silicon element.Further requirements include that the coloring pigment includes a blue pigment, that a reflective layer including silicon dioxide is provided between the aluminum and iron oxide of the glittering pigment, and that the mass of the silicon element in the glittering pigment is 5 to 50 parts by mass per 100 parts by mass of the aluminum element. Effect of the Invention

[0006] The present invention can provide a unique metallic luster thermochromic toy in which a highly luminous metallic luster color can be visually recognized as a highly luminous metallic luster color of a different color by moving the viewpoint, and in which a variety of changes in appearance can be visually recognized due to color changes caused by temperature changes. [Brief description of the drawings]

[0007] [Figure 1] 1 is a graph illustrating hysteresis characteristics in a color density-temperature curve of a heat-discolorable, reversible thermochromic composition. [Diagram 2] 1 is a graph illustrating the hysteresis characteristics in a color density-temperature curve of a reversible thermochromic composition having color memory properties. [Diagram 3] 1 is a graph illustrating hysteresis characteristics in a color density-temperature curve of a reversible thermochromic composition that develops color upon heating. [Figure 4] 1 is a longitudinal sectional view of an embodiment of a metallic luster thermochromic toy according to the present invention; [Diagram 5]FIG. 13 is a longitudinal sectional view illustrating another embodiment of a metallic luster thermochromic toy according to the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] The inventors have discovered that by laminating a reversible thermochromic layer containing a reversible thermochromic composition and a metallic luster layer containing a specific photoluminescent pigment and a coloring pigment, it is possible to obtain a metallic luster thermochromic toy that not only changes color with temperature of the reversible thermochromic composition, but also has a highly luminous metallic luster that changes color depending on the viewing angle, and that by linking these color changes, can produce a variety of appearance changes.

[0009] The reversible thermochromic composition may be a thermally decolorizable (decolorizing by heating and coloring by cooling) reversible thermochromic composition containing at least three essential components: (i) an electron-donating color-forming organic compound, (ii) an electron-accepting compound, and (iii) a reaction medium that determines the temperature at which the color-forming reaction between the two occurs. The reversible thermochromic composition may be a reversible thermochromic composition of a heat-discoloring type (discolored by heating and colored by cooling) having a relatively small hysteresis width (ΔH) of 1 to 7° C., which is described in JP-B-51-44706, JP-B-51-44707, JP-B-1-29398, etc. and which changes color around a certain temperature (discoloration point), exhibits a discolored state in a temperature range above the high-temperature discoloration point, and exhibits a colored state in a temperature range below the low-temperature discoloration point, and of the two states, only one specific state exists in the room temperature range, and the other state is maintained while the heat or cold required to express that state is applied, but returns to the state exhibited in the room temperature range when the application of the heat or cold is removed (see FIG. 1).

[0010] In addition, hysteresis width (ΔH) described in JP-B-4-17154, JP-A-7-179777, JP-A-7-33997, JP-A-8-39936, JP-A-2005-1369, JP-A-2008-280523, etc. shows a relatively large characteristic of 8°C to 80°C, that is, the shape of the curve plotting the change in color density due to temperature change is as follows: A reversible thermochromic composition of the heat-discoloring type (discolors when heated and develops color when cooled) that has color memory in a specific temperature range [temperature range between t2 and t3 (temperature range where two phases are substantially maintained)], in which the color changes along a route that is significantly different when the temperature is lowered from a higher temperature side than the discoloration temperature range and the colored state is in a low temperature range below the complete color-developing temperature (t1) or in a decolored state is in a high temperature range above the complete decolorization temperature (t4) (see Figure 2).

[0011] The hysteresis characteristic in the color density-temperature curve of the reversible thermochromic composition will now be described. In Fig. 2, the vertical axis represents color density, and the horizontal axis represents temperature. The change in color density due to temperature change progresses along the arrow. Here, A is a point indicating the density at temperature t4 (hereinafter referred to as complete decolorization temperature) where a completely decolorized state is reached, B is a point indicating the density at temperature t3 (hereinafter referred to as decolorization onset temperature) where decolorization begins, C is a point indicating the density at temperature t2 (hereinafter referred to as color development onset temperature) where color development begins, and D is a point indicating the density at temperature t1 (hereinafter referred to as complete color development temperature) where a completely colored state is reached. The discoloration temperature range is as above t The temperature range between t1 and t4, in which the material can exhibit either a colored state or a decolored state, and the temperature range between t2 and t3, which is the region in which the difference in color density is large, is the actual discoloration temperature range. The length of the line segment EF is a measure of the contrast of the discoloration, and the length of the line segment HG passing through the midpoint of the line segment EF is a temperature range indicating the degree of hysteresis (hereinafter referred to as hysteresis range ΔH). If this ΔH value is small, only one of the two states before and after the discoloration can exist in the room temperature range. If the ΔH value is large, it is easy to maintain each state before and after the discoloration.

[0012] Components (a), (b) and (c) contained in the reversible thermochromic composition will be specifically described below. The component (A), ie, the electron-donating organic color-forming compound, is a component that determines the color, and is a compound that develops color by donating electrons to the component (B), which is a color developer. Examples of the electron-donating color-forming organic compound include phthalide compounds, fluoran compounds, styrinquinoline compounds, diazarhodamine lactone compounds, pyridine compounds, quinazoline compounds, and bisquinazoline compounds. Of these, phthalide compounds, fluoran compounds, styrinquinoline compounds, and diazarhodamine lactone compounds are preferred. Examples of the phthalide compound include diphenylmethane phthalide compounds, phenylindolyl phthalide compounds, indolyl phthalide compounds, diphenylmethane azaphthalide compounds, phenylindolyl azaphthalide compounds, and derivatives thereof. Among these, phenylindolyl azaphthalide compounds and derivatives thereof are preferred. Examples of these compounds are given below. 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(1-n-butyl-2-methylindol-3-yl)phthalide, 3,3-bis(2-ethoxy-4-diethylaminophenyl)-4-azaphthalide, 3-(2-ethoxy-4-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-Np-tolylamino)fluoran, 3-chloro-6-cyclohexylaminofluoran, 2-methyl-6-cyclohexylaminofluoran, 2-(2-chloroamino)-6-dibutylaminofluoran, 2-(2-chloroanilino)-6-di-n-butylaminofluoran, 2-(3-trifluoromethylanilino)-6-diethylaminofluoran, 2-(3-trifluoromethylanilino)-6-dipentylaminofluoran, 2-(dibenzylamino)-6-diethylaminofluoran, 2-(N-methylanilino)-6-(N-ethyl-Np-tolylamino)fluoran, 1,3-dimethyl-6-diethylaminofluoran, 2-chloro-3-methyl-6-diethylaminofluoran, 2-anilino-3-methyl-6-diethylaminofluoran, 2-anilino-3-methoxy-6-diethylaminofluoran, 2-anilino-3-methyl-6-di-n-butylaminofluoran, 2-anilino-3-methoxy-6-di-n-butylaminofluoran, 2-xylidino-3-methyl-6-diethylaminofluoran, 2-anilino-3-methyl-6-(N-ethyl-Np-tolylamino)fluoran, 1,2-Benz-6-diethylaminofluoran, 1,2-Benz-6-(N-ethyl-N-isobutylamino)fluoran, 1,2-Benz-6-(N-ethyl-N-isoamylamino)fluoran, 2-(3-methoxy-4-dodecoxystyryl)quinoline, Spiro[5H-(1)benzopyrano(2,3-d)pyrimidin-5,1′(3′H)isobenzofuran]-3′-one, 2-(diethylamino)-8-(diethylamino)-4-methyl, Spiro[5H-(1)benzopyrano(2,3-d)pyrimidin-5,1′(3′H)isobenzofuran]-3′-one, 2-(di-n-butylamino)-8-(di-n-butylamino)-4-methyl, Spiro[5H-(1)benzopyrano(2,3-d)pyrimidin-5,1′(3′H)isobenzofuran]-3′-one, 2-(di-n-butylamino)-8-(diethylamino)-4-methyl, Spiro[5H-(1)benzopyrano(2,3-d)pyrimidin-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)pyrimidin-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-indol-3-yl)-1(3H)-isobenzofuranone, 4,5,6,7-tetrachloro-3-[4-(diethylamino)-2-ethoxyphenyl]-3-(1-ethyl-2-methyl-1H-indol-3-yl)-1(3H)-isobenzofuranone, 4,5,6,7-tetrachloro-3-[4-(diethylamino)-2-ethoxyphenyl]-3-(1-pentyl-2-methyl-1H-indol-3-yl)-1(3H)-isobenzofuranone, 4,5,6,7-tetrachloro-3-[4-(diethylamino)-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, 2,6-bis(2′-ethyloxyphenyl)-4-(4′-dimethylaminophenyl)pyridine, 2,6-bis(2′,4′-diethyloxyphenyl)-4-(4′-dimethylaminophenyl)pyridine, 2-(4′-dimethylaminophenyl)-4-methoxy-quinazoline, 4,4'-(Ethylenedioxy)-bis[2-(4-diethylaminophenyl)quinazoline] etc. can be mentioned. In addition to the above-mentioned compounds having a substituent on the phenyl group forming the xanthene ring, the fluorans may also be compounds that have a substituent on the phenyl group forming the xanthene ring and also have a substituent (e.g., an alkyl group such as a methyl group, or a halogen atom such as a chloro group) on the phenyl group forming the lactone ring, and exhibit a blue or black color.

[0013] The component (b), ie, the electron accepting compound, is a compound that accepts electrons from the component (a) and functions as a developer for the component (a). The electron-accepting compound may be a compound selected from a group of compounds having an active proton and derivatives thereof, a group of pseudo-acidic compounds (a group of compounds which are not acids but act as an acid in the composition to cause component (A) to develop color), a group of compounds having an electron vacancy, and the like. Among these, a compound selected from a group of compounds having an active proton is preferred. Examples of compounds having an active proton and derivatives thereof include compounds having a phenolic hydroxyl group and metal salts thereof, carboxylic acids and metal salts thereof, preferably aromatic carboxylic acids, aliphatic carboxylic acids having 2 to 5 carbon atoms and metal salts thereof, acidic phosphate esters and metal salts thereof, as well as azole compounds and derivatives thereof, and 1,2,3-triazole and derivatives thereof. Among these, compounds having a phenolic hydroxyl group are preferred because they can exhibit effective thermochromic properties. The compounds having a phenolic hydroxyl group include a wide range of compounds from monophenol compounds to polyphenol compounds, and further include bis-type and tris-type phenols and phenol-aldehyde condensation resins. Among the compounds having a phenolic hydroxyl group, those having at least two benzene rings are preferred. In addition, these compounds may have a substituent, and examples of the substituent include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, a carboxyl group and its ester or amide group, a halogen group, and the like. Examples of the metal contained in the metal salt of the compound having an active proton include sodium, potassium, calcium, zinc, zirconium, aluminum, magnesium, nickel, cobalt, tin, copper, iron, vanadium, titanium, lead, and molybdenum.

[0014] Some specific examples are given below. Phenol, o-cresol, tertiary butyl catechol, 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-dihydroxydiphenyl sulfone, 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)n-butyl ... 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, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1-phenyl-1,1-bi 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, 2,2-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, 3,3-bis(3-methyl-4-hydroxyphenyl)butane, etc. The compound having a phenolic hydroxyl group is capable of exhibiting the most effective thermal discoloration properties, but it may also be a compound 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-triazole and its derivatives.

[0015] The component (iii) of the reaction medium that reversibly induces an electron donor-acceptor reaction by the components (a) and (b) in a specific temperature range will now be described. Examples of the component (iii) include alcohols, esters, ketones, ethers, and acid amides. When component (C) is used for the microencapsulation and secondary processing described below, compounds having a carbon number of 10 or more are preferably used in order to stably retain the component in the capsule, since low molecular weight compounds tend to evaporate outside the capsule when subjected to high heat treatment. As the alcohols, aliphatic monohydric saturated alcohols having 10 or more carbon atoms are effective, and specific examples thereof include decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, heptadecyl alcohol, octadecyl alcohol, eicosyl alcohol, docosyl alcohol, etc.

[0016] As the esters, esters having 10 or more carbon atoms are effective, and examples thereof include esters obtained from any combination of a monovalent carboxylic acid having an aliphatic, alicyclic or aromatic ring and a monohydric alcohol having an aliphatic, alicyclic or aromatic ring, esters obtained from any combination of a polyvalent carboxylic acid having an aliphatic, alicyclic or aromatic ring and a monohydric alcohol having an aliphatic, alicyclic or aromatic ring, esters obtained from any combination of a monovalent carboxylic acid having an aliphatic, alicyclic or aromatic ring and a monohydric alcohol having an aliphatic, alicyclic or aromatic ring, and any combination of a monovalent carboxylic acid having an aliphatic, alicyclic or aromatic ring and a polyhydric alcohol having an aliphatic, alicyclic or aromatic ring. Specific examples of the esters include ethyl caprylate, octyl caprylate, stearyl caprylate, myristyl caprate, docosyl caprate, 2-ethylhexyl laurate, n-decyl laurate, 3-methylbutyl myristate, cetyl myristate, isopropyl palmitate, neopentyl palmitate, nonyl palmitate, cyclohexyl palmitate, n-butyl stearate, 2-methylbutyl stearate, 3,5,5-trimethylhexyl stearate, stearyl stearate, ethyl ... n-Undecyl phosphate, pentadecyl stearate, stearyl stearate, cyclohexylmethyl stearate, isopropyl behenate, hexyl behenate, lauryl behenate, behenyl behenate, cetyl benzoate, stearyl p-tert-butylbenzoate, dimyristyl phthalate, distearyl phthalate, dimyristyl oxalate, dicetyl oxalate, dicetyl malonate, dilauryl succinate, dilauryl glutarate, diundecyl adipate, dilauryl azelate, di-(n-nonyl) sebacate, Examples of such monomers include 1,18-octadecylmethylenedicarboxylate 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, and xylene glycol distearate.

[0017] Also effective are esters of saturated fatty acids and branched fatty alcohols, esters of unsaturated fatty acids or branched or substituted saturated fatty acids and branched fatty alcohols or fatty alcohols having 16 or more carbon atoms, and ester compounds selected from cetyl butyrate, stearyl butyrate, and behenyl butyrate. 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-ethylpropyl 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 of suitable oleic acid esters include ethyl octyl, 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-bromostearinate, isostearyl 2-ketomyristate, 2-ethylhexyl 2-fluoromyristate, cetyl butyrate, stearyl butyrate, and behenyl butyrate.

[0018] Furthermore, in order to change color while exhibiting a large hysteresis characteristic with respect to the color density-temperature curve and to impart color memory depending on temperature change, carboxylic acid ester compounds exhibiting a ΔT value (melting point-cloud point) of 5° C. or more and less than 50° C. as described in JP-B-4-17154 may be mentioned, 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, trimyristin, tristearin, dimyristin, distearin, etc.

[0019] Fatty acid ester compounds obtained from an odd-numbered aliphatic monohydric alcohol having 9 or more carbon atoms and an aliphatic carboxylic acid having an even number of carbon atoms, and fatty acid ester compounds having a total of 17 to 23 carbon atoms obtained from n-pentyl alcohol or n-heptyl alcohol and an even-numbered aliphatic carboxylic acid having 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 Examples of the glyceryl stearate include n-nonyl myristate, 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-undelsyl eicosanoate, n-tridecyl eicosanoate, n-pentadecyl eicosanoate, n-nonyl behenate, n-undecyl behenate, n-tridecyl behenate, and n-pentadecyl behenate.

[0020] As the ketones, aliphatic ketones having a total carbon number of 10 or more are effective, and examples thereof include 2-decanone, 3-decanone, 4-decanone, 2-undecanone, 3-undecanone, 4-undecanone, 5-undecanone, 2-dodecanone, 3-dodecanone, 4-dodecanone, 5-dodecanone, 2-tridecanone, 3-tridecanone, 2-tetradecanone, 2-pentadecanone, 8-pentadecanone, 2-hexadecanone, 3-hexadecanone, 9-heptadecanone, 2-pentadecanone, 2-octadecanone, 2-nonadecanone, 10-nonadecanone, 2-eicosanone, 11-eicosanone, 2-heneicosanone, 2-docosanone, laurone, stearone, and the like. Further, aryl alkyl ketones having a total carbon number of 12 to 24, for example, n-octadecanophenone, n-heptadecanophenone, n-hexadecanophenone, n-pentadecanophenone, n-tetradecanophenone, 4-n-dodecaacetophenone, n-tridecanophenone, 4-n-undecanoacetophenone, n-laurophenone, 4-n-decanoacetophenone, n-undecanophenone, 4-n-nonylacetophenone, n-decanophenone, 4-n-octylacetophenone, n ... nophenone, 4-n-heptylacetophenone, n-octanophenone, 4-n-hexylacetophenone, 4-n-cyclohexylacetophenone, 4-tert-butylpropiophenone, n-heptaphenone, 4-n-pentylacetophenone, cyclohexyl phenyl ketone, benzyl-n-butyl ketone, 4-n-butylacetophenone, n-hexanophenone, 4-isobutylacetophenone, 1-acetonaphthone, 2-acetonaphthone, cyclopentyl phenyl ketone, and the like.

[0021] As the ethers, aliphatic ethers having a total of 10 or more carbon atoms are effective, and examples thereof 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.

[0022] Examples of acid amides include acetamide, propionic acid amide, butyric acid 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, and caproic acid N-methylamide. Caprylic acid N-methylamide, capric acid N-methylamide, lauric acid N-methylamide, myristic acid N-methylamide, palmitic acid N-methylamide, stearic acid N-methylamide, behenic acid N-methylamide, oleic acid N-methylamide, erucic acid N-methylamide, lauric acid N-ethylamide, myristic acid N-ethylamide, palmitic acid N-ethylamide, stearic acid N-ethylamide, oleic acid N-ethylamide, lauric acid N-butylamide, myristic acid N-butylamide, palmitic acid N-butylamide, stearic acid N-ethylamide, Phosphoric acid N-butylamide, oleic acid N-butylamide, lauric acid N-octylamide, myristic acid N-octylamide, palmitic acid N-octylamide, stearic acid N-octylamide, oleic acid N-octylamide, lauric acid N-dodecylamide, myristic acid N-dodecylamide, palmitic acid N-dodecylamide, stearic acid N-dodecylamide, oleic acid N-dodecylamide, dilauric acid amide, dimyristic acid amide, dipalmitic acid amide, distearic acid amide, dioleic acid amide, trilauric acid amide, 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 of the amides include adipic acid N-butylamide, glutaric acid N-butylamide, malonic acid N-butylamide, adipic acid N-octylamide, and adipic acid N-dodecylamide.

[0023] Furthermore, as the component (iii), a compound represented by the following general formula (1) can also be used. [ka] [In the formula, R1 represents a hydrogen atom or a methyl group, m represents an integer of 0 to 2, and either X1 or X2 represents -(CH2) n OCOR2 or -(CH2) n COOR2, the other represents a hydrogen atom, n represents an integer of 0 to 2, R2 represents an alkyl or alkenyl group having 4 or more carbon atoms, Y1 and Y2 represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, or a halogen, and r and p represent integers of 1 to 3. Among the compounds represented by the formula (1), when R1 is a hydrogen atom, a reversible thermochromic composition having a wider hysteresis width can be obtained, which is preferable, and further when R1 is a hydrogen atom and m is 0, it is more preferable. Among the compounds represented by formula (1), it is more preferable to use a compound represented by the following general formula (2). [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 compound 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.

[0024] Furthermore, as the component (iii), 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 of 1 to 3, and X and Y each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen.) Specific examples of the compound 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.

[0025] Furthermore, a compound represented by the following general formula (4) can also be used as the component (iii). [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 of 1 to 3, and n represents an integer of 1 to 20.) Examples of the compound include a diester of malonic acid and 2-[4-(4-chlorobenzyloxy)phenyl]ethanol, a diester of succinic acid and 2-(4-benzyloxyphenyl)ethanol, a diester of succinic acid and 2-[4-(3-methylbenzyloxy)phenyl]ethanol, a diester of glutaric acid and 2-(4-benzyloxyphenyl)ethanol, a diester of glutaric acid and 2-[4-(4-chlorobenzyloxy)phenyl]ethanol, a diester of adipic acid and 2-(4-benzyloxyphenyl)ethanol, a diester of pimelic acid and 2-(4-benzyloxyphenyl)ethanol, a diester of suberic acid and 2-(4-benzyloxyphenyl)ethanol, a diester of suberic acid and 2-[4-(3-methylbenzyloxy)phenyl]ethanol, and a diester of malonic acid and 2-[4-(4-chlorobenzyloxy)phenyl]ethanol. Examples of such esters include a diester of 2-(4-benzyloxyphenyl)ethanol with suberic acid, a diester of 2-(4-(2,4-dichlorobenzyloxy)phenyl)ethanol with suberic acid, a diester of 2-(4-benzyloxyphenyl)ethanol with suberic acid, a diester of 2-(4-benzyloxyphenyl)ethanol with azelaic acid, a diester of 2-(4-benzyloxyphenyl)ethanol with sebacic acid, a diester of 1,10-decanedicarboxylic acid and 2-(4-benzyloxyphenyl)ethanol with 1,18-octadecanedicarboxylic acid, and a diester of 1,18-octadecanedicarboxylic acid and 2-(4-benzyloxyphenyl)ethanol with 2-[4-(2-methylbenzyloxy)phenyl)]ethanol.

[0026] Furthermore, a compound represented by the following general formula (5) can also be used as the component (iii). [ka] (In the formula, R represents an alkyl group or alkenyl group having 1 to 21 carbon atoms, and n represents an integer of 1 to 3.) Examples of the compound include a diester of 1,3-bis(2-hydroxyethoxy)benzene and capric acid, a diester of 1,3-bis(2-hydroxyethoxy)benzene and undecanoic acid, a diester of 1,3-bis(2-hydroxyethoxy)benzene and lauric acid, a diester of 1,3-bis(2-hydroxyethoxy)benzene and myristic acid, a diester of 1,4-bis(hydroxymethoxy)benzene and butyric acid, a diester of 1,4-bis(hydroxymethoxy)benzene and isovaleric acid, a diester of 1,4-bis(2-hydroxyethoxy)benzene and acetic acid, and a diester of 1,4-bis(hydroxymethoxy)benzene and acetic acid. Examples include a diester of 4-bis(2-hydroxyethoxy)benzene and propionic acid, a diester of 1,4-bis(2-hydroxyethoxy)benzene and valeric acid, a diester of 1,4-bis(2-hydroxyethoxy)benzene and caproic acid, a diester of 1,4-bis(2-hydroxyethoxy)benzene and caprylic acid, a diester of 1,4-bis(2-hydroxyethoxy)benzene and capric acid, a diester of 1,4-bis(2-hydroxyethoxy)benzene and lauric acid, and a diester of 1,4-bis(2-hydroxyethoxy)benzene and myristic acid.

[0027] Furthermore, as the component (iii), a compound represented by the following general formula (6) can also be used. [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 of 1 to 3, and n represents an integer of 1 to 20.) Examples of the compound include a diester of succinic acid and 2-phenoxyethanol, a diester of suberic acid and 2-phenoxyethanol, a diester of sebacic acid and 2-phenoxyethanol, a diester of 1,10-decanedicarboxylic acid and 2-phenoxyethanol, and a diester of 1,18-octadecanedicarboxylic acid and 2-phenoxyethanol.

[0028] Furthermore, a compound represented by the following general formula (7) can also be used as the component (iii). [ka] (In the formula, R represents any one of an alkyl group having 4 to 22 carbon atoms, a cycloalkylalkyl group, a cycloalkyl group, and an alkenyl group having 4 to 22 carbon atoms; X represents any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom; and n represents 0 or 1.) Examples of the compound 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.

[0029] Furthermore, as the component (iii), a compound represented by the following general formula (8) can also be used. [ka] (In the formula, R represents any one of an alkyl group having 3 to 18 carbon atoms and an aliphatic acyl group having 3 to 18 carbon atoms; X represents any one of a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 or 2 carbon atoms, and a halogen atom; Y represents any one of a hydrogen atom and a methyl group; and Z represents any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 or 2 carbon atoms, and a halogen atom.) Examples of the compound include phenoxyethyl 4-butoxybenzoate, phenoxyethyl 4-pentyloxybenzoate, phenoxyethyl 4-tetradecyloxybenzoate, an ester of phenoxyethyl 4-hydroxybenzoate with dodecanoic acid, and dodecyl ether of phenoxyethyl vanillate.

[0030] Furthermore, as the component (iii), a compound represented by the following general formula (9) can also be used. [ka] (In the formula, R represents any one of an alkyl group having 4 to 22 carbon atoms, an alkenyl group having 4 to 22 carbon atoms, a cycloalkylalkyl group, and a cycloalkyl group; X represents any one of a hydrogen atom, an alkyl group, an alkoxy group, and a halogen atom; Y represents any one of a hydrogen atom, an alkyl group, an alkoxy group, and a halogen atom; and n represents 0 or 1.) Examples of the compound include the benzoate ester of octyl p-hydroxybenzoate, the benzoate ester of decyl p-hydroxybenzoate, the p-methoxybenzoate ester of heptyl p-hydroxybenzoate, the o-methoxybenzoate ester of dodecyl p-hydroxybenzoate, and the benzoate ester of cyclohexylmethyl p-hydroxybenzoate.

[0031] Furthermore, as the component (iii), a compound represented by the following general formula (10) can also be used. [ka] (In the formula, R represents any one of 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, and an alkenyl group having 3 to 18 carbon atoms; X represents any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a halogen atom; and Y represents any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, an ethoxy group, and a halogen atom.) Examples of the compound 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.

[0032] Furthermore, as the component (iii), a compound represented by the following general formula (11) can also be used. [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 of 1 to 3.) Examples of the compound include a diester of 1,3-bis(2-hydroxyethoxy)benzene and cyclohexanecarboxylic acid, a diester of 1,4-bis(2-hydroxyethoxy)benzene and cyclohexanepropionic acid, and a diester of 1,3-bis(2-hydroxyethoxy)benzene and cyclohexanepropionic acid.

[0033] Furthermore, as the component (iii), a compound represented by the following general formula (12) can also be used. [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 of 1 to 3.) Examples of the compound include a diester of 4-phenylphenol ethylene glycol ether and cyclohexane carboxylic acid, a diester of 4-phenylphenol diethylene glycol ether and lauric acid, a diester of 4-phenylphenol triethylene glycol ether and cyclohexane carboxylic acid, a diester of 4-phenylphenol ethylene glycol ether and octanoic acid, a diester of 4-phenylphenol ethylene glycol ether and nonanoic acid, a diester of 4-phenylphenol ethylene glycol ether and decanoic acid, and a diester of 4-phenylphenol ethylene glycol ether and myristic acid.

[0034] Furthermore, reversible thermochromic compositions of the heat-coloring type (which develops color when heated and loses color when cooled) that use specific alkoxyphenol compounds having a straight-chain or side-chain alkyl group having 3 to 18 carbon atoms as the electron-accepting compound (JP Patent Publication Nos. 11-129623 and 11-5973), specific hydroxybenzoic acid esters (JP Patent Publication No. 2001-105732), or gallic acid esters (JP Patent Publication Nos. 51-44706 and 2003-253149) can also be applied (see FIG. 3).

[0035] The ratio of each component of the reversible thermochromic composition depends on the concentration, color change temperature, color change form, and type of each component, but generally, the component ratio that gives the desired properties is in the range of 1 part of component (a) to 0.1 to 100, preferably 0.1 to 50, and more preferably 0.5 to 20, of component (b) and 1 to 800, preferably 5 to 200, and more preferably 10 to 100, of component (c) (all the above ratios are parts by mass).

[0036] Furthermore, various light stabilizers can be added as necessary. The light stabilizer is contained in order to prevent photodegradation of the reversible thermochromic composition consisting of components (a), (b) and (c), and is contained in a ratio of 0.3 to 24 mass%, preferably 0.3 to 16 mass%, per 1 mass% of component (a). Among the light stabilizers, the ultraviolet absorber effectively blocks ultraviolet rays contained in sunlight and the like, and prevents photodegradation caused by the excited state due to the photoreaction of component (a). The antioxidant, singlet oxygen quencher, superoxide anion quencher, ozone quencher and the like suppress oxidation reactions caused by light. The light stabilizers may be used alone or in combination of two or more kinds.

[0037] The reversible thermochromic composition can be used as a reversible thermochromic pigment by being dispersed in a thermoplastic resin or a thermosetting resin, or by being encapsulated in a microcapsule. Microencapsulation may be carried out by any of the known methods, such as interfacial polymerization, in situ polymerization, liquid curing coating, phase separation from an aqueous solution, phase separation from an organic solvent, melt dispersion cooling, air suspension coating, spray drying, etc., and may be appropriately selected depending on the application. Furthermore, a secondary resin film may be provided on the surface of the microcapsule depending on the purpose to impart durability or modify the surface properties for practical use. The microcapsule pigment preferably has a mass ratio of inclusions / wall film of 7 / 1 to 1 / 1. By having the wall film ratio within this range, it is possible to prevent a decrease in color density and vividness during color development, and more preferably, the mass ratio of inclusions / wall film is 6 / 1 to 1 / 1. By encapsulating the pigment in the microcapsules, a chemically and physically stable pigment can be obtained.

[0038] The reversible thermochromic layer can be formed by a known method using a liquid composition such as ink or paint in which the reversible thermochromic composition is dispersed in a vehicle. Furthermore, a molded product formed by blending a microcapsule pigment encapsulating the reversible thermochromic composition with a thermoplastic resin or a thermosetting resin may be used as the reversible thermochromic layer. In addition, a suitable amount of a non-thermochromic color pigment may be mixed in the reversible thermochromic layer to produce more diverse color changes.

[0039] The above-mentioned luster pigment is a luster pigment in which the surface of flat aluminum particles is coated with iron oxide, or a luster pigment in which the surface of flat silicon dioxide particles is coated with iron oxide, and the mass of iron element in the luster pigment is 5 to 400 parts by mass, preferably 10 to 350 parts by mass, and more preferably 15 to 300 parts by mass, per 100 parts by mass of aluminum element or silicon element. If the mass of the iron element exceeds 400 parts by mass, the flat shape is lost and the change in color and brightness becomes poor, whereas if it is less than 5 parts by mass, the strength is reduced and the pigment becomes more likely to crack during molding. The ratio of aluminum and iron content in iron oxide-coated aluminum, or the ratio of silicon and iron content in iron oxide-coated silicon dioxide, was determined by quantitative analysis using an energy dispersive X-ray fluorescence analyzer (Shimadzu Corporation, EDX-720) with carbon set as the balance element and the aluminum and iron content, and the silicon and iron content were quantified by fundamental parameter method (FP method).

[0040] The average particle size of the bright pigment is from 1 to 70 μm, preferably from 5 to 40 μm, and more preferably from 10 to 20 μm. The average particle size is determined by observing the surfaces of 50 pigment particles using a scanning electron microscope (SEM), taking the maximum diameter as the particle size, and averaging the maximum diameter. The maximum particle size may also be determined using image analysis software. The average thickness of the bright pigment is from 1 to 3500 nm, preferably from 1 to 2000 nm, and more preferably from 2 to 1000 nm. The average thickness is determined by observing the cross sections of 20 pigment particles with a transmission electron microscope (TEM) to measure the thickness, and averaging the measured values. The aspect ratio (average particle size / average thickness) of the bright pigment is 20-5,000, preferably 25-3,000, and more preferably 30-2,000.

[0041] The color pigment is a pigment contained in the metallic luster layer and is appropriately selected depending on the color of the luster pigment. For example, when a yellow to red brilliant pigment is used, the color change will be greater if a color pigment whose color is the complementary color of the brilliant pigment or a color close to the complementary color is used as the color pigment. As the color pigment, blue pigments are preferred, and examples thereof include organic pigments such as phthalocyanine pigments, quinacridone pigments, dioxazine pigments, and perylene pigments, and inorganic pigments such as composite oxides such as bismuth vanadium oxide, ultramarine blue, and cobalt blue. Among these, phthalocyanine pigments are preferred from the viewpoints of coloring properties and transparency. The color pigment may contain pigments other than blue pigments, and examples of the color pigment include organic pigments such as azo pigments and isoindolinone pigments, and inorganic pigments such as composite oxides, titanium oxide, red iron oxide, and red vermilion. The average particle size of the color pigment is 0.01 to 2 μm, preferably 0.01 to 1.5 μm, and more preferably 0.02 to 1 μm. The average particle size is determined by observing 50 pigment particles with a transmission electron microscope (TEM), taking the maximum diameter as the particle size, and averaging the maximum diameter. The maximum particle size may be determined using image analysis software. The metallic luster layer can be formed by a known method using a liquid composition such as ink or paint in which the above-mentioned luster pigment and color pigment are dispersed in a vehicle. Furthermore, a molded product formed by blending the above-mentioned luster pigment and color pigment into a thermoplastic resin or a thermosetting resin may be used as the metallic luster layer.

[0042] When the metallic luster layer is irradiated with light from one direction, the light reflected by the luster pigment and the color pigment is mainly reflected in the regular reflection direction. Due to the luster of the luster pigment, the light reflected by the luster pigment is mainly observed in the regular reflection direction or in a direction close to the regular reflection direction, whereas in a direction far away from the regular reflection direction, the reflected light is weaker, so that the color of the color pigment is mainly observed in comparison to the light reflected from the luster pigment. Incidentally, if a reflective layer containing silicon dioxide is provided between the aluminum and iron oxide, the reflective layer increases the brightness and makes the color of the luster pigment appear more intense. Furthermore, the brightness and color of a toy vary greatly depending on its transparency. In areas with low transparency, the color of the glittering pigment is more easily visible, while in areas with high transparency, the color of the coloring pigment is more easily visible. In the above-mentioned state where the luminance and color change occurs, in combination with the color change caused by the reversible thermochromic composition, more diverse brilliance and color changes can be expressed.

[0043] When at least one of the metallic luster layer and the reversible thermochromic layer is a molded article, no support is particularly required. However, when each layer is formed from a liquid composition such as ink, a substrate is required. The substrate is selected from materials such as paper, synthetic paper, metal, ceramics, stone, wood, glass, resin, and fabric, and its shape is not particularly limited. When an opaque substrate is used, the reversible thermochromic layer and the metallic luster layer are laminated in this order on the substrate. When a transparent substrate is used, a metallic luster layer and a reversible thermochromic layer can be laminated in that order, in which case, as viewed from the support side, excellent color flop properties are obtained as described above. Furthermore, when a transparent substrate is used, the transparent substrate can be interposed between the reversible thermochromic layer and the metallic luster layer. The transparent substrate may be made of glass or resin, and is preferably a resin molded product or a resin film. The transparency may be colorless transparency, semi-transparency, colored transparency, or colored semi-transparency.

[0044] It is preferable to provide a top coat layer on the uppermost layer of the toy to improve durability and water resistance. Furthermore, a light stabilizer layer can be provided as appropriate on the top layer of the toy or between each layer. Specifically, the light stabilizer layer is a layer in which a light stabilizer selected from an ultraviolet absorber, an antioxidant, an antiaging agent, a singlet oxygen quencher, a superoxide anion quencher, an ozone decolorizer, a visible light absorber, and an infrared absorber is fixed in a dispersed state, and can be formed in accordance with the preparation of the reversible thermochromic layer or the metallic luster layer described above. It is more preferable to provide a light stabilizer layer on the uppermost layer, since this can impart light resistance to the reversible thermocolor changing layer in addition to durability and water resistance. EXAMPLES

[0045] Example 1 Creation of a thermochromic toy with metallic luster (see Figure 4) A reversible thermochromic oil-based spray paint was applied to the surface of a transparent toy car as the substrate 2, and the paint was dried to form a reversible thermochromic layer 3. The paint was then ... oil-based spray paint, the paint being a mixture of 20 parts of a reversible thermochromic microcapsule pigment that changes color to black at 15°C or lower and colorless at 32°C or higher, the reversible thermochromic composition being composed of 3 parts of 2-anilino-3-methyl-6-dibutylaminofluoran, 6 parts of 4,4'-(2-methyl-propylidene)bisphenol, and 50 parts of neopentyl stearate encapsulated in microcapsules. The reversible thermochromic oil-based spray paint was then dried to form a reversible thermochromic layer 3. Next, the reversible thermochromic layer was painted with a metallic luster oil-controlling spray paint containing 20 parts of red flat iron oxide-coated aluminum particles (average particle diameter 16 μm, average thickness 300 nm, aspect ratio 53, amount of iron contained in the particles is 160 parts by mass per 100 parts by mass of aluminum element), 2 parts of blue pigment, 50 parts of acrylic resin / xylene solution, 58 parts of xylene, and 10 parts of an isocyanate-based hardener, and dried to form a metallic luster layer 4, thereby obtaining a metallic luster thermochromic toy 1. When the metallic luster thermochromic toy is heated to 32° C. or higher, the reversible thermochromic layer becomes colorless, and purple to red metallic luster colors and blue colors are seen depending on the viewing angle. In particular, the blue color of the color pigment was visually emphasized in areas where the substrate was thin (highly transparent). At temperatures below 15°C, the reversible thermochromic layer turns black, and depending on the viewing angle, a metallic gloss color ranging from purple to red is visible. At temperatures between 15 and 32°C, the reversible thermochromic layer can be viewed alternatively as either a decolorized state or a colored state. This change in appearance could be repeated by changing the temperature.

[0046] Example 2 Creating a metallic luster thermochromic toy The surface of a transparent accessory toy substrate was painted with a reversible thermochromic oil-based spray paint made of a mixture of 20 parts of a reversible thermochromic microcapsule pigment that changes color to black at 15°C or lower and colorless at 32°C or higher, 50 parts of an acrylic resin / xylene solution, 60 parts of xylene, and 10 parts of an isocyanate-based hardener, the mixture containing a reversible thermochromic composition consisting of 3 parts of 2-anilino-3-methyl-6-dibutylaminofluoran, 6 parts of 4,4'-(2-methyl-propylidene)bisphenol, and 50 parts of neopentyl stearate encapsulated in microcapsules, and the paint was then dried to form a reversible thermochromic layer. Next, the reversible thermochromic layer was painted with a metallic luster oil-controlling spray paint containing 20 parts of orange flat iron oxide-coated aluminum particles (average particle diameter 19 μm, average thickness 170 nm, aspect ratio 112, amount of iron contained in the particles is 24 parts by mass per 100 parts by mass of aluminum element), 3 parts of blue pigment, 50 parts of acrylic resin / xylene solution, 57 parts of xylene, and 10 parts of an isocyanate-based hardener, and then dried to form a metallic luster layer, thereby obtaining a metallic luster thermochromic toy. When the above-mentioned thermochromic toy with metallic luster is heated to 32° C. or higher, the reversible thermochromic layer becomes colorless, and depending on the viewing angle, a metallic luster color of green to orange or blue appears. In particular, the blue color of the color pigment was visually emphasized in areas where the substrate was thin (highly transparent). At temperatures below 15°C, the reversible thermochromic layer turns black, and depending on the viewing angle, a metallic luster color ranging from green to orange is visible. At temperatures between 15 and 32°C, the reversible thermochromic layer can be seen to alternate between a decolorized state and a colored state. This change in appearance could be repeated by changing the temperature.

[0047] Example 3 Creating a metallic luster thermochromic toy A reversible thermochromic oil-based spray paint was applied to the surface of a transparent dinosaur toy as a substrate, and the paint was dried to form a reversible thermochromic layer. The paint was a mixture of 20 parts of a reversible thermochromic microcapsule pigment that changes color to black at 25°C or less and colorless at 35°C or more, and contains a reversible thermochromic composition consisting of 3 parts of 2-(2-chloroanilino)-6-di-n-butylaminofluoran, 6 parts of 4,4'-(2-methyl-propylidene)bisphenol, 25 parts of stearyl caprate, and 25 parts of cetyl alcohol encapsulated in a microcapsule, 50 parts of an acrylic resin / xylene solution, 60 parts of xylene, and 10 parts of an isocyanate-based hardener. Next, the reversible thermochromic layer was painted with a metallic luster oil-controlling spray paint containing 15 parts of yellow flat iron oxide-coated aluminum particles (average particle diameter 16 μm, average thickness 150 nm, aspect ratio 107, amount of iron contained in the particles is 19 parts by mass per 100 parts by mass of aluminum element), 2 parts of blue pigment, 50 parts of acrylic resin / xylene solution, 58 parts of xylene, and 10 parts of an isocyanate-based hardener, and then dried to form a metallic luster layer, thereby obtaining a metallic luster thermochromic toy. When the metallic luster thermochromic toy is heated to 35° C. or higher, the reversible thermochromic layer becomes colorless, and depending on the viewing angle, a metallic luster color of green to yellow or blue appears. In particular, the blue color of the color pigment was visually emphasized in areas where the substrate was thin (highly transparent). At temperatures below 25°C, the reversible thermochromic layer turns black, and depending on the viewing angle, a metallic luster color ranging from green to yellow can be seen. At temperatures between 25 and 35°C, the reversible thermochromic layer can be seen to alternate between a decolorized state and a colored state. This change in appearance could be repeated by changing the temperature.

[0048] Example 4 Creating a metallic luster thermochromic toy The surface of a transparent insect toy substrate was painted with a reversible thermochromic oil-based spray paint containing 20 parts of a reversible thermochromic microcapsule pigment that changes color to black at 25°C or less and colorless at 35°C or more, 50 parts of an acrylic resin / xylene solution, 60 parts of xylene, and 10 parts of an isocyanate-based hardener, the reversible thermochromic layer being formed by mixing the reversible thermochromic microcapsule pigment that changes color to black at 25°C or less and colorless at 35°C or more, the reversible thermochromic composition being composed of 3 parts of 2-(2-chloroanilino)-6-di-n-butylaminofluoran, 6 parts of 4,4'-(2-methyl-propylidene)bisphenol, 25 parts of stearyl caprate, and 25 parts of cetyl alcohol, and then dried to form a reversible thermochromic layer. Next, the reversible thermochromic layer was painted with a metallic luster oil-controlling spray paint containing 20 parts of dark red flat iron oxide-coated aluminum particles (average particle diameter 16 μm, average thickness 320 nm, aspect ratio 50, amount of iron contained in the particles is 357 parts by mass per 100 parts by mass of aluminum element), 2 parts of blue pigment, 50 parts of acrylic resin / xylene solution, 58 parts of xylene, and 10 parts of an isocyanate-based hardener, and then dried to form a metallic luster layer, thereby obtaining a metallic luster thermochromic toy. When the metallic luster thermochromic toy is heated to 35° C. or higher, the reversible thermochromic layer becomes colorless, and a metallic luster color ranging from deep purple to deep red and blue appears depending on the viewing angle. In particular, the blue color of the color pigment was visually emphasized in areas where the substrate was thin (highly transparent). At temperatures below 25°C, the reversible thermochromic layer turns black, and depending on the viewing angle, a metallic gloss color ranging from deep purple to deep red is visible. At temperatures between 25 and 35°C, the reversible thermochromic layer can be viewed alternatively as either a decolorized state or a colored state. This change in appearance could be repeated by changing the temperature.

[0049] Example 5 Creation of a thermochromic toy with metallic luster (see Figure 5) A reversible thermochromic microencapsulated pigment (20 parts) that changes color from black at 18°C ​​or less to colorless at 30°C or more, in which a reversible thermochromic composition consisting of 3 parts of 2-(2-chloroanilino)-6-di-n-butylaminofluoran, 6 parts of 2,2-bis(4-hydroxyphenyl)hexafluoropropane, and 50 parts of n-nonyl palmitate is encapsulated in a microcapsule, 2 parts of a benzotriazole-based ultraviolet absorber, and 1,000 parts of high-density polyethylene with a Vicat softening point of 119°C were mixed uniformly, and then molded using an extrusion molding machine under conditions of a cylinder temperature of 165°C and a gate temperature of 160°C to obtain a metallic luster-toned thermochromic molding resin composition (pellets). The pellets were used to mold a spherical toy base material (reversible thermocolor changing layer 3) having a thickness of about 2 mm and an outer diameter of 5 cm at a cylinder temperature of 175° C. using a blow molding machine. Next, the reversible thermochromic layer was painted with a metallic luster oil-controlling spray paint containing 15 parts of pale yellow flat iron oxide-coated aluminum particles (average particle diameter 16 μm, average thickness 140 nm, aspect ratio 114, amount of iron contained in the particles 10 parts by mass per 100 parts by mass of aluminum element), 2 parts of blue pigment, 50 parts of acrylic resin / xylene solution, 60 parts of xylene, and 10 parts of isocyanate-based hardener, and dried to form a metallic luster layer 4, thereby obtaining a metallic luster thermochromic toy 1. When the metallic luster thermochromic toy is heated to 30°C or higher, the reversible thermochromic layer becomes colorless, and a metallic luster color of green to yellow or blue is visually observed depending on the viewing angle. At 18°C ​​or lower, the reversible thermochromic layer turns black, and a metallic luster color of green to yellow is visually observed depending on the viewing angle. In the range of 18 to 30°C, the reversible thermochromic layer can be visually observed alternatively in a decolorized state or a colored state. This change in appearance could be repeated by changing the temperature.

[0050] Example 6 Creating a metallic luster thermochromic toy A reversible thermochromic oil-based spray paint was applied to the surface of a transparent toy car as a substrate, and the paint was dried to form a reversible thermochromic layer. The paint was a mixture of 20 parts of a reversible thermochromic microcapsule pigment that changes color to black at 18°C ​​or lower and colorless at 30°C or higher, the microcapsule pigment containing a reversible thermochromic composition consisting of 3 parts of 2-(2-chloroanilino)-6-di-n-butylaminofluoran, 6 parts of 2,2-bis(4-hydroxyphenyl)hexafluoropropane, and 50 parts of n-nonyl palmitate encapsulated in microcapsules, the reversible thermochromic oil-based spray paint being a mixture of 50 parts of an acrylic resin / xylene solution, 60 parts of xylene, and 10 parts of an isocyanate-based hardener. Next, the reversible thermochromic layer was painted with a metallic luster oil-controlling spray paint containing 20 parts of red flat iron oxide-coated silicon dioxide particles, 3 parts of blue pigment, 50 parts of acrylic resin / xylene solution, 57 parts of xylene, and 10 parts of an isocyanate-based hardener, and then dried to form a metallic luster layer, thereby obtaining a metallic luster thermochromic toy. When the above-mentioned thermochromic toy with metallic luster is heated to 30° C. or higher, the reversible thermochromic layer becomes colorless, and purple to red metallic luster colors and blue are visually observed depending on the viewing angle. In particular, the blue color of the color pigment was visually emphasized in areas where the substrate was thin (highly transparent). At temperatures below 18°C, the reversible thermochromic layer turns black, and depending on the viewing angle, a metallic gloss color ranging from purple to red is visible. At temperatures between 18 and 30°C, the reversible thermochromic layer can be viewed alternatively as either a decolorized state or a colored state. This change in appearance could be repeated by changing the temperature. [Explanation of symbols]

[0051] t1 Complete color development temperature of heat-discolorable reversible thermochromic composition t2 Color development start temperature of heat-discolorable reversible thermochromic composition t3: The starting temperature of discoloration of reversible thermochromic composition that discolors when heated t4 Complete decolorization temperature of heat-decolorizing type reversible thermochromic composition T1 Complete decolorization temperature of heat-coloring type reversible thermochromic composition T2: The starting temperature of discoloration of a reversible thermochromic composition that develops color by heating T3: Color development start temperature of heat-coloring type reversible thermochromic composition T4 Complete color development temperature of heat-coloring type reversible thermochromic composition ΔH Hysteresis width 1. Metallic gloss thermochromic toy 2 Base material 3. Reversible thermochromic layer 4 Metallic gloss layer

Claims

1. A metallic luster thermochromic toy comprising a reversible thermochromic layer containing a reversible thermochromic composition consisting of an electron-donating organic color-forming compound, an electron-accepting compound, and an organic compound medium that reversibly induces a color-changing reaction between the two, and a metallic luster layer containing a glittering pigment and a coloring pigment, the glittering pigment being a glittering pigment having flat aluminum surfaces coated with iron oxide, or a glittering pigment having flat silicon dioxide surfaces coated with iron oxide, the mass of iron element in the glittering pigment being 5 to 400 parts by mass per 100 parts by mass of aluminum element or silicon element.

2. 2. The thermochromic toy according to claim 1, wherein said color pigment comprises a blue pigment.

3. 3. The metallic luster thermochromic toy according to claim 1, further comprising a reflective layer containing silicon dioxide between the aluminum and iron oxide of said glittering pigment.

4. 4. The metallic luster thermochromic toy according to claim 3, wherein the mass of silicon element in the glittering pigment is 5 to 50 parts by mass per 100 parts by mass of aluminum element.

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