Temperature-sensitive multicolor-changing toy

Abstract

[Problem] To provide a temperature-sensitive multicolor-changing toy having colors that are richly vivid before and after a color change, and in which changes into multiple colors can be visually recognized sharply and clearly. [Solution] A temperature-sensitive multicolor-changing toy in which a pigment A containing a reversible thermochromic composition a and a pigment B containing a reversible thermochromic composition b are dispersed in a vinyl chloride resin, and the toy is formed with a hollow interior, wherein the reversible thermochromic compositions a and b are such that at the complete color development temperature of one of the reversible thermochromic compositions, the color development concentration of the other reversible thermochromic composition is 40% or less, or at the complete decolorization temperature of one of the reversible thermochromic compositions, the color development concentration of the other reversible thermochromic composition is 60% or more.

Description

Temperature-sensitive multicolor color-changing toy

[0001] The present invention relates to a temperature-sensitive multi-color-changing toy, and more particularly to a temperature-sensitive multi-color-changing toy that exhibits a variety of color changes in response to temperature changes.

[0002] Conventionally, a reversible thermosensitive multicolor-changing composition that manifests multiple colors in response to a temperature change and a toy using the same have been disclosed (see, for example, Patent Document 1). The toy using the reversible thermosensitive multicolor-changing composition exhibits multiple color changes, and each color before and after the color change is highly vivid.

[0003] Japanese Patent Application Laid-Open No. 2000-80359

[0004] The present invention aims to provide a temperature-sensitive multi-color-changing toy that exhibits this type of multi-color change, has rich vividness of each color before and after the color change, and has excellent visibility of the multi-color change.

[0005] The present invention relates to a toy having a hollow interior, which is made by dispersing a pigment A containing a reversible thermochromic composition a and a pigment B containing a reversible thermochromic composition b in a vinyl chloride resin, and the reversible thermochromic compositions a and b have a color development initiation temperature (T ２ or t ２ ) color begins to develop, and the complete color development temperature (T １ or t １ ) the color is completely developed, and the temperature rises from the colored state to the color-decoloring starting temperature (T ３ or t ３ ) the color begins to fade, and the complete fade temperature (T ４ or t ４), and the thermosensitive multicolor-changing toy is required to have a color density of 40% or less at the complete color development temperature of one reversible thermochromic composition, or a color density of 60% or more at the complete color development temperature of one reversible thermochromic composition. Further, in other embodiments, the thermosensitive multicolor-changing toy according to the present invention has an uneven surface, the hysteresis curves of reversible thermochromic compositions a and b do not overlap, the hysteresis curve of reversible thermochromic composition b is inherent in the hysteresis curve of reversible thermochromic composition a, and the hysteresis width (ΔH ａ ) and the hysteresis width (ΔH ｂ ) satisfies the following conditions (1) and (2), or the hollow part of the toy is not in communication with the outside, and the ratio of the volume of the vinyl chloride resin to the volume of the hollow part is 85:15 to 10:90. ａ = [(T ４ +T ３ ) / 2-(T ２ +T １ ) / 2]=10~50℃ (1) ΔH ｂ = [(t ４ +t ３ ) / 2-(t ２ +t １ ) / 2]=0.5~20℃(2) (T １ , T ２ , T ３ , T ４ represent the complete color development temperature, color development initiation temperature, color disappearance initiation temperature, and complete color disappearance temperature of the reversible thermochromic composition a, respectively, and t １ , t ２ , t ３ , t ４indicate the complete color-changing temperature, color-changing onset temperature, color-fading onset temperature, and complete color-fading temperature of reversible thermochromic composition b, respectively.) Furthermore, the toy set according to the present invention is required to comprise a temperature-sensitive, multi-color-changing toy and a temperature-changing member that changes the temperature of part or all of the temperature-sensitive, multi-color-changing toy, and as another embodiment, it also includes one that is required to have the temperature-changing member apply cold water or hot water to the temperature-sensitive, multi-color-changing toy.

[0006] To provide a toy set and a thermosensitive multi-color-changing toy with high commercial value, which is a toy made of vinyl chloride resin and has a hollow interior, and which has rich vividness of colors before and after color change and allows the multi-color color change to be visually recognized sharply and clearly.

[0007] 1 is a graph illustrating the color density-temperature curve of a reversible thermochromic composition. 2 is a graph illustrating the color density-temperature curve of a temperature-sensitive, multi-color-changing toy comprising the reversible thermochromic composition a and the reversible thermochromic composition b of the present invention. 3 is a graph illustrating the color density-temperature curve of a temperature-sensitive, multi-color-changing toy comprising the other reversible thermochromic composition a and the reversible thermochromic composition b of the present invention. 4 is a graph illustrating the color density-temperature curve of a temperature-sensitive, multi-color-changing toy comprising the other reversible thermochromic composition a and the reversible thermochromic composition b of the present invention.

[0008] The reversible thermochromic compositions a and b are thermochromic compositions containing three components: (α) an electron-donating organic color-forming compound, (β) an electron-accepting compound, and (γ) an organic compound medium that reversibly induces a color-forming reaction due to the electron donor / acceptor reaction of (α) and (β). Specific examples include thermochromic compositions with relatively small hysteresis widths described in JP-B-51-35414, JP-B-51-44706, JP-B-1-17154, and JP-A-7-186546, and highly sensitive thermochromic compositions exhibiting a hysteresis width of 3°C or less described in JP-B-1-29398. This type of thermochromic composition changes color around a color-changing temperature, and only one of the two states before and after the color change can exist at room temperature. That is, the thermochromic composition maintains the other state while the heat or cold required to manifest that state is applied, but returns to its original state at room temperature once the application of heat or cold is removed. Also usable are thermochromic color-memory compositions that exhibit large hysteresis characteristics and change color, as described in JP-B-4-17154, JP-A-7-179777, JP-A-7-33997, JP-A-8-39936, etc., i.e., thermochromic compositions in which the shape of the curve plotting the change in color density with temperature follows significantly different paths when the temperature is increased from a lower side than the color-change temperature range and when the temperature is decreased from a higher side than the color-change temperature range, and which can alternately memorize and retain the changed color state. The hysteresis characteristics of the color density-temperature curve of the reversible thermochromic composition are now described in detail. In Figure 1, the vertical axis represents color density and the horizontal axis represents temperature. The vertical axis is in arbitrary units, and the area where the color density is high is the fully colored density (100%), while the area where the color density is low is the fully decolored density (0%). The change in color density due to temperature changes progresses along the arrow. Here, A is the lowest temperature T at which the fully decolored state is reached. ４ (hereinafter referred to as the complete decolorization temperature), and B is the maximum temperature T ３ (hereinafter referred to as the decolorization starting temperature), and C is the lowest temperature T２ (hereinafter referred to as the color development starting temperature), and D is the maximum temperature T １ (hereinafter referred to as the complete color development temperature). Ａ At this temperature T Ａ The temperature range in which the colored and decolored states can coexist, including the temperature range in which the discoloration can be maintained, is the temperature range in which the discoloration can be maintained. The length of line segment EF is a measure of the contrast in 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 width ΔH). If this ΔH value is small, only one specific state between the two states before and after the discoloration can exist in the room temperature range. Furthermore, if the ΔH value is large (8 to 80°C), it is easier to maintain both the pre- and post-discoloration states. Note that the reversible thermochromic compositions a and b used may be configured to produce shades of color using compositions of the same color tone, but compositions using different colors to produce a variety of color changes are preferred because they can further enhance commercial value.

[0009] The components (α), (β), and (γ) contained in the reversible thermochromic composition are specifically described below. The component (α), i.e., the electron-donating color-forming organic compound, is the component that determines the color and donates electrons to the component (β), which is the color developer, to develop color. Examples of the electron-donating color-forming organic compound include phthalide compounds, fluoran compounds, styrinoquinoline compounds, diazarhodamine lactone compounds, pyridine compounds, quinazoline compounds, and bisquinazoline compounds. Of these, phthalide compounds, fluoran compounds, styrinoquinoline compounds, and diazarhodamine lactone compounds are preferred. Examples of the phthalide compounds include diphenylmethane phthalide compounds, phenylindolyl phthalide compounds, indolyl phthalide compounds, diphenylmethane azaphthalide compounds, phenylindolyl azaphthalide compounds, and derivatives thereof. Of these, phenylindolyl azaphthalide compounds and derivatives thereof are preferred. Examples of these compounds are listed 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-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-N-p-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-N-p-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-N-i-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]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-methoxy-quinazoline, 4,4'-(ethylenedioxy)-bis[2-(4-diethylaminophenyl)quinazoline]. Fluorans may include, in addition to the above-mentioned compounds having a substituent on the phenyl group forming the xanthene ring, compounds that exhibit a blue or black color and have a substituent on the phenyl group forming the xanthene ring and also have a substituent on the phenyl group forming the lactone ring (for example, an alkyl group such as a methyl group, or a halogen atom such as a chloro group).

[0010] The component (β), i.e., the electron-accepting compound, is a compound that accepts electrons from the component (α) and functions as a color developer for the component (α). Examples of the electron-accepting compound include compounds selected from the group consisting of compounds having an active proton and their derivatives, pseudo-acidic compounds (compounds that are not acids but act as acids in the composition to cause the component (α) to develop color), and compounds having electron vacancies. Among these, compounds selected from the group consisting of compounds having an active proton are preferred. Examples of compounds having an active proton and their derivatives include compounds having a phenolic hydroxyl group 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, azole compounds and their derivatives, and 1,2,3-triazole and their derivatives. 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 monophenolic compounds to polyphenolic compounds, and further include bis- and tris-phenols, phenol-aldehyde condensation resins, and the like. Among compounds having a phenolic hydroxyl group, those having at least two or more 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, etc. Examples of metals contained in the metal salts of the compounds having the active proton include sodium, potassium, calcium, zinc, zirconium, aluminum, magnesium, nickel, cobalt, tin, copper, iron, vanadium, titanium, lead, and molybdenum.

[0011] Specific examples are listed 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 ... ) propane, 1,1-bis(4-hydroxyphenyl) n-butane, 1,1-bis(4-hydroxyphenyl) n-pentane, 1,1-bis(4-hydroxyphenyl) n-hexane, 1,1-bis(4-hydroxyphenyl) n-heptane, 1,1-bis(4-hydroxyphenyl) n-octane, 1,1-bis(4-hydroxyphenyl) n-nonane, 1,1-bis(4-hydroxyphenyl) n-decane, 1,1-bis(4-hydroxyphenyl) n-dodecane, 1,1-bis(4-hydroxyphenyl)-2-methylpropane, 1 , 1-bis(4-hydroxyphenyl)-3-methylbutane, 1,1-bis(4-hydroxyphenyl)-3-methylpentane, 1,1-bis(4-hydroxyphenyl)-2,3-dimethylpentane, 1,1-bis(4-hydroxyphenyl)-2-ethylbutane, 1,1-bis(4-hydroxyphenyl)-2-ethylhexane, 1,1-bis(4-hydroxyphenyl)-3,7-dimethyloctane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylsilyl Cyclohexane, 1-phenyl-1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)n-butane, 2,2-bis(4-hydroxyphenyl)n-pentane, 2,2-bis(4-hydroxyphenyl)n-hexane, 2,2-bis(4-hydroxyphenyl)n-heptane, 2,2-bis(4-hydroxyphenyl)n-octane, 2,2-bis(4-hydroxyphenyl)n-nonane, 2,2-bis(4-hydroxyphenyl)n-decane, 2,Examples include 2-bis(4-hydroxyphenyl)n-dodecane, 2,2-bis(4-hydroxyphenyl)ethyl propionate, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 2,2-bis(4-hydroxyphenyl)-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 compounds having a phenolic hydroxyl group are capable of exhibiting the most effective thermochromic 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-triazole and its derivatives, etc. may also be used.

[0012] The (γ) component of the reaction medium, which reversibly induces an electron transfer reaction between the (α) and (β) components within a specific temperature range, is described below. Examples of the (γ) component include alcohols, esters, ketones, ethers, and acid amides. When using the (γ) component for microencapsulation and secondary processing (described below), low-molecular-weight compounds tend to evaporate outside the capsule when subjected to high-temperature treatment. Therefore, compounds with 10 or more carbon atoms are preferably used to stably retain the component within the capsule. Effective alcohols include aliphatic monohydric saturated alcohols with 10 or more carbon atoms, such as decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, heptadecyl alcohol, octadecyl alcohol, eicosyl alcohol, and docosyl alcohol.

[0013] As the esters, esters having 10 or more carbon atoms are effective, and examples thereof include esters obtained from any combination of a monocarboxylic 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 polycarboxylic acid having an aliphatic and alicyclic or aromatic ring and a monohydric alcohol having an aliphatic and alicyclic or aromatic ring, and esters obtained from any combination of a monocarboxylic acid having an aliphatic and alicyclic or aromatic ring and a polyhydric alcohol having an aliphatic and alicyclic or aromatic ring. Specific examples thereof include esters obtained from 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, stearyl p-tert-butylbenzoate, dimyristyl phthalate, distearyl phthalate, dimyristyl oxalate, dicetyl oxalate, dicetyl malonate, dilauryl succinate, dilauryl glutarate, diundecyl adipate, dilauryl azelate, di-(n-noni) sebacate 1,18-octadecylmethylenedicarboxylate, 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 dicaprylate, xylene glycol distearate, and the like.

[0014] 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-Dimethyl Behenate Examples thereof include octyl 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.

[0015] Furthermore, in order to cause a color change with a large hysteresis characteristic in the color density-temperature curve and to impart color memory properties depending on temperature changes, carboxylic acid ester compounds having a ΔT value (melting point-cloud point) of 5°C or more and less than 50°C as described in Japanese Patent Publication No. 4-17154 may be used, 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, and distearin.

[0016] Fatty acid ester compounds obtained from an odd-numbered aliphatic monohydric alcohol having 9 or more carbon atoms and an even-numbered aliphatic carboxylic acid, 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, myristate Examples thereof 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-undelci eicosanoate, n-tridecyl eicosanoate, n-pentadecyl eicosanoate, n-nonyl behenate, n-undecyl behenate, n-tridecyl behenate, and n-pentadecyl behenate.

[0017] 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, and stearone. 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 ... acetophenone, 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.

[0018] 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.

[0019] 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 include adipic acid N-butylamide, glutaric acid N-butylamide, malonic acid N-butylamide, adipic acid N-octylamide, and adipic acid N-dodecylamide.

[0020] The reversible thermochromic composition can be dispersed in a thermoplastic resin or a thermosetting resin to be used as a thermochromic pigment, or encapsulated in microcapsules to be used as a thermochromic microcapsule pigment. The microcapsule pigment can be obtained by applying known microencapsulation techniques, 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, and spray drying. By dispersing the reversible thermochromic composition in a resin or encapsulating it in microcapsules, the reversible thermochromic material can maintain the same composition and exhibit the same effects under various usage conditions, resulting in a chemically and physically stable pigment. The pigment has an average particle size of 0.5 to 30 μm, preferably 1 to 20 μm, and more preferably 1 to 10 μm, which is effective due to its excellent color change sensitivity.

[0021] The reversible thermochromic composition is a heat-discoloring composition that exhibits the aforementioned hysteresis curve, and at least two or more compositions with different color change temperatures are used in combination in the ink composition. Therefore, by ensuring that the color density of one reversible thermochromic composition is 40% or less at the complete color development temperature of the other reversible thermochromic composition, or that the color density of one reversible thermochromic composition is 60% or more at the complete color loss temperature of the other reversible thermochromic composition, the visibility for visually distinguishing the color change state of the thermochromic composition is properly maintained and the color change is recognized. If the color density is not satisfied, the color development or discoloration of thermochromic compositions a and b becomes continuous, making it difficult to recognize the color change. Here, the color density of the other reversible thermochromic composition being 40% or less or 60% or more refers to the color density when the color density of the other reversible thermochromic composition at the complete color development temperature is taken as 100%.

[0022] This will be explained in more detail using the color density-temperature curve in Figure 2. For convenience, the reversible thermochromic composition whose hysteresis curve is in a relatively high temperature range will be referred to as reversible thermochromic composition a, and the reversible thermochromic composition whose hysteresis curve is in a relatively low temperature range will be referred to as reversible thermochromic composition b. １ , T ２ , T ３ , and T ４ are the complete color development temperature, color development initiation temperature, color disappearance initiation temperature, and complete disappearance temperature of the reversible thermochromic composition a, and t １ , t ２ , t ３ , and t ４ are the complete color development temperature, the color development initiation temperature, the color disappearance initiation temperature, and the complete disappearance temperature of the reversibly thermochromic composition b. １ >t １ and T ４ >t ４ and t ３ >T １ and t ４ >T ２ The complete color development temperature (T １ In the system where the color density of the reversible thermochromic composition b is 40% or less, the reversible thermochromic compositions a and b are T ４ In the above temperature range, all of the compounds are colorless, and when the temperature is lowered, the T ２ When the temperature reaches T １ When the temperature reaches t, the color changes completely. At this point, the color change from colorless to colored (1) is visible. Since the color concentration of the reversibly thermochromic composition b is 40% or less at this point, the color of the reversibly thermochromic material b is difficult to visually recognize. １ When the temperature reaches 100°C, the color develops completely, and the color tone of color (2) mixed with color (1) is visible.

[0023] Next, the complete decolorization temperature (t ４ In the system where the color density of the reversible thermochromic composition a is 60% or more, the reversible thermochromic compositions a and b are t １ In the temperature range below, it becomes colored (2), and when the temperature is increased from this state, t３ When the temperature reaches t, the reversible thermochromic composition b starts to lose its color, and t ４ When the temperature reaches T , the color is completely lost and the color (1) is obtained. At this point, the color concentration of the reversibly thermochromic composition a is 60% or more, so that the color of the reversibly thermochromic material a is easily visible. ４ When the temperature reaches this value, the reversible thermochromic compositions a and b completely lose their color, and a color change from colored (1) to colorless is visually observed. Therefore, by using the reversible thermochromic compositions a and b that exhibit the hysteresis characteristics shown in Figure 2, a clear and highly visible color change between the three states of colorless, colored (1), and colored (2) is visually observed. Note that by adding a non-color-changing colorant to the vinyl chloride resin, any of the reversible thermochromic compositions, or any of the reversible thermochromic pigments, a color change between colored (1), colored (2), and colored (3) is visually observed.

[0024] Furthermore, even when the hysteresis curves of the reversible thermochromic compositions a and b as shown in Figure 3 do not overlap each other, the color change of multiple colors is visible. １ >t １ and T ４ >t ４ and T １ >t ４ During the temperature drop process, which satisfies the above-mentioned conditions, three color changes can be visually recognized: from colorless to colored (1) and then from colored (1) to colored (2), as well as color changes from colored (1), colored (2), and colored (3) when a non-color-changing colorant is added. During the temperature rise process, three color changes can be visually recognized: from colored (2) to colored (1) and then from colored (1) to colorless, as well as color changes from colored (3), colored (2), and colored (1) when a non-color-changing colorant is added.

[0025] Here, the complete decolorization temperature (T ４ ) is in the temperature range of 25°C to 37°C, and the complete color development temperature (T １ When the temperature (T ) of the reversible thermochromic composition a is in the range of 20°C or higher and lower than 25°C, the color can be changed by touching it with the body heat, and the color change can be more easily recognized visually. ４ ) is in the temperature range of 26°C to 37°C, and the complete color development temperature (T１ ) is in a temperature range of 25°C or more and less than 26°C, and the complete decolorization temperature (t ４ When the temperature is 24°C or less, the color change due to the body heat of the hand or the like and various color changes can be visually recognized by using a cooling means in combination, and this is highly practical.

[0026] In addition, the hysteresis curve of one reversible thermochromic composition as shown in Figure 4 may be such that the hysteresis curve of reversible thermochromic composition b is located inside the hysteresis curve of reversible thermochromic composition a. For convenience, the reversible thermochromic composition whose hysteresis curve is in a relatively wide temperature range will be referred to as reversible thermochromic composition a, and the reversible thermochromic composition whose hysteresis curve is in a relatively narrow temperature range will be referred to as reversible thermochromic composition b. In this case, specifically, t １ T １ higher than t ４ T ４ In this case, T ４ In the above temperature range, it becomes colorless, and when the temperature is lowered, it becomes colorless. ２ When the temperature reaches t, the reversible thermochromic composition b starts to develop color, and １ When the temperature reaches T, the color develops completely. At this point, the color change from colorless to colored (1) is visible. ２ When the temperature reaches T １ When the temperature reaches t, the color develops completely, and the color tone of color (2) mixed with color (1) is visible. ３ When the temperature reaches t, the reversible thermochromic composition b starts to lose its color, and t ４ When the temperature reaches T, the color completely disappears, and the color change from colored (2) to colored (3) is visible. ３ When the temperature reaches T ４When the temperature reaches 100°C, the color is completely lost, and a color change from colored (3) to colorless is visually recognized. Therefore, by using the reversible thermochromic compositions a and b that exhibit the hysteresis characteristics shown in Figure 4, four color changes of colorless, colored (1), colored (2), and colored (3) can be visually recognized, and if necessary, by adding a non-color-changing colorant to the vinyl chloride resin, any of the reversible thermochromic compositions, or any of the reversible thermochromic pigments, the color changes of colored (1), colored (2), colored (3), and colored (4) can be visually recognized. In addition, the t １ is 25°C or higher, ΔH ｂ is 0.5 to 5°C, and t ４ When the temperature is 36°C to 37°C or lower, the color exhibited by composition b disappears when touched with a finger or the like at body temperature (36°C to 37°C), but remains in a colored state at room temperatures below that temperature, so that from the first color, a second color appears when touched with a finger or the like at body temperature, a third color appears when heated by friction or with hot water, etc., a fourth color appears when the temperature drops to room temperature, and the composition can be returned to the first color by room temperature, tap water, ice water, etc. As described above, various color changes can be easily exhibited and visible by heat or cold means in the temperature range of the living environment, and no special color-changing device or the like is required.

[0027] In addition, in a system in which the hysteresis curve of the reversible thermochromic composition a and the hysteresis curve of the reversible thermochromic composition b are contained within the hysteresis curve of the reversible thermochromic composition a as shown in FIG. 4, a large hysteresis width (ΔH ａ ) and the ΔH of the thermochromic composition a. ａ Smaller hysteresis width (ΔH ｂ ) and a thermochromic composition b that changes color within the color-changing temperature range of the thermochromic composition a, and by satisfying the specific temperature characteristics between the thermochromic compositions a and b, it is possible to effectively achieve highly sensitive color-changing properties in a specific temperature range, color memory, multicolor color-changing properties, unexpected color changes, and the appeal of color changes. ａBy specifying the value to be in the range of 10 to 50°C, preferably 15 to 35°C, the color can be developed or decolorized at ambient temperature or by simple heat or cold means, and the appearance resulting from the color change in the colored or decolorized state can be alternately stored and maintained in the room temperature range. ａ If the ΔH value is less than 10°C, the color memory function is insufficient, and if it exceeds 50°C, the color memory function is achieved, but it is difficult to achieve the color memory function by changing the temperature of the living environment or by simple heat or cold means. ｂ The ΔH value of thermochromic composition b is in the range of 0.5 to 20°C, preferably 0.5 to 12°C, and is in the range of the color change temperature of the thermochromic composition a. ｂ By specifying the value within the above range, the color is sensitive to temperature changes, and when the application of heat or cold required for the change is removed, the color quickly returns to its original color, and the color change is within ΔH ａ The ΔH ａ The color of the thermochromic composition a stored in the region is mixed with the color of the thermochromic composition a, and various color changes are visually observed. More specifically, a large hysteresis width (ΔH ａ ) and changes color. ４ is 28℃ to 70℃, T １ By satisfying the range of -20°C to 23°C, the change in appearance accompanying the color change in the temperature range of the living environment can be suitably visually recognized in the normal temperature range, and a small hysteresis width (ΔH ｂ t of thermochromic composition b which changes color by exhibiting １ is 25°C or higher, and ΔH ｂ When the temperature satisfies the range of 0.5 to 12°C, the change in appearance due to the color change caused by body temperature can be easily seen.

[0028] Pigment A containing the reversible thermochromic composition a and pigment B containing the reversible thermochromic composition b are dispersed in a vinyl chloride resin molding resin and molded to produce a thermosensitive multicolor-changing toy. 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 (α), (β), and (γ), and is included in an amount of 0.3 to 24 wt %, preferably 0.8 to 16 wt %. Among the light stabilizers, ultraviolet absorbers effectively block ultraviolet light contained in sunlight, etc., to prevent photodegradation caused by the excited state due to the photoreaction of component (α). Antioxidants, singlet oxygen quenchers, superoxide anion quenchers, ozone quenchers, etc. inhibit oxidation reactions. The light stabilizers may be used alone or in combination. The light stabilizer may be encapsulated in a microcapsule together with the reversible thermochromic composition, or may be encapsulated in a microcapsule and added to the molding resin.

[0029] The thermosensitive multicolor-changing toy is a hollow toy made of vinyl chloride resin. Vinyl chloride resin is inexpensive and widely used as a general-purpose resin. It is also used for toys because of its excellent properties and the fact that it can easily be made flexible by adding plasticizers. Various additives such as conventional stabilizers, fillers, flame retardants, lubricants, impact modifiers, and plasticizers can be added to vinyl chloride resin as needed depending on the purpose. Examples of stabilizers include lead-based stabilizers such as tribasic lead sulfate, dibasic lead phosphite, basic lead sulfite, and lead silicate; metal soap-based stabilizers derived from metals such as potassium, magnesium, barium, zinc, cadmium, and lead and fatty acids such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, ricinoleic acid, linoleic acid, and behenic acid; organotin-based stabilizers having an alkyl group, an ester group, a fatty acid group, a maleic acid group, a sulfide-containing group, and the like; complex metal soap-based stabilizers such as Ba-Zn-based, Ca-Zn-based, Ba-Ca-Sn-based, Ca-Mg-Sn-based, Ca-Zn-Sn-based, Pb-Sn-based, and Pb-Ba-Ca-based stabilizers; and stabilizers derived from metal groups such as barium and zinc and 2-ethylhexanoic acid, isodecaacetic acid, and the like. Examples of metal-based stabilizers include metal salt-based stabilizers derived from two or more organic acids, such as branched fatty acids such as carboxylic acid and trialkylacetic acid, unsaturated fatty acids such as oleic acid, ricinoleic acid, and linoleic acid, alicyclic acids such as naphthenic acid, and aromatic acids such as phenolic acid, benzoic acid, salicylic acid, and their substituted derivatives; and metal salt liquid stabilizers obtained by dissolving these stabilizers in organic solvents such as petroleum hydrocarbons, alcohols, and glycerin derivatives and further blending them with stabilizing aids such as phosphites, epoxy compounds, color-development inhibitors, transparency improvers, light stabilizers, antioxidants, bleed-out inhibitors, and lubricants. Other examples include non-metallic stabilizers such as epoxy resins, epoxy compounds such as epoxidized fatty acid alkyl esters, and organic phosphites, which may be used singly or in combination. The amount of stabilizer added is not particularly limited, but is preferably 1 to 15 parts by weight, and more preferably 1 to 8 parts by weight, per 100 parts by weight of vinyl chloride resin.By making the amount 1 part by mass or more, it is possible to suppress thermal decomposition during processing, and by making the amount 15 parts by mass or less, it is possible to prevent a decrease in the mechanical properties of the molded body (toy).

[0030] Examples of fillers that can be used include inorganic fillers such as carbonates (e.g., talc, heavy calcium carbonate, precipitated calcium carbonate, and colloidal calcium carbonate), aluminum hydroxide, magnesium hydroxide, titanium oxide, clay, mica, wollastonite, zeolite, silica, zinc oxide, magnesium oxide, carbon black, graphite, glass beads, glass fiber, carbon fiber, and metal fiber, as well as organic fibers (e.g., polyamide), and these can be used alone or in combination of two or more. The amount of filler added is not particularly limited, but is preferably 1 to 150 parts by weight, and more preferably 10 to 100 parts by weight, per 100 parts by weight of vinyl chloride resin. An amount of 1 part by weight or more can impart appropriate rigidity to the molded body (toy), while an amount of 150 parts by weight or less can prevent a decrease in the flexibility of the molded body (toy).

[0031] Examples of flame retardants that can be used include metal hydroxides, bromine-based compounds, triazine ring-containing compounds, zinc compounds, phosphorus-based compounds, halogen-based flame retardants, silicon-based flame retardants, intumescent flame retardants, and antimony oxide. These can be used alone or in combination of two or more. There are no particular restrictions on the amount of flame retardant added, but it is preferably 1 to 150 parts by mass, and more preferably 10 to 100 parts by mass, per 100 parts by mass of vinyl chloride resin. By adding an amount of 1 part by mass or more, the flame retardancy of the molded article (toy) can be improved, and by adding an amount of 150 parts by mass or less, it is possible to prevent a decrease in the flexibility of the molded article (toy).

[0032] Examples of lubricants include pure hydrocarbon lubricants such as liquid paraffin, natural paraffin, microwax, synthetic paraffin, and low-molecular-weight polyethylene; halogenated hydrocarbon lubricants; fatty acid lubricants such as higher fatty acids and oxyfatty acids; fatty acid amide lubricants such as fatty acid amides and bisfatty acid amides; ester lubricants such as lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids such as glycerides, polyglycol esters of fatty acids, and fatty alcohol esters of fatty acids (ester waxes); as well as metal soaps, fatty alcohols, polyhydric alcohols, polyglycols, polyglycerols, partial esters of fatty acids and polyhydric alcohols, and partial esters of fatty acids and polyglycols or polyglycerols. These can be used alone or in combination of two or more. The amount of lubricant added is not particularly limited, but is preferably 0.1 to 15 parts by weight, and more preferably 0.1 to 5 parts by weight, per 100 parts by weight of vinyl chloride resin. Adding 0.1 parts by weight or more can reduce adhesion of the resin composition to the molding machine, while adding 15 parts by weight or less can prevent a decrease in processability.

[0033] When an impact resistance modifier is compounded, examples of suitable rubbers include chlorinated polyethylene, polybutadiene, polyisoprene, polychloroprene, fluororubber, styrene-butadiene copolymer rubber, acrylonitrile-styrene-butadiene copolymer rubber, methyl methacrylate-styrene-butadiene copolymer rubber, acrylic core-shell rubbers such as acrylate-methacrylate copolymers, silicone core-shell rubbers such as silicone-acrylate-methacrylate copolymers and silicone-acrylate-acrylonitrile-styrene copolymers, styrene-butadiene-styrene block copolymer rubber, styrene-isoprene-styrene block copolymer rubber, styrene-ethylene-butylene-styrene block copolymer rubber, ethylene-propylene copolymer rubber, and ethylene-propylene-diene copolymer rubber (EPDM). Examples of suitable dienes for EPDM include 1,4-hexadiene, dicyclopentadiene, methylene norbornene, ethylidene norbornene, and propenyl norbornene. These impact resistance modifiers can be used alone or in combination of two or more. The amount of impact resistance modifier added is not particularly limited, but is preferably 1 to 20 parts by mass, and more preferably 1 to 15 parts by mass, per 100 parts by mass of vinyl chloride resin. By adding an amount of 1 part by mass or more, it is possible to improve the impact strength of the molded article (toy), and by adding an amount of 20 parts by mass or less, it is possible to prevent deterioration in the appearance of the molded article (toy).

[0034] As the plasticizer, plasticizers for vinyl chloride resins can be appropriately used, and examples thereof include phthalate ester plasticizers such as di-2-ethylhexyl phthalate (DOP), di-normal octyl phthalate, dibutyl phthalate, diisononyl phthalate (DINP), and butyl benzyl phthalate; phosphate ester plasticizers such as tricresyl phosphate and tri-2-ethylhexyl phosphate; adipate ester plasticizers such as di-2-ethylhexyl adipate and diisononyl adipate; sebacate ester plasticizers such as di-2-ethylhexyl sebacate; azelaate ester plasticizers such as di-2-ethylhexyl azelate; and tri-2-ethylhexyl trimellitate. Examples of such plasticizers include trimellitic acid ester-based plasticizers, polyester-based plasticizers, benzoic acid ester-based plasticizers such as di-2-ethylhexyl benzoate, diethylene glycol dibenzoate, and 2,2,4-trimethyl-1,3-pentanediol isobutyrate benzoate, citrate ester-based plasticizers such as acetyl tributyl citrate and acetyl tri-2-ethylhexyl citrate, glycolic acid ester-based plasticizers, chlorinated paraffin-based plasticizers, chlorinated fatty acid ester-based plasticizers, epoxy-based plasticizers, and texanol isobutyrate. Of these, diisononyl adipate, acetyl tributyl citrate, and acetyl tri-2-ethylhexyl citrate, which are highly safe, are preferably used.

[0035] In addition, a release agent, a flow improver, an antistatic agent, a surfactant, an antifogging agent, an antibacterial agent, a foaming agent, and the like may be optionally blended depending on the purpose, as long as the effects of the present invention are not impaired.

[0036] The thermosensitive multicolor-changing toy of the present invention is a toy with a hollow interior formed using vinyl chloride resin. Compared to solid toys filled with resin to the center (interior), the color change in response to temperature is more sensitive and clear. The multicolor change in the resin containing multiple reversible thermochromic compositions used in the present invention is highly visible. The hollow portion may be either connected to the outside or not. The thermosensitive multicolor-changing toy of the present invention may also have a hollow structure defined by vinyl chloride resin containing multiple reversible thermochromic compositions and other materials. Specifically, the hollow structure may be defined by a combination of vinyl chloride resin containing multiple reversible thermochromic compositions with other materials such as a color-non-changing resin, metal, or wood. In the present invention, a hollow structure may also be defined when the hollow portion is not completely isolated from the outside and has an opening. This is because, if the opening is small, it may be possible to float it on water, for example, to limit airflow between the hollow portion and the outside. The hollow portion of the toy is not connected to the outside, and the volume ratio of the vinyl chloride resin to the hollow portion is 85:15 to 10:90, preferably 75:25 to 15:85, and more preferably 65:35 to 20:80. This allows for a sharp and clear color change, excellent visibility of the multicolor color change, and the toy floats in water. The toy exhibits unexpected color changes in response to temperature changes, making it suitable for use in hot and cold water bathtubs and other play environments. The toy does not sink in bathtubs and other environments, allowing for safer play. To ensure water buoyancy, the toy's apparent specific gravity must be less than 1. By forming an uneven surface on the temperature-sensitive multicolor-changing toy, complex color changes can be achieved, resulting in a wide variety of toys. Examples of the toy's form include dolls, animal toys, vehicle toys, building and scenery toys, cooking toys, accessories, costumes, and other small toys.

[0037] Furthermore, a toy set can be created by combining the temperature-sensitive, multi-color-changing toy of the present invention with a temperature-changing member that changes the temperature of part or all of the toy. This color-changing member is not particularly limited as long as it can change the temperature of part or all of the toy, i.e., heat or cool. For example, it can be a dropper-shaped member made of flexible resin that contains a liquid and can spray the liquid by applying external pressure. Such a member can be used as both a heating member and a cooling member by changing the liquid contained therein to cold or hot water. Furthermore, when the toy is used in a bathtub or the like, it can easily be converted into either a cooling member or a heating member. Furthermore, other temperature-changing members can be used, such as a bucket-shaped container that can be filled with liquid and immersed entirely in the toy, a brush that can apply cold or hot water to the member, or a container with both ends open that sprays water from the upper opening when the lower opening is pressed against the water surface. Other temperature-changing members that can be used include a cooling spray and an electric heater.

[0038] Examples are shown below, but the present invention is not limited to these examples. In the examples, parts are parts by mass. To determine the discoloration temperature, a measurement sample was placed in the measurement section of a color difference meter (TC-3600 color difference meter, manufactured by Tokyo Denshoku Co., Ltd.), the sample section was heated and cooled at a rate of 2°C / min, and the brightness value was measured as the color density at each temperature, and a color density-temperature curve was created. From the color density-temperature curve, each temperature, hysteresis width, and color density were determined. Example 1 Preparation of a Thermosensitive Multicolor-Changing Toy Thermochromic pigment A (ΔH ) was prepared by microencapsulating a reversible thermochromic composition comprising 1.5 parts of 9-ethyl-(3-methylbutyl)amino-spiro[12H-benzo[a]xanthen-12,1'(3H)-isobenzofuran]-3'-one as the component (α), 5 parts of 2,2-bis(4'-hydroxyphenyl)hexafluoropropane as the component (β), and 50 parts of neopentyl stearate as the component (γ) by an interfacial polymerization method. ａ : 18 ° C, T １ : 10 ° C, T ２ : 16 ° C, T ３ : 27 ° C, T ４: 35°C, reversible color change from pink to colorless) 17.0 parts, thermochromic pigment B (ΔH: 35°C, reversible color change from pink to colorless) in which a reversible thermochromic composition consisting of 1.2 parts of 3,3-bis(2-ethoxy-4-diethylaminophenyl)-4-azaphthalide as the (α) component, 6 parts of 4,4'-(2-ethylhexylidene)bisphenol as the (β) component, 30 parts of cetyl decanoate and 20 parts of stearyl decanoate as the (γ) component is encapsulated in microcapsules by an interfacial polymerization method. ｂ : 3.5 ° C, t １ : 18 ° C, t ２ : 24 ° C, t ３ : 21 ° C, t ４ A thermochromic PVC plastisol was prepared by dispersing 14.0 parts of a non-thermochromic colorant C (yellow fluorescent pigment (product name: Epocolor FP-117, manufactured by Nippon Shokubai Co., Ltd.) at 28°C, reversible color change from blue-green to colorless) and 5.0 parts of a non-thermochromic colorant C in PVC plastisol. The color density of thermochromic pigment A at the complete color development temperature of thermochromic pigment B was 0%, and the color density of thermochromic pigment A at the complete decolorization temperature of thermochromic pigment B was 80%. The thermochromic PVC plastisol was slush molded in a mold for a dinosaur-shaped object with an irregular surface to obtain a hollow animal toy. The ratio of the volume of the vinyl chloride resin to the volume of the hollow portion of the toy was 20:80. The toy exhibited a dark green color at temperatures below 10°C. When the toy was successively immersed in water at 27°C to 28°C, water above 35°C, water at 16°C to 18°C, and water below 10°C, it rapidly and clearly changed color to red, yellow, green, and dark green, respectively. Next, when 35°C water was applied to the dark green toy surface using a brush, the color began to change from the convex parts to red, then to yellow, and the toy turned yellow. When water at 16°C to 18°C ​​was applied to the yellow toy surface, the color began to change to green from the convex parts, and the toy turned green. Furthermore, when water below 10°C was applied, the toy turned dark green. Since the toy exhibited the above-described color change behavior with temperature change, the four color changes of dark green, red, yellow, and green could be repeatedly reproduced and visually observed by changing the ambient temperature or by using familiar thermal methods such as ice water, tap water, or body temperature, imparting a charming and unexpected color change.

[0039] Example 2: Preparation of a thermosensitive multicolor toy Thermochromic pigment A (ΔH ) was prepared by microencapsulating a reversible thermochromic composition comprising 0.8 parts of 3,3-bis(2-ethoxy-4-diethylaminophenyl)-4-azaphthalide as the component (α), 5 parts of 4,4'-(2-ethylhexylidene)bisphenol and 1 part of 4,4'-(1-phenylethylidene)bisphenol as the component (β), and 50 parts of neopentyl stearate as the component (γ) by an interfacial polymerization method. ａ : 16 ° C, T １ : 14 ° C, T ２ : 16 ° C, T ３ : 28 ° C, T ４ Thermochromic pigment B (ΔH: 34°C, reversible color change from cyan to colorless) 15.0 parts, (α) component 1.5 parts of 9-ethyl-(3-methylbutyl)amino-spiro[12H-benzo[a]xanthene-12,1'(3H)-isobenzofuran]-3'-one, (β) component 6 parts of 4,4'-(2-ethylhexylidene)bisphenol, (γ) component 30 parts of cetyl decanoate and 20 parts of stearyl decanoate, which are microencapsulated by an interfacial polymerization method. ｂ : 2 ° C, t １ : 21 ° C, t ２ : 25 ° C, t ３ : 22 ° C, t ４A thermochromic PVC plastisol was prepared by dispersing 20.0 parts of Thermochromic Pigment A (reversible color change from magenta to colorless at 28°C) in PVC plastisol. The color density of Thermochromic Pigment A at the complete color development temperature of Thermochromic Pigment B was 0%, and the color density of Thermochromic Pigment A at the complete decolorization temperature of Thermochromic Pigment B was 95%. Using the thermochromic PVC plastisol, a vehicle toy was obtained using a mold with an automobile-shaped shape having an uneven surface. The ratio of the volume of the vinyl chloride resin to the volume of the hollow portion of the toy was 75:25. The toy exhibited a purple color at temperatures below 14°C. When immersed sequentially in water at 27-28°C, water above 34°C, water between 16-18°C, and water below 14°C, the toy exhibited a sharp and clear color change to cyan, white, magenta, and purple, respectively. Next, when water at 35°C was applied to the purple toy surface, the color began to change from the convex parts to cyan and then to white, and the toy turned white. When water at 16°C to 18°C ​​was applied to the white toy surface, the color began to change to magenta from the convex parts, and the toy turned magenta. Furthermore, when water at 10°C or below was applied to the toy, it turned purple. Since the toy exhibits the above-mentioned color change behavior in response to temperature changes, it is possible to repeatedly reproduce and visually display the four color changes of purple, cyan, white, and magenta by using familiar thermal methods such as environmental temperature changes, ice water, tap water, or body temperature, thereby imparting an appealing and unexpected color change.

[0040] Example 3: Preparation of a thermosensitive multicolor toy Thermochromic pigment A (ΔH ) was prepared by microencapsulating a reversible thermochromic composition comprising 0.8 parts of 3,3-bis(2-ethoxy-4-diethylaminophenyl)-4-azaphthalide as the component (α), 5 parts of 4,4'-(2-ethylhexylidene)bisphenol and 1 part of 4,4'-(1-phenylethylidene)diphenol as the component (β), and 50 parts of neopentyl stearate as the component (γ) by an interfacial polymerization method. ａ : 16 ° C, T １ : 14 ° C, T ２ : 16 ° C, T ３ : 28 ° C, T ４Thermochromic pigment B (ΔH: 34°C, reversible color change from cyan to colorless) 17.0 parts, (α) component 1.5 parts of 4-[2,6-bis(2-ethoxyphenyl)-4-pyridinyl]-N,N-dimethylbenzenamine, (β) component 4.8 parts of 4'-tert-butyl-2,4-dihydroxybenzophenone and 1.2 parts of 4,4'-(1-phenylethylidene)bisphenol, (γ) component 30 parts of cetyl decanoate and 20 parts of stearyl decanoate, microencapsulated by an interfacial polymerization method. ｂ : 1.5 ° C, t １ : 21 ° C, t ２ : 25 ° C, t ３ : 21 ° C, t ４A thermochromic PVC plastisol was prepared by dispersing 16.0 parts of a non-thermochromic colorant C (pink fluorescent pigment (product name: Epocolor FP-1000N, manufactured by Nippon Shokubai Co., Ltd.) at 28°C, reversible color change from yellow to colorless) and 1.8 parts of a non-thermochromic colorant C (pink fluorescent pigment (product name: Epocolor FP-1000N, manufactured by Nippon Shokubai Co., Ltd.)) in PVC plastisol. The color density of thermochromic pigment A at the complete color development temperature of thermochromic pigment B was 0%, and the color density of thermochromic pigment A at the complete decolorization temperature of thermochromic pigment B was 95%. The thermochromic PVC plastisol was rotationally molded in a beetle-shaped mold with an uneven surface to obtain an insect toy. The ratio of the volume of the vinyl chloride resin to the volume of the hollow portion of the toy was 65:35. The toy was green at temperatures below 14°C, and when immersed sequentially in water at 27°C to 28°C, water above 34°C, water at 16°C to 18°C, and water below 14°C, it rapidly and clearly changed color to blue, pink, orange, and green, respectively. Next, when 35°C water was applied to the green toy surface using a brush, the color began to change from the convex parts to blue and then to pink, and the toy turned pink. When water at 16°C to 18°C ​​was applied to the pink toy surface, the color began to change from the convex parts to orange, and finally turned orange. Furthermore, when water at 10°C or below was applied, the toy turned green. Since the toy exhibited the above-mentioned color change behavior with temperature change, the four color changes of green, blue, pink, and orange could be repeatedly reproduced and visually visualized by changing the ambient temperature or by using familiar thermal methods such as ice water, tap water, or body temperature, imparting a charming and unexpected color change.

[0041] Example 4: Preparation of a thermosensitive multicolor toy Thermochromic pigment A (ΔH ) was prepared by microencapsulating a reversible thermochromic composition comprising 1.5 parts of 9-ethyl-(3-methylbutyl)amino-spiro[12H-benzo[a]xanthen-12,1'(3H)-isobenzofuran]-3'-one as the (α) component, 3 parts of 4,4'-(2-methylpropylidenebisphenol, 2 parts of 4,4'-(1-phenylethylidene)bisphenol, and 2 parts of 4,4'-(2-ethylhexylidene)bisphenol as the (β) component, and 50 parts of neopentyl stearate as the (γ) component, by an interfacial polymerization method. ａ : 16.5℃, T１ : 13 ° C, T ２ : 16 ° C, T ３ : 27 ° C, T ４ Thermochromic pigment B (ΔH: 35°C, reversible color change from pink to colorless) in which 17.0 parts of a reversible thermochromic composition consisting of 1.2 parts of 3,3-bis(2-ethoxy-4-diethylaminophenyl)-4-azaphthalide as the (α) component, 6 parts of 4,4'-(2-ethylhexylidene)bisphenol as the (β) component, 30 parts of cetyl decanoate and 20 parts of stearyl decanoate as the (γ) component are encapsulated in microcapsules by an interfacial polymerization method. ｂ : 3.5 ° C, t １ : 18 ° C, t ２ : 24 ° C, t ３ : 21 ° C, t ４A thermochromic PVC plastisol was prepared by dispersing 14.0 parts of a non-thermochromic colorant C (yellow fluorescent pigment (trade name: Epocolor FP-117, manufactured by Nippon Shokubai Co., Ltd.) at 28°C, reversible color change from blue-green to colorless), 5.0 parts of a non-thermochromic colorant C (yellow fluorescent pigment (trade name: Epocolor FP-117, manufactured by Nippon Shokubai Co., Ltd.)), and 0.7 parts of acetyl tributyl citrate as a plasticizer in PVC plastisol. The color density of thermochromic pigment A at the complete color development temperature of thermochromic pigment B was 0%, and the color density of thermochromic pigment A at the complete decolorization temperature of thermochromic pigment B was 80%. The thermochromic PVC plastisol was slush molded in a mold for a miniature car tire to form a hollow body, which was then attached to the tire of the miniature car to obtain a toy car. The ratio of the volume of the vinyl chloride resin in the tire to the volume of the hollow portion was 20:80. The toy exhibited a dark green color at temperatures below 13°C. When the toy was successively immersed in water at 27°C to 28°C, water above 35°C, water at 16°C to 18°C, and water below 13°C, it rapidly and clearly changed color to red, yellow, green, and dark green, respectively. Next, when water at 35°C filled in a container-shaped temperature-changing member was applied to the surface of the toy, which was still dark green, the color began to change to red and then yellow, and the toy turned yellow. When water at 16°C to 18°C ​​was applied to the yellow toy surface, the color began to change to green, and the toy turned green. Furthermore, when water at 13°C or below was applied, the toy turned dark green. Because the toy exhibited the above-described color change behavior with temperature changes, the four color changes of dark green, red, yellow, and green could be repeatedly reproduced and visually visualized by using familiar thermal methods such as environmental temperature changes, ice water, tap water, and body temperature, imparting a charming and unexpected color change.

[0042] Example 5: Preparation of a thermosensitive multicolor toy Thermochromic pigment A (ΔH ) was prepared by microencapsulating a reversible thermochromic composition comprising 0.8 parts of 3,3-bis(2-ethoxy-4-diethylaminophenyl)-4-azaphthalide as the component (α), 3 parts of 4,4'-(2-methylpropylidene)bisphenol, 2 parts of 4,4'-(2-ethylhexylidene)bisphenol, and 1 part of 4,4'-(1-phenylethylidene)bisphenol as the component (β), and 50 parts of neopentyl stearate as the component (γ) by an interfacial polymerization method. ａ : 16 ° C, T １ : 14 ° C, T ２ : 16 ° C, T ３ : 28 ° C, T ４ Thermochromic pigment B (ΔH: 34°C, reversible color change from cyan to colorless) 15.0 parts, (α) component 1.5 parts of 9-ethyl-(3-methylbutyl)amino-spiro[12H-benzo[a]xanthen-12,1'(3H)-isobenzofuran]-3'-one, (β) component 6 parts of 4,4'-(2-ethylhexylidene)bisphenol, (γ) component 30 parts of cetyl decanoate and 20 parts of stearyl decanoate, which are microencapsulated by an interfacial polymerization method. ｂ : 2 ° C, t １ : 21 ° C, t ２ : 25 ° C, t ３ : 22 ° C, t ４A thermochromic PVC plastisol was prepared by dispersing 20.0 parts of PVC plastisol (reversible color change from magenta to colorless at 28°C) and 0.7 parts of acetyl tributyl citrate as a plasticizer. The color density of thermochromic pigment A at the complete color development temperature of thermochromic pigment B was 0%, and the color density of thermochromic pigment A at the complete decolorization temperature of thermochromic pigment B was 95%. The thermochromic PVC plastisol was slush molded in a dinosaur-shaped mold with an irregular surface to obtain a hollow animal toy. The ratio of the volume of the vinyl chloride resin to the volume of the hollow portion of the toy was 20:80. The toy exhibited a purple color at temperatures below 14°C. When the toy was successively immersed in water at 28°C, water above 34°C, water between 16°C and 21°C, and water below 14°C, it rapidly and clearly changed color to cyan, white, magenta, and purple, respectively. Next, when water at 34°C was applied to the purple toy surface, the color began to change from the convex parts to cyan and then to white, and the toy turned white. When water at 16°C to 21°C was applied to the white toy surface, the color began to change to magenta from the convex parts, and the toy turned magenta. Furthermore, when water at 10°C or below was applied, the toy turned purple. Because the toy exhibited the above-described color change behavior with temperature changes, the four color changes of purple, cyan, white, and magenta could be repeatedly reproduced and visually visualized by changing the ambient temperature or by using familiar thermal methods such as ice water, tap water, or body temperature, imparting a charming and unexpected color change.

[0043] Example 6: Preparation of a toy set A toy set was obtained, comprising the temperature-sensitive, multi-color-changing toy obtained in Example 5, a bucket-shaped container as a temperature-changing member in which the entire toy can be immersed in cold or hot water, a brush for applying cold or hot water to the toy, a container with open ends that sprays water from the upper opening when the lower opening is pressed against the water surface, and a floating member for floating the temperature-sensitive, multi-color-changing toy on the water surface. The toy set was able to change color by immersing the temperature-sensitive, multi-color-changing toy in a bucket filled with cold or hot water indoors, or by contacting the surface of the toy with a brush with cold or hot water attached, and repeatedly reproducing the four color changes of purple, cyan, white, and magenta, giving the toy a unique and unexpected color change. In addition, a temperature-sensitive, multi-color color-changing toy that has previously been color-changed purple in the bathtub with cold water is placed on a floating member and floated in the bathtub, and then the container has openings on both ends, and when the lower opening is pressed against the water surface, water is sprayed from the upper opening.By pressing the container against the water surface, water is sprayed from the upper opening and comes into contact with the surface of the toy, causing it to change color, and the four color changes of purple, cyan, white, and magenta can be repeatedly and visually reproduced, giving the toy a unique and unexpected color change.

[0044] Comparative Example 1 Preparation of a Thermosensitive Multicolor-Changing Toy A thermochromic pigment A (ΔH ) was prepared by microencapsulating a reversible thermochromic composition comprising 1.5 parts of 9-ethyl-(3-methylbutyl)amino-spiro[12H-benzo[a]xanthen-12,1'(3H)-isobenzofuran]-3'-one as the (α) component, 3 parts of 4,4'-(2-methylpropylidenebisphenol, 2 parts of 4,4'-(1-phenylethylidene)bisphenol, and 2 parts of 4,4'-(2-ethylhexylidene)bisphenol as the (β) component, and 50 parts of neopentyl stearate as the (γ) component, by an interfacial polymerization method. ａ : 16.5℃, T １ : 13 ° C, T ２ : 16 ° C, T ３ : 27 ° C, T ４Thermochromic pigment B (ΔH: 35°C, reversible color change from pink to colorless) in which 17.0 parts of a reversible thermochromic composition consisting of 1.2 parts of 3,3-bis(2-ethoxy-4-diethylaminophenyl)-4-azaphthalide as the (α) component, 6 parts of 4,4'-(2-ethylhexylidene)bisphenol as the (β) component, 20 parts of cetyl decanoate and 30 parts of stearyl decanoate as the (γ) component are encapsulated in microcapsules by an interfacial polymerization method. ｂ : 4.5 ° C, t １ : 24 ° C, t ２ : 26 ° C, t ３ : 28 ° C, t ４ A thermochromic PVC plastisol was prepared by dispersing 14.0 parts of a non-thermochromic colorant C (yellow fluorescent pigment (product name: Epocolor FP-117, manufactured by Nippon Shokubai Co., Ltd.) at 31°C, reversible color change from blue-green to colorless) and 5.0 parts of a non-thermochromic colorant C in PVC plastisol. The color density of thermochromic pigment A at the complete color development temperature of thermochromic pigment B was 0%, and the color density of thermochromic pigment A at the complete decolorization temperature of thermochromic pigment B was 40%. The thermochromic PVC plastisol was slush molded in a dinosaur-shaped mold with an irregular surface to obtain a hollow animal toy. The ratio of the volume of the vinyl chloride resin to the volume of the hollow portion of the toy was 20:80. The toy was dark green at temperatures below 13°C, and when it was successively immersed in water between 27°C and 31°C, water above 35°C, water between 16°C and 24°C, and water below 13°C, it changed color to red, yellow, green, and dark green, respectively. However, when it changed color from dark green to red, no clear red color was visible because the color development density of the thermochromic pigment A was low.

[0045] Comparative Example 2 Preparation of a Thermosensitive Multicolor-Changing Toy Thermochromic pigment A (ΔH ) was prepared by microencapsulating a reversible thermochromic composition comprising 0.8 parts of 3,3-bis(2-ethoxy-4-diethylaminophenyl)-4-azaphthalide as the component (α), 3 parts of 4,4'-(2-methylpropylidene)bisphenol, 2 parts of 4,4'-(2-ethylhexylidene)bisphenol, and 1 part of 4,4'-(1-phenylethylidene)bisphenol as the component (β), and 50 parts of neopentyl stearate as the component (γ) by an interfacial polymerization method.ａ : 16.5℃, T １ : 13 ° C, T ２ : 16 ° C, T ３ : 28 ° C, T ４ Thermochromic pigment B (ΔH: 34°C, reversible color change from cyan to colorless) 15.0 parts, (α) component 1.5 parts of 9-ethyl-(3-methylbutyl)amino-spiro[12H-benzo[a]xanthene-12,1'(3H)-isobenzofuran]-3'-one, (β) component 6 parts of 4,4'-(2-ethylhexylidene)bisphenol, (γ) component 25 parts of n-nonyl palmitate and 25 parts of decyl myristate, which are microencapsulated by an interfacial polymerization method. ｂ : 4.5 ° C, t １ : 14 ° C, t ２ : 19 ° C, t ３ : 18 ° C, t ４ A thermochromic PVC plastisol was prepared by dispersing 20.0 parts of Thermochromic Pigment A (reversible color change from magenta to colorless at 24°C) in PVC plastisol. The color density of Thermochromic Pigment A at the complete color development temperature of Thermochromic Pigment B was 75%, and the color density of Thermochromic Pigment A at the complete decolorization temperature of Thermochromic Pigment B was 0%. Using the thermochromic PVC plastisol, a vehicle-shaped mold with an uneven surface was produced. The ratio of the volume of the vinyl chloride resin to the volume of the hollow portion of the toy was 75:25. The toy exhibited a purple color at temperatures below 13°C, and when it was successively immersed in water between 18°C ​​and 24°C, water above 34°C, water between 14°C and 16°C, and water below 13°C, the color changed to cyan, white, magenta, and purple, respectively. However, when the toy changed from white to magenta, no clear magenta color was visible due to the high color development density of the thermochromic pigment A.

[0046] T １ Complete discoloration temperature of reversible thermochromic composition a T ２ Discoloration starting temperature of reversible thermochromic composition a T ３ Color development initiation temperature of reversible thermochromic composition a T ４ Complete color development temperature t of reversible thermochromic composition a １ Complete color development temperature t of reversible thermochromic composition b２ The color development starting temperature t of the reversible thermochromic composition b ３ The discoloration starting temperature t of the reversible thermochromic composition b ４ Complete decolorization temperature of reversible thermochromic composition b

Claims

1. A toy formed by dispersing a pigment A containing a reversible thermochromic composition a and a pigment B containing a reversible thermochromic composition b in a vinyl chloride resin, and having a hollow interior, wherein the reversible thermochromic compositions a and b have a color development start temperature (T ２ or t ２ ) at which they start to develop color when reaching the temperature-lowering process from the decolorized state in the color density-temperature curve, and reach a completely developed color state when reaching the complete color development temperature (T １ or t １ ), and start to decolorize when reaching the decolorization start temperature (T ３ or t ３ ) in the temperature-rising process from the developed color state, and reach a completely decolorized state when reaching the complete decolorization temperature (T ４ or t ４ ), which is a heat-decolorizing type composition showing a hysteresis curve, and the color density of the other reversible thermochromic composition is 40% or less at the complete color development temperature of one reversible thermochromic composition, or the color density of the other reversible thermochromic composition is 60% or more at the complete decolorization temperature of one reversible thermochromic composition. A temperature-sensitive multicolor-changing toy characterized by this.

2. The thermosensitive multicolor discoloring toy according to claim 1, having unevenness on the surface.

3. The thermosensitive multicolor discoloring toy according to claim 1 or 2, wherein the hysteresis curves of the reversible thermochromic compositions a and b do not overlap with each other.

4. The thermosensitive multicolor discoloring toy according to claim 1 or 2, wherein the hysteresis curve of the reversible thermochromic composition b is inherent in the hysteresis curve of the reversible thermochromic composition a.

5. The hysteresis width (ΔH ａ ) of the reversible thermochromic composition a and the hysteresis width (ΔH ｂ ) of the reversible thermochromic composition b satisfy the conditions (1) and (2) as described in claim 4, and the thermosensitive multicolor variable color toy is provided. ΔH ａ = [(T ４ + T ３ ) / 2 - (T ２ + T １ ) / 2] = 10 to 50 °C (1) ΔH ｂ = [(t ４ + t ３ ) / 2 - (t ２ + t １ ) / 2] = 0.5 to 20 °C (2) (T １ , T ２ , T ３ , T ４ respectively represent the complete color development temperature, color development start temperature, color fading start temperature, and complete color fading temperature of the reversible thermochromic composition a, and t １ , t ２ , t ３ , t ４ respectively represent the complete color development temperature, color development start temperature, color fading start temperature, and complete color fading temperature of the reversible thermochromic composition b) 6. The thermosensitive multicolor discoloring toy according to claim 1 or 2, wherein the hollow portion of the toy does not communicate with the outside, and the ratio of the volume of the vinyl chloride resin to the volume of the hollow portion is 85:15 to 10:

90.

7. A toy set comprising the thermosensitive multicolor discoloring toy according to claim 1 or 2, and a temperature-changing member for changing the temperature of part or all of the thermosensitive multicolor discoloring toy.

8. The toy set according to claim 7, wherein the temperature-changing member applies cold water or warm water to the thermosensitive multicolor discoloring toy.

Images