Reversible thermochromic microcapsule pigment

Abstract

The object of the present invention is to provide a reversible thermochromic microcapsule pigment which easily shows a reversible color change behavior from a decolorized state to a coloring state by heating and then returns to the decolorized state at a temperature in the living environment temperature range or near the daily living temperature, and has a high color concentration when the color is developed. The solution is a reversible thermochromic microcapsule pigment which contains a reversible thermochromic composition, wherein the reversible thermochromic composition comprises: (a) an electron-donating color-developing organic compound; (b) a hydroxyphenylacetic acid ester compound represented by the following general formula (1) as an electron-accepting compound; (c) a compound selected from chain hydrocarbons, alicyclic hydrocarbons, and halogenated hydrocarbons as a reaction medium for reversibly causing an electron transfer reaction between the above-mentioned components (a) and (b); and (d) a styrene compound having a softening point of 5°C or more and a weight average molecular weight of 200 to 100,000. (In the formula, R represents a linear or branched alkyl group having 12 to 22 carbon atoms, X, Y, and Z are each independently hydrogen or hydroxyl, and two or three of them are hydroxyl)#imgabs0#

Description

Technical Field

[0001] The present invention relates to a reversible thermochromic microcapsule pigment, and more particularly to a reversible thermochromic microcapsule pigment that develops color from a decolorized state by heating. Background Art

[0002] In the past, a reversible thermochromic composition comprising (a) an electron-donating color-developing organic compound, (b) an electron-accepting compound, and (c) a reaction medium that causes an electron transfer reaction between components (a) and (b) to reversibly occur has been disclosed, wherein, by using a hydroxybenzoic acid ester as component (b), the composition exhibits a color change behavior of changing from a decolorized state to a color-developing state by heating and returning to the decolorized state by cooling, and a microcapsule pigment containing the reversible thermochromic composition (for example, refer to Patent Document 1).

[0003] Although these reversible thermochromic compositions show a color development state by heating, the color development temperature is high, and it is difficult to easily develop color at daily living temperatures or temperatures near daily living temperatures. In addition, even if a reversible thermochromic composition that develops color at daily living temperatures or temperatures near daily living temperatures is obtained, the color concentration in the color development state is low, which does not meet practicality.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2001-105732 Summary of the invention

[0007] Problems to be solved by the invention

[0008] The present inventors have conducted intensive studies on a reversible thermochromic composition that develops color from a decolorized state by heating, and as a result, have found that by using a specific hydroxyphenylacetic acid ester compound as the component (b) and adding a specific compound as the component (d), a reversible thermochromic microcapsule pigment containing a reversible thermochromic composition that exhibits a color change behavior that easily changes from a decolorized state to a colorized state by heating at a temperature in the living environment temperature range and near the daily living temperature, and then returns to the decolorized state again, and has a high color concentration when developing color, thereby completing the present invention.

[0009] Methods for solving problems

[0010] The reversible thermochromic microcapsule pigment of the present invention contains a reversible thermochromic composition, and the reversible thermochromic composition comprises:

[0011] (a) an electron-donating color-developing organic compound;

[0012] (b) a hydroxyphenylacetic acid ester compound represented by the following general formula (1) as an electron-accepting compound;

[0013] (c) a compound selected from the group consisting of chain hydrocarbons, alicyclic hydrocarbons and halogenated hydrocarbons, which is a reaction medium for reversibly causing an electron transfer reaction between the components (a) and (b); and

[0014] (d) A styrene compound having a softening point of 5° C. or higher and a weight average molecular weight of 200 to 100,000.

[0015]

[0016] (Where,

[0017] R represents a linear or branched alkyl group having 12 to 22 carbon atoms,

[0018] X, Y, and Z are each independently hydrogen or hydroxy, two of them are hydroxy and the rest are hydrogen, or three of them are hydroxy)

[0019] The reversible thermochromic liquid composition of the present invention comprises the reversible thermochromic microcapsule pigment and a carrier.

[0020] The laminated body according to the present invention comprises: a support; and a reversible thermochromic layer, wherein the reversible thermochromic layer contains the microcapsule pigment.

[0021] The molded article according to the present invention contains the above-mentioned microcapsule pigment in a support.

[0022] Effects of the Invention

[0023] The present invention can provide a reversible thermochromic microcapsule pigment which can be applied in various fields such as teaching elements, toys, decorations, etc., and can easily change from a decolorized state to a colorized state by heating at a temperature in the living environment temperature range and near the daily living temperature, and then return to the decolorized state again, and has a high color concentration when coloring. DETAILED DESCRIPTION

[0024] Specific examples of compounds are given below for each component.

[0025] The component (a) of the present invention, that is, the electron-donating color-developing organic compound, is a component that determines color and is a compound that donates electrons to the component (b) as a color developer to develop color.

[0026] Examples of the electron donating color-developing organic compound include phthalide compounds, fluoran compounds, styrylquinoline compounds, diazarhodamine lactone compounds, pyridine compounds, quinazoline compounds, bisquinazoline compounds, and the like. Among these, phthalide compounds and fluoran compounds are preferred.

[0027] Examples of the phthalide compound include diphenylmethanephthalide compounds, phenylindolylphthalide compounds, indolylphthalide compounds, diphenylmethaneazaphthalide compounds, phenylindolylazaphthalide compounds, and derivatives thereof. Among these, phenylindolylazaphthalide compounds and derivatives thereof are preferred.

[0028] In addition, examples of the fluoran compound include aminofluoran compounds, alkoxyfluoran compounds, and derivatives thereof.

[0029] These compounds are exemplified below.

[0030] 3,3-Bis(p-dimethylaminophenyl)-6-dimethylaminophthalide,

[0031] 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide,

[0032] 3,3-Bis(1-n-butyl-2-methylindol-3-yl)phthalide,

[0033] 3,3-Bis(2-ethoxy-4-diethylaminophenyl)-4-azaphthalide,

[0034] 3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide,

[0035] 3-(2-Hexyloxy-4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide,

[0036] 3-[2-ethoxy-4-(N-ethylanilino)phenyl]-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide,

[0037] 3-(2-acetamido-4-diethylaminophenyl)-3-(1-propylindol-3-yl)-4-azaphthalide,

[0038] 3,6-bis(diphenylamino)fluoran,

[0039] 3,6-Dimethoxyfluoran,

[0040] 3,6-di-n-butoxyfluoran,

[0041] 2-methyl-6-(N-ethyl-N-p-tolylamino)fluoran,

[0042] 3-Chloro-6-cyclohexylaminofluoran,

[0043] 2-methyl-6-cyclohexylaminofluoran,

[0044] 2-(2-Chloroamino)-6-dibutylaminofluoran,

[0045] 2-(2-chloroanilino)-6-di-n-butylaminofluoran,

[0046] 2-(3-trifluoromethylanilino)-6-diethylaminofluoran,

[0047] 2-(3-trifluoromethylanilino)-6-dipentylaminofluoran,

[0048] 2-(Dibenzylamino)-6-diethylaminofluoran,

[0049] 2-(N-methylanilino)-6-(N-ethyl-N-p-tolylamino)fluoran,

[0050] 1,3-Dimethyl-6-diethylaminofluoran,

[0051] 2-Chloro-3-methyl-6-diethylaminofluoran,

[0052] 2-anilino-3-methyl-6-diethylaminofluoran,

[0053] 2-anilino-3-methoxy-6-diethylaminofluoran,

[0054] 2-anilino-3-methyl-6-di-n-butylaminofluoran,

[0055] 2-anilino-3-methoxy-6-di-n-butylaminofluoran,

[0056] 2-Dimethylanilino-3-methyl-6-diethylaminofluoran,

[0057] 2-anilino-3-methyl-6-(N-ethyl-N-p-tolylamino)fluoran,

[0058] 1,2-Benzo-6-diethylaminofluoran,

[0059] 1,2-Benzo-6-(N-ethyl-N-isobutylamino)fluoran,

[0060] 1,2-Benzo-6-(N-ethyl-N-isopentylamino)fluoran,

[0061] 2-(3-methoxy-4-dodecyloxyphenylvinyl)quinoline,

[0062] Spiro[5H-(1)benzopyrano(2,3-d)pyrimidine-5,1'(3'H)isobenzofuran]-3'-one, 2-(diethylamino)-8-(diethylamino)-4-methyl,

[0063] Spiro[5H-(1)benzopyrano(2,3-d)pyrimidine-5,1'(3'H)isobenzofuran]-3'-one, 2-(di-n-butylamino)-8-(di-n-butylamino)-4-methyl,

[0064] Spiro[5H-(1)benzopyrano(2,3-d)pyrimidine-5,1'(3'H)isobenzofuran]-3'-one, 2-(di-n-butylamino)-8-(diethylamino)-4-methyl,

[0065] Spiro[5H-(1)benzopyrano(2,3-d)pyrimidine-5,1'(3'H)isobenzofuran]-3'-one, 2-(di-n-butylamino)-8-(N-ethyl-N-isopentylamino)-4-methyl,

[0066] Spiro[5H-(1)benzopyrano(2,3-d)pyrimidine-5,1'(3'H)isobenzofuran]-3'-one, 2-(dibutylamino)-8-(dipentylamino)-4-methyl,

[0067] 4,5,6,7-tetrachloro-3-[4-(dimethylamino)-2-methoxyphenyl]-3-(1-butyl-2-methyl-1H-indol-3-yl)-1(3H)-isobenzofuranone,

[0068] 4,5,6,7-tetrachloro-3-[4-(diethylamino)-2-ethoxyphenyl]-3-(1-ethyl-2-methyl-1H-indol-3-yl)-1(3H)-isobenzofuranone,

[0069] 4,5,6,7-tetrachloro-3-[4-(diethylamino)-2-ethoxyphenyl]-3-(1-pentyl-2-methyl-1H-indol-3-yl)-1(3H)-isobenzofuranone,

[0070] 4,5,6,7-tetrachloro-3-[4-(diethylamino)-2-methylphenyl]-3-(1-ethyl-2-methyl-1H-indol-3-yl)-1(3H)-isobenzofuranone,

[0071] 3',6'-Bis[phenyl(2-methylphenyl)amino]-spiro[isobenzofuran-1(3H),9'-[9H]xanthene]-3-one,

[0072] 3',6'-Bis[phenyl(3-methylphenyl)amino]-spiro[isobenzofuran-1(3H),9'-[9H]xanthene]-3-one,

[0073] 3',6'-Bis[phenyl(3-ethylphenyl)amino]-spiro[isobenzofuran-1(3H),9'-[9H]xanthene]-3-one,

[0074] 2,6-bis(2'-ethyloxyphenyl)-4-(4'-dimethylaminophenyl)pyridine,

[0075] 2,6-bis(2',4'-diethyloxyphenyl)-4-(4'-dimethylaminophenyl)pyridine,

[0076] 2-(4'-dimethylaminophenyl)-4-methoxy-quinazoline,

[0077] 4,4'-(Ethylenedioxy)-bis[2-(4-diethylaminophenyl)quinazoline]

[0078] etc.

[0079] In addition, as fluorans, in addition to the above-mentioned compounds having a substituent on the phenyl group forming the xanthene ring, there can also be compounds that have a substituent on the phenyl group forming the xanthene ring and a substituent (for example, an alkyl group such as a methyl group, a halogen atom such as a chloro group) on the phenyl group forming the lactone ring, which exhibit blue or black colors.

[0080] As the (b) electron-accepting compound, a hydroxyphenylacetic acid ester compound represented by the general formula (1) is used.

[0081]

[0082] In the formula,

[0083] R represents a linear or branched alkyl group having 12 to 22 carbon atoms,

[0084] X, Y and Z are each independently hydrogen or hydroxy, two or three of them are hydroxy,

[0085] It is preferred that among X, Y and Z, two are hydroxyl groups and one is hydrogen.

[0086] More preferably, X and Y are hydroxyl groups, and Z is hydrogen. Specifically, a 3,4-dihydroxyphenylacetic acid ester compound represented by the general formula (2) is preferred, and can be suitably used because of its high color density when developing color.

[0087]

[0088] In the formula, R is the same as R in formula (1).

[0089] The alkyl group of the hydroxyphenylacetic acid ester compound is a linear or branched alkyl group having 12 to 22 carbon atoms, and preferably a linear or branched alkyl group having 14 to 22 carbon atoms. Compounds having an alkyl group having less than 12 carbon atoms or more than 22 carbon atoms have low crystallinity and therefore do not satisfy practicality. In addition, in consideration of practical performance such as excellent color change characteristics and color development density, a linear alkyl group having 12 to 22 carbon atoms is preferred, a linear alkyl group having 16 to 22 carbon atoms is more preferred, a linear alkyl group having 16 to 20 carbon atoms is further preferred, and a linear alkyl group having 16 to 18 carbon atoms is further preferred.

[0090] Examples of the hydroxyphenylacetic acid ester compound include 3,4-dihydroxyphenylacetic acid dodecyl ester, 3,4-dihydroxyphenylacetic acid tridecyl ester, 3,4-dihydroxyphenylacetic acid tetradecyl ester, 3,4-dihydroxyphenylacetic acid 2-methyl tridecyl ester, 3,4-dihydroxyphenylacetic acid pentadecyl ester, 3,4-dihydroxyphenylacetic acid hexadecyl ester, 3,4-dihydroxyphenylacetic acid 2-ethyl tetradecyl ester, 3,4-dihydroxyphenylacetic acid heptadecyl ester, 3,4-dihydroxyphenylacetic acid 2-methyl hexadecyl ester, 3,4-dihydroxyphenylacetic acid octadecyl ester, 3,4-dihydroxyphenylacetic acid 2-methyl heptadecanyl ester, 3,4-dihydroxyphenylacetic acid 2-ethyl hexadecyl ester, 3,4-dihydroxyphenylacetic acid nonadecanyl ester, 3,4-dihydroxyphenylacetic acid eicosyl ester, 3,4-dihydroxyphenylacetic acid 2-methyl nonadecanyl ester, 3,4-dihydroxyphenylacetic acid 2-ethyl octadecyl ester, 3,4-dihydroxyphenylacetic acid heneicos ... 3,5-dihydroxyphenylacetic acid behenyl ester, 3,5-dihydroxyphenylacetic acid dodecyl ester, 3,5-dihydroxyphenylacetic acid tridecyl ester, 3,5-dihydroxyphenylacetic acid tetradecyl ester, 3,5-dihydroxyphenylacetic acid 2-methyl tridecyl ester, 3,5-dihydroxyphenylacetic acid pentadecyl ester, 3,5-dihydroxyphenylacetic acid hexadecyl ester, 3,5-dihydroxyphenylacetic acid 2-ethyl tetradecyl ester, 3,5-dihydroxyphenylacetic acid heptadecyl ester, 3,5-dihydroxyphenylacetic acid 2-methyl hexadecyl ester , 3,5-dihydroxyphenylacetic acid octadecyl ester, 3,5-dihydroxyphenylacetic acid 2-methylheptadecyl ester, 3,5-dihydroxyphenylacetic acid 2-ethylhexadecyl ester, 3,5-dihydroxyphenylacetic acid nonadecyl ester, 3,5-dihydroxyphenylacetic acid eicosyl ester, 3,5-dihydroxyphenylacetic acid 2-methylnonadecyl ester, 3,5-dihydroxyphenylacetic acid 2-ethyloctadecyl ester, 3,5-dihydroxyphenylacetic acid heneicosyl ester, 3,5-dihydroxyphenylacetic acid docosyl ester.Furthermore, as the substance in which all of X, Y, and Z are hydroxyl groups, 3,4,5-trihydroxyphenylacetic acid dodecyl ester, 3,4,5-trihydroxyphenylacetic acid tridecyl ester, 3,4,5-trihydroxyphenylacetic acid tetradecyl ester, 3,4,5-trihydroxyphenylacetic acid 2-methyl tridecyl ester, 3,4,5-trihydroxyphenylacetic acid pentadecyl ester, 3,4,5-trihydroxyphenylacetic acid hexadecyl ester, 3,4,5-trihydroxyphenylacetic acid 2-ethyl tetradecyl ester, 3,4,5-trihydroxyphenylacetic acid heptadecyl ester, 3,4,5-trihydroxyphenylacetic acid heptadecyl ester, 3,4,5-trihydroxyphenylacetic acid 2-ethyl tetradecyl ester, 3,4,5-trihydroxyphenylacetic acid heptadecyl ester, 3,4,5-trihydroxyphenylacetic acid 2-ethyl 2-methylhexadecyl acetate, 3,4,5-trihydroxyphenylacetic acid octadecyl ester, 3,4,5-trihydroxyphenylacetic acid 2-methylheptadecyl ester, 3,4,5-trihydroxyphenylacetic acid 2-ethylhexadecyl ester, 3,4,5-trihydroxyphenylacetic acid nonadecyl ester, 3,4,5-trihydroxyphenylacetic acid eicosyl ester, 3,4,5-trihydroxyphenylacetic acid 2-methylnonadecyl ester, 3,4,5-trihydroxyphenylacetic acid 2-ethyloctadecyl ester, 3,4,5-trihydroxyphenylacetic acid heneicosyl ester, 3,4,5-trihydroxyphenylacetic acid docosyl ester, etc. In general, compounds having many hydroxyl groups tend to have a high color density when developing color.

[0091] (c) As the reaction medium for causing the electron transfer reaction between the component (a) and the component (b) to reversibly occur, a compound selected from the group consisting of chain hydrocarbons, alicyclic hydrocarbons and halogenated hydrocarbons is used.

[0092] By using the compound of component (c), the desensitization to the color development caused by the reaction of components (a) and (b) is small, and the color change behavior and color density of the color development caused by heating are effectively improved.

[0093] The larger the carbon number of the alkyl group of the hydroxybenzoic acid ester of the component (b) is, the higher the crystallinity tends to be. By adding the component (c), a hydroxybenzoic acid ester with high crystallinity can be used at a color change temperature in a low temperature range.

[0094] Examples of the chain hydrocarbons include saturated chain hydrocarbons such as pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, heneicosane, docosane, tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane and triacontan; and unsaturated chain hydrocarbons such as 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-heneicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, 1-nonacosene and 1-triacosene.

[0095] Examples of the alicyclic hydrocarbons include cyclooctane, cyclododecane, n-pentadecylcyclohexane, n-octadecylcyclohexane, n-nonadecylcyclohexane, and decalin.

[0096] Examples of the halogenated hydrocarbons include 1-bromodecane, 1-bromodecane, 1-bromododecane, 1-bromodridecane, 1-bromodecane, 1-chlorotetradecane, 1-bromodecane, 1-bromopentadecane, 1-bromohexadecane, 1-chlorohexadecane, 1-iodohexadecane, 1-bromoheptadecane, 1-bromooctadecane, 1-chlorooctadecane, 1-iodooctadecane, 1-bromoeicosane, 1-chloroeicosane, 1-bromodocosane, and 1-chlorodocosane.

[0097] (d) Styrene compounds having a softening point of 5° C. or higher and a weight average molecular weight of 200 to 100,000 are exemplified below.

[0098] As the styrene compound, a compound having a weight average molecular weight of 200 to 6,000 is preferably used.

[0099] In addition, the weight average molecular weight is measured by the GPC method (gel permeation chromatography).

[0100] Examples of the styrene-based compound include low molecular weight polystyrene, styrene-α-methylstyrene-based copolymers, α-methylstyrene polymers, and copolymers of α-methylstyrene and vinyltoluene.

[0101] As the low molecular weight polystyrene, trade names of Himax SB-75 (weight average molecular weight 2000) and Himax ST-95 (weight average molecular weight 4000) manufactured by Sanyo Chemical Industries, Ltd. can be used.

[0102] As the styrene-α-methylstyrene-based copolymer, available are Physico-Hydraulics Co., Ltd. trade name: Phosphorus A5 (weight average molecular weight: 317), Coruscans A75 (weight average molecular weight: 917), Physics and Chemical Industries Co., Ltd. trade name: Coruscans D125 (weight average molecular weight: 3000), etc.

[0103] As the α-methylstyrene polymer, it is possible to use a product manufactured by RIKEN HOLDINGS CO., LTD. (trade name: KHREX 3085 (weight average molecular weight 6)). 64), クリスタレックス3100 (weight average molecular weight 1020), クリスタレックス1120 (weight average molecular weight 2420), etc.

[0104] As the copolymer of α-methylstyrene and vinyltoluene, trade names: Picotex LC (weight average molecular weight: 950), Picotex 100 (weight average molecular weight: 1740), etc., manufactured by Rika Hakuresu Co., Ltd. can be used.

[0105] The styrene-based compounds may be used alone or in combination of two or more.

[0106] By adding the component (d), the polarity of the compound selected from the group consisting of chain hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons and halogenated hydrocarbons as the reaction medium changes, so that the solubility of the component (b) in the reaction medium decreases, and the crystallization of the component (b) proceeds slowly. Therefore, the reversible thermochromic microcapsule pigment (hereinafter, sometimes simply referred to as microcapsule pigment) containing the reversible thermochromic composition, which is cooled from the color development state to the decolorization inducing temperature during the temperature reduction process, decolorizes after being left to stand.

[0107] The microcapsule pigment of the present invention preferably further comprises (e) a compound having a melting point of 50° C. or higher and selected from alcohols, esters, ethers, ketones, acid amides and aromatic hydrocarbons (hereinafter, sometimes simply referred to as component (e)). Component (e) is exemplified below.

[0108] Examples of the alcohols include hexadecane 1-ol, heptadecan 1-ol, octadecan 1-ol, nonadecan 1-ol, eicosanol, heneicosanol, docosanol, tetracosanol, hexacosanol, octacosanol, triacontanol, and the like.

[0109] Examples of the esters include eicosyl laurate, behenyl laurate, lignoceryl laurate, hexacosyl laurate, octacosyl laurate, cetyl myristate, stearyl myristate, eicosyl myristate, behenyl myristate, lignoceryl myristate, hexacosyl myristate, octacosyl myristate, myristyl palmitate, cetyl palmitate, stearyl palmitate, eicosyl palmitate, behenyl palmitate, lignoceryl palmitate, hexacosyl palmitate, octacosyl palmitate, cetyl stearate, stearyl stearate, eicosyl stearate, behenyl stearate, lignoceryl stearate, hexacosyl stearate, and octacosyl stearate. , octadecyl stearate, decyl eicosate, undecyl eicosate, tridecyl eicosate, myristyl eicosate, cetyl eicosate, stearyl eicosate, eicosate, behenyl eicosate, tetradecyl eicosate, hexadecyl eicosate, octadecyl eicosate, methyl behenate, hexyl behenate, octyl behenate, decyl behenate, undecyl behenate, lauryl behenate, tridecyl behenate, myristyl behenate, cetyl behenate, stearyl behenate, eicosate, behenyl behenate, lauryl behenate, tridecyl behenate, myristyl behenate, cetyl behenate, stearyl behenate, eicosate, behenyl behenate, lauryl behenate, hexadecyl behenate, octadecyl behenate, distearyl oxalate, di-eicosyl oxalate , behenyl oxalate, distearyl succinate, eicosyl succinate, behenyl succinate, distearyl glutarate, eicosyl glutarate, behenyl glutarate, dimyristyl adipate, dicetyl adipate, distearyl adipate, eicosyl adipate, behenyl adipate, dicetyl suberate, distearyl suberate Esters, diarachidyl suberate, behenyl suberate, myristyl azelaic acid, dicetyl azelaic acid, distearyl azelaic acid, arachidyl azelaic acid, behenyl azelaic acid, dimyristyl sebacate, dicetyl sebacate, distearyl sebacate, diarachidyl sebacate, dibehenyl sebacate, 1,14-tetradecyl 1,14-tetradecamethylethylenedicarboxylic acid ditridecyl ester, 1,14-tetradecamethylethylenedicarboxylic acid dimyristyl ester, 1,14-tetradecamethylethylenedicarboxylic acid dicetyl ester, 1,14-tetradecamethylethylenedicarboxylic acid dipalmityl ester, 1,14-tetradecamethylethylenedicarboxylic acid distearyl ester, 1,14-tetradecamethylethylenedicarboxylic acid dieicosyl ester, 1,14-tetradecamethylethylenedicarboxylic acid dibehenyl ester, 1,16-hexadecamethylethylenedicarboxylic acid dilauryl ester, 1,16-hexadecamethylethylenedicarboxylic acid ditridecyl ester, 1,16-hexadecamethylethylenedicarboxylic acid dimyristyl ester, 1,16-hexadecamethylethylenedicarboxylic acid dicetyl ester, 1,16-hexadecamethylethylenedicarboxylic acid dipalmityl ester, 1,16-hexadecamethylethylenedicarboxylic acid distearyl ester, 1,16-hexadecamethylethylenedicarboxylic acid16-hexadecyl methylene dicarboxylate, dibehenyl 1,16-hexadecyl methylene dicarboxylate, didecyl 1,18-octadecyl methylene dicarboxylate, dilauryl 1,18-octadecyl methylene dicarboxylate, ditridecyl 1,18-octadecyl methylene dicarboxylate, dimyristyl 1,18-octadecyl methylene dicarboxylate, dicetyl 1,18-octadecyl methylene dicarboxylate, dipalmityl 1,18-octadecyl methylene dicarboxylate, distearyl 1,18-octadecyl methylene dicarboxylate, dieicosyl 1,18-octadecyl methylene dicarboxylate, dibehenyl 1,18-octadecyl methylene dicarboxylate, didecyl 1,20-eicosyl methylene dicarboxylate, dilauryl 1,20-eicosyl methylene dicarboxylate, 1 ,20-eicosyl di(tridecyl) ester, 1,20-eicosyl dimyristyl ester, 1,20-eicosyl dicarboxylic acid dicetyl ester, 1,20-eicosyl dipalmityl ester, 1,20-eicosyl dicarboxylic acid distearyl ester, 1,20-eicosyl dicarboxylic acid di(eicosyl) ester, 1,20-eicosyl dibehenyl ester, glyceryl trimyristate, glyceryl tripalmitate, glyceryl tristearate, triglyceride nonadecanoate, cholesteryl caproate, cholesteryl caprylate, cholesteryl caprate, cholesteryl undecanoate, cholesteryl laurate, cholesteryl myristate, cholesteryl palmitate, cholesteryl stearate, cholesteryl eicosanoate, cholesteryl behenate, etc. ,

[0110] Examples of the ethers include pentadecyl ether, hexadecyl ether, dioctadecyl ether, diicosyl ether, and didocosyl ether.

[0111] Examples of the ketones include dioctyl ketone, dinonyl ketone, diundecyl ketone, ditridecyl ketone, dipentadecyl ketone, diheptadecyl ketone, dinonadecyl ketone, phenyloctyl ketone, phenylundecyl ketone, phenyltridecyl ketone, phenylpentadecyl ketone and phenylheptadecyl ketone.

[0112] Examples of the acid amides include hexylamide, heptylamide, octylamide, nonylamide, decylamide, undecylamide, laurylamide, tridecylamide, myristylamide, palmitylamide, stearylamide, eicosylamide, behenylamide, hexacosylamide, and octacosylamide.

[0113] Examples of the aromatic hydrocarbons include biphenyl, o-terphenyl, m-terphenyl, p-terphenyl, and terthiophene.

[0114] As the component (e), the compounds described in the following table can also be used.

[0115] Table 1

[0116]

[0117] The component (e) is preferably a compound selected from esters, ethers, and aromatic hydrocarbons, and more preferably an aromatic hydrocarbon.

[0118] In the process of cooling from the colored state, the component (b) crystallizes due to the component (d) and the color is removed. However, it may take time to completely remove the color. By adding the component (e), the crystallization can be further promoted, and the color removal sensitivity can be improved.

[0119] The ratio of components (a), (b), (c), and (d) is affected by color concentration, color change temperature, color change form, and the type of each component, but in general, the ratio of components to obtain the desired characteristics is in the following range: relative to 1 part of component (a), component (b) is 0.1 to 50 parts, preferably 0.5 to 20 parts, component (c) is 1 to 200 parts, preferably 5 to 100 parts, component (d) is 0.1 to 10.0 parts, preferably 0.5 to 5.0 parts, and component (e) is 0.1 to 5.0 parts, preferably 0.1 to 3.0 parts (the above ratios are all parts by mass).

[0120] The reversible thermochromic composition is used in the form of being encapsulated in microcapsules. This is because even if it comes into contact with chemically active substances such as acidic substances, alkaline substances, peroxides, or other solvent components, its function will not be reduced, and its heat resistance stability can be maintained. Therefore, the reversible thermochromic composition maintains the same composition under various use conditions and can exert the same effect.

[0121] The microcapsule pigment encapsulating the reversible thermochromic composition has a particle size in the range of 0.1 to 100 μm, preferably 0.5 to 30 μm, and more preferably 1 to 20 μm to meet practical needs.

[0122] In addition, the determination of particle diameter and average particle diameter refers to, using the image analysis type particle size distribution measurement software " Mac-view " of Mountech company system to determine particle area, calculate the projection area equivalent circle diameter (Heywood diameter) by the area of ​​particle area, measure the particle diameter and average particle diameter value of the equivalent particles of the equal volume sphere obtained by this value. In addition, when the particle diameter of all particles or most particles exceeds 0.2 μm, it is also possible to use particle size distribution measurement device (Beckman Coulter Co., Ltd. system, product name: Multisizer 4e) to measure the particle diameter and average particle diameter as the equivalent particles of the equal volume sphere by Coulter method.

[0123] Furthermore, the volume-based particle size and average particle size (median particle size) can be measured using a laser diffraction / scattering particle size distribution analyzer (apparatus name: LA-300, manufactured by Horiba, Ltd.) calibrated based on values ​​measured using a measuring apparatus using the Coulter method.

[0124] In addition, each component may be a mixture of two or more compounds, and a light stabilizer may be further added within a range that does not impair the function.

[0125] As the light stabilizer, there can be mentioned ultraviolet light absorbers, visible light absorbers, infrared light absorbers, antioxidants, singlet oxygen quenchers such as carotenes, pigments, amines, phenols, nickel coordination compounds, thioethers, superoxide anion quenchers such as complexes of oxidative dismutase and cobalt and complexes of oxidative dismutase and nickel, and compounds that inhibit oxidation reactions such as ozone quenchers, and the mixing ratio is 0.3 to 24% by mass, preferably 0.8 to 16% by mass. Among them, in the case of a system in which an ultraviolet light absorber and an antioxidant and / or a singlet oxygen quencher are used in combination, it is particularly effective to improve the light resistance.

[0126] Furthermore, an antioxidant, an antistatic agent, a polarity imparting agent, a thixotropy imparting agent, a defoaming agent, etc. may be added as necessary to improve the function.

[0127] Furthermore, dye pigments (non-thermochromic) can generally be mixed.

[0128] The color changing properties of a microcapsule pigment encapsulating a reversible thermochromic composition containing components (a), (b), (c), and (d), or components (a), (b), (c), (d), and (e) are described.

[0129] The reversible thermochromic composition in a decolorized state starts to color from the color development start temperature (T1) during the heating process, and becomes a completely colored state when the complete color development temperature (T2) is reached. The reversible thermochromic composition that is cooled to the decolorization inducing temperature during the cooling process decolorizes after being left standing.

[0130] T1 is preferably 15 to 35°C, more preferably 15 to 27°C. T2 is preferably 25 to 50°C, more preferably 25 to 40°C.

[0131] The reversible thermochromic microcapsule pigment is dispersed in a carrier containing an additive as needed to form a liquid composition, and can be used in (i) printing inks used for screen printing, lithography, color plate printing, gravure printing, coater, pad printing, etc., (ii) coatings used for brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, dip coating, etc., (iii) inks for writing instruments such as markers, ballpoint pens, fountain pens, and brushes, (iv) inks for coating tools, (v) painting pigments, (vi) cosmetics, or (vii) coloring liquids for fibers.

[0132] Examples of the additives include resins, crosslinking agents, curing agents, desiccants, plasticizers, viscosity modifiers, dispersants, ultraviolet absorbers, infrared absorbers, antioxidants, light stabilizers, solubilizers, anti-settling agents, lubricants, gelling agents, defoaming agents, matting agents, penetrants, pH adjusters, foaming agents, coupling agents, humectants, mildew inhibitors, preservatives, and rust inhibitors.

[0133] Examples of the carrier of the liquid composition of the present invention include an oily carrier containing an organic solvent, and an aqueous carrier containing water and, if necessary, an organic solvent.

[0134] Examples of the organic solvent that can be used in the present invention include ethanol, propanol, butanol, glycerol, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiglycol, polyethylene glycol, propylene glycol, butylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, sulfolane, 2-pyrrolidone, and N-methyl-2-pyrrolidone.

[0135] Examples of the liquid composition include a shear-reducing viscosity-imparting agent in a carrier and a coagulable liquid composition in which a water-soluble polymer coagulant is contained in a carrier and a pigment is suspended in a slowly coagulated state.

[0136] When the liquid composition contains the shear-reducing viscosity-imparting agent, for example, when the composition is used as an ink composition, aggregation and sedimentation of the pigment can be suppressed, and bleeding of handwriting can be suppressed, so that good handwriting can be formed.

[0137] Furthermore, when a ballpoint pen is filled with an ink composition containing a shear-reducing viscosity-imparting agent, it is possible to prevent the ink from leaking out of the gap between the ball and the pen tip when not in use, or to prevent the ink composition from flowing back when the writing tip is placed upward (in an upright position).

[0138] Examples of the shear-reducing viscosity-imparting agent include xanthan gum, welan gum, succinoglycan (average molecular weight of about 1 million to 8 million) of organic acid-modified heteropolysaccharides whose constituent monosaccharides are glucose and galactose, guar gum, locust bean gum and its derivatives, hydroxyethylcellulose, alginic acid alkyl esters, polymers having a molecular weight of 100,000 to 150,000 and containing alkyl esters of methacrylic acid as a main component, thickening polysaccharides having gelling ability extracted from seaweed such as glucomannan, agar, and carrageenan, benzylidene sorbitol, and Nonionic surfactants having an HLB value of 8 to 12 such as benzyl xylitol or its derivatives, cross-linked acrylic acid polymers, inorganic fine particles, polyglycerol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyethylene glycol fatty acid esters, polyoxyethylene alkyl ethers, polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, fatty acid amides, etc., salts of dialkyl or diene sulfosuccinic acid, mixtures of N-alkyl-2-pyrrolidone and anionic surfactants, and mixtures of polyvinyl alcohol and acrylic resins.

[0139] Examples of the water-soluble polymer flocculant that can be used in the present invention include polyvinyl pyrrolidone, polyethylene oxide, and water-soluble polysaccharides.

[0140] Examples of the water-soluble polysaccharides include tragacanth gum, guar gum, pullulan, cyclodextrin, and water-soluble cellulose derivatives. Specific examples of the water-soluble cellulose derivatives include methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxyethylmethylcellulose, and hydroxypropylmethylcellulose.

[0141] In addition, when the liquid composition is used as an ink composition filled in a ballpoint pen, it is preferred to add a lubricant such as oleic acid or other higher fatty acids, a nonionic surfactant having a long-chain alkyl group, a polyether-modified silicone oil, a thiophosphite triester such as tris(alkoxycarbonylmethyl thiophosphite) and tris(alkoxycarbonylethyl thiophosphite), a phosphate monoester of a polyoxyethylene alkyl ether or a polyoxyethylene alkyl aryl ether, a phosphate diester of a polyoxyethylene alkyl ether or a polyoxyethylene alkyl aryl ether, or a metal salt, ammonium salt, amine salt, alcohol amine salt or the like to prevent wear of the ball holder.

[0142] Furthermore, by containing 2,5-dimercapto-1,3,4-thiadiazole and / or its salt, even if the pH of the ink is in the acidic or alkaline region, the poor dispersion and aggregation of the microcapsule pigments that occur after the ink that has been frozen is thawed can be suppressed, and the increase in the viscosity of the ink and the accompanying blurring and lightening of the handwriting can be prevented. In addition, when used in a ballpoint pen, the corrosion of the ballpoint can be prevented.

[0143] In addition, as necessary, (i) a resin that imparts adhesiveness or viscosity to the paper surface, such as acrylic resin, styrene maleic acid copolymer, cellulose derivative, polyvinyl pyrrolidone, polyvinyl alcohol, dextrin, etc., (ii) a pH adjuster, such as an inorganic salt, such as sodium carbonate, sodium phosphate, sodium acetate, or an organic alkaline compound, such as a water-soluble amine compound, (iii) a rust inhibitor, such as benzotriazole, methylbenzotriazole, dicyclohexyl ammonium nitrite, diisopropyl ammonium nitrite, or saponin, (iv) phenol, sodium 1,2-benzothiazoline-3-one, etc. (v) urea, a nonionic surfactant, a reduced or non-reduced starch hydrolyzate, an oligosaccharide such as trehalose, a wetting agent such as sucrose, cyclodextrin, glucose, dextrin, sorbitol, mannitol, sodium pyrophosphate, (vi) a defoaming agent, (vii) a dispersing agent, and (viii) a fluorine-based surfactant or a nonionic surfactant for improving the permeability of the ink composition.

[0144] The reversible thermochromic microcapsule pigment may be contained in an amount of preferably 5 to 40% by mass, more preferably 10 to 40% by mass, and still more preferably 10 to 30% by mass relative to the total mass of the liquid composition. When the content of the microcapsule pigment is within the above range, the desired color development concentration can be achieved, and when used as an ink composition, the decrease in the outflow property can be prevented.

[0145] A writing implement that can accommodate the liquid composition of the present invention is described. In one embodiment, the writing implement has a barrel that accommodates the ink composition and a pen body that guides the ink in the barrel. As the pen body, a marker pen body, a ballpoint pen body, a writing brush body, etc. can be cited. As the marker pen body, a fiber pen tip, a felt pen tip, a plastic pen tip, etc. can be cited. As the ballpoint pen body, a ballpoint pen tip can be cited.

[0146] The microcapsule pigment of the present invention can be combined with a support to form a laminated body, which includes a reversible thermochromic layer containing the microcapsule pigment and a support. In addition, it can be a molded body containing the microcapsule pigment in the support.

[0147] Specifically, microcapsule pigments can be dispersed in a medium containing an adhesive as a film-forming material and applied as a reversible thermochromic material for ink, coating, etc., by methods that have always been known, for example, screen printing, lithography, gravure printing, coater, pad printing, transfer and other printing means, brushing, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, dip coating and other means to form a reversible thermochromic layer on a support such as paper, synthetic paper, cloth, flocking or fleece cloth, non-woven fabric, synthetic leather, leather, plastic, glass, ceramics, wood, stone, etc. to obtain a laminate, or dispersed in a support to obtain a molded body.

[0148] Furthermore, a molded product may be obtained as a material that is integrated by kneading into a molten thermoplastic.

[0149] Specific examples of products to which microcapsule pigments are applied include the following.

[0150] (1) Toys

[0151] Dolls and animal-shaped toys, hair for dolls and animal-shaped toys, doll furniture, clothes, hats, handbags, shoes and other doll accessories, decorative toys, cloth toys, painting toys, toy picture books, puzzles and other educational toys, building blocks, block toys, clay toys, mobile toys, spinning tops, kites, musical instrument toys, cooking toys, gun toys, capture toys, background toys, toys imitating vehicles, animals, plants, buildings, food, etc., etc.

[0152] (2) Clothing

[0153] Clothes such as T-shirts, training suits, blouses, ladies’ dresses, swimsuits, raincoats, ski suits, shoes, shoelaces, handkerchiefs, towels, cloth bags, gloves, ties, hats, etc.,

[0154] (3)Indoor decorations

[0155] Carpets, curtains, curtain cords, tablecloths, upholstery fabrics, cushions, decorative frames, artificial flowers, photo frames, etc.

[0156] (4) Furniture

[0157] Bedding, pillows, mattresses and other bedding, lighting fixtures, cooling and heating equipment, etc.

[0158] (5) Decorations

[0159] Rings, bracelets, headwear, earrings, hairpins, false nails, ribbons, bow ties, watches, glasses, etc.

[0160] (6) Stationery

[0161] Writing tools, stamp tools, erasers, pads, rulers, adhesive tapes, etc.

[0162] (7) Daily necessities

[0163] Lipstick, eye shadow, nail polish, hair dye, false nails, false nail paint and other cosmetics, toothbrushes, etc.

[0164] (8) Kitchen supplies

[0165] Cups, plates, chopsticks, spoons, forks, pots, frying pans, etc.

[0166] (9) Others

[0167] Calendars, labels, cards, recording materials, various printed materials for anti-counterfeiting, picture books and other books, handbags, packaging containers, embroidery thread, sports equipment, fishing gear, coasters, musical instruments, pocket warmers, coolants, bags such as wallets, umbrellas, transportation vehicles, buildings, temperature detection indicators, teaching aids, etc.

[0168] Example

[0169] Examples 1 to 14

[0170] The composition used for the reversible thermochromic composition of the present invention is shown in the following table.

[0171] In addition, the numbers in parentheses in the table represent parts by mass, and the numbers representing the blending amounts below are all parts by mass.

[0172] Table 2

[0173]

[0174] Regarding the component (d) in the table, Picrostick A75 is a low molecular weight polystyrene resin with a softening point of 75°C, Picrostick D125 is a low molecular weight polystyrene resin with a softening point of 125°C, and Picrostick A5 is a low molecular weight polystyrene resin with a softening point of 5°C.

[0175] The compounds 1, 2, and 6 described as the component (e) in the table are compounds described in the table exemplifying the component (e).

[0176] After each reversible thermochromic composition is heated and melted to prepare a compatibilizer, a microcapsule pigment in the form of microcapsules enclosed in an epoxy resin film is obtained by interfacial polymerization of an epoxy resin and an amine curing agent.

[0177] Regarding the microcapsule pigment, the following measurement samples were prepared, and the color change temperature was measured by the following measurement method.

[0178] Measurement sample

[0179] Regarding the color change characteristics of the microcapsule pigment, a reversible thermochromic ink prepared by dispersing 40 parts of the microcapsule pigment in 60 parts of ethylene-vinyl acetate emulsion was used, and the resultant was printed on high-quality paper by screen printing, and the printed matter was used as a measurement sample.

[0180] Determination method

[0181] The measurement samples of Examples 1 to 14 were placed in a predetermined position of a colorimeter [TC-3600 colorimeter, manufactured by Tokyo Denshoku Co., Ltd.] and heated at a rate of 10°C / min in a temperature range of 0°C to 40°C.

[0182] After heating to 40° C., the mixture was cooled to the decolorization inducing temperature and allowed to stand to decolorize.

[0183] The color change, color development start temperature (T1), complete color development temperature (T2), decolorization induction temperature, and color density (lightness value) during color development of each example are shown in the following table.

[0184] Table 3

[0185]

[0186] Comparative Examples 1, 2

[0187] The compositions of the reversible thermochromic compositions used are shown in the following table.

[0188] In addition, the numbers in parentheses in the table represent parts by mass, and the numbers representing the blending amounts below are all parts by mass.

[0189] Table 4

[0190]

[0191] After each reversible thermochromic composition is heated and melted to prepare a compatibilizer, a microcapsule pigment in the form of microcapsules enclosed in an epoxy resin film is obtained by interfacial polymerization of an epoxy resin and an amine curing agent.

[0192] Regarding the microcapsule pigment, the following measurement samples were prepared, and the color change temperature was measured by the following measurement method.

[0193] Measurement sample

[0194] Regarding the color change characteristics of the microcapsule pigment, a reversible thermochromic ink prepared by dispersing 40 parts of the microcapsule pigment in 60 parts of ethylene-vinyl acetate emulsion was used, and the resultant was printed on high-quality paper by screen printing, and the printed matter was used as a measurement sample.

[0195] Determination method

[0196] The measurement samples of Comparative Examples 1 and 2 were placed in a predetermined position of a colorimeter [TC-3600 colorimeter, manufactured by Tokyo Denshoku Co., Ltd.] and heated at a rate of 10°C / min in a temperature range of 0°C to 40°C.

[0197] After heating to 40° C., the mixture was cooled to the decolorization inducing temperature and allowed to stand to decolorize.

[0198] The color change, color development start temperature (T1), complete color development temperature (T2), decolorization induction temperature, and color density (lightness value) during color development of each example are shown in the following table.

[0199] In addition, it is shown that the smaller the lightness value in the table, the higher the concentration, and the larger the lightness value, the lower the concentration.

[0200] Table 5

[0201]

[0202] Application Example 1

[0203] A reversible thermochromic screen ink was prepared, which consisted of 30.0 parts of the microcapsule pigment containing the reversible thermochromic composition prepared in Example 1, 2.0 parts of a fluorescent pigment (pink), 50.0 parts of an acrylic resin emulsion, 3.0 parts of a defoaming agent, and 15.0 parts of a turpentine emulsion.

[0204] A reversible thermochromic sheet was obtained by screen printing on polyester taffeta using a reversible thermochromic screen ink to form a reversible thermochromic layer.

[0205] The reversible thermochromic sheet turns purple when heated to above 26°C.

[0206] After the reversible thermochromic sheet was cooled to 18° C., it was left to stand and the reversible thermochromic sheet exhibited a pink color.

[0207] Application Example 2

[0208] 50.0 parts of the microcapsule pigment containing the reversible thermochromic composition prepared in Example 2 was uniformly dispersed and mixed in 50.0 parts of a linseed oil-based offset ink vehicle to prepare a reversible thermochromic offset ink.

[0209] The above-mentioned offset ink was used to perform lithographic printing on high-quality paper to form a reversible thermochromic layer, thereby obtaining a reversible thermochromic sheet.

[0210] If the film is heated to above 38°C, it will turn blue.

[0211] After the reversible thermochromic sheet was cooled to 26° C., the reversible thermochromic sheet became colorless when left to stand.

[0212] Application Example 3

[0213] 33.3 parts of the microcapsule pigment containing the reversible thermochromic composition prepared in Example 3, 66.4 parts of a hard liquid epoxy resin, and 0.3 parts of a defoaming agent are uniformly dispersed and kneaded to obtain a reversible thermochromic epoxy ink. 20.0 parts of a normal temperature curing aliphatic polyamide are added to the ink, and the mixture is stirred and mixed to prepare a reversible thermochromic epoxy ink.

[0214] The reversible thermochromic epoxy ink was used to print the curved surface of the ceramic cup using a stainless steel 100-mesh screen plate, and the reversible thermochromic layer was formed by heat curing at 70° C. for 60 minutes to obtain a reversible thermochromic cup.

[0215] The reversible thermochromic cup turns blue if heated to above 50°C.

[0216] After the reversible thermochromic cup is cooled to 35° C., the reversible thermochromic cup becomes colorless after being left standing.

[0217] Application Example 4

[0218] A reversible thermochromic spray coating is prepared by stirring and mixing a carrier consisting of 10.0 parts of microcapsule pigment containing a reversible thermochromic composition prepared in Example 4, 1.0 part of fluorescent pigment (pink), 45.0 parts of 50% acrylic resin / xylene solution, 15.0 parts of xylene, 23.0 parts of methyl isobutyl ketone, and 6.0 parts of a polyisocyanate curing agent.

[0219] The reversible thermochromic spray paint was spray-coated on the entire train model to form a reversible thermochromic layer, thereby obtaining a reversible thermochromic train model.

[0220] The reversible thermochromic tram model turns purple if heated to above 32°C.

[0221] After the reversible thermochromic electric car model was cooled to 24° C., the reversible thermochromic electric car model turned pink after being left to stand.

[0222] Application Example 5

[0223] A reversible thermochromic spray coating is prepared by stirring and mixing a carrier consisting of 10.0 parts of microcapsule pigment containing a reversible thermochromic composition prepared in Example 7, 1.0 part of a blue pigment, 45.0 parts of a 50% acrylic resin / xylene solution, 15.0 parts of xylene, 23.0 parts of methyl isobutyl ketone, and 6.0 parts of a polyisocyanate curing agent.

[0224] The reversible thermochromic spray paint was spray-coated on the entire electric car model to form a reversible thermochromic layer, thereby obtaining a reversible thermochromic car model.

[0225] The reversible thermochromic car model turns purple if heated above 38°C.

[0226] After the reversible thermochromic car model is cooled to 26°C, the reversible thermochromic car model appears blue after being left standing.

[0227] Application Example 6

[0228] 50.0 parts of the microcapsule pigment containing the reversible thermochromic composition prepared in Example 5, 0.04 parts of yellow pigment, 1000.0 parts of 12 nylon resin (melting point 178°C), and 10.0 parts of ultraviolet absorber were mixed, dispersed with a Henschel mixer, and then used to obtain reversible thermochromic 12 nylon resin particles (reversible thermochromic molding resin composition) using an extruder.

[0229] The reversible thermochromic molding resin composition was melt-spun to obtain a reversible thermochromic filament as a molded product.

[0230] Hair transplantation was performed on the doll's head using filaments.

[0231] If the filament is heated to above 32°C, it will appear green, a mixture of blue and yellow.

[0232] After the filaments were cooled to 10°C, they turned yellow after being left to stand.

[0233] Application Example 7

[0234] 30.0 parts of the microcapsule pigment containing the reversible thermochromic composition prepared in Example 6 was mixed with 45.0 parts of an acrylic resin emulsion, 1.0 part of a defoamer, and 23.0 parts of dilution water, and filtered through a 180-mesh sieve to obtain a reversible thermochromic spray paint.

[0235] The spray paint was filled in a spray gun (diameter 0.6 mm) and applied to the entire surface of a white cloth (support), followed by drying to form a reversible thermochromic layer, thereby obtaining a reversible thermochromic cloth.

[0236] Sewing cloth to make swimsuits.

[0237] If the swimsuit is heated to above 38°C, it will turn blue.

[0238] After the swimsuit was cooled to 20°C and left to stand, the swimsuit appeared white.

[0239] Application Example 8

[0240] 50.0 parts of the microcapsule pigment containing the reversible thermochromic composition prepared in Example 8 was uniformly dispersed and mixed in 50.0 parts of a linseed oil-based offset ink vehicle to prepare a reversible thermochromic offset ink.

[0241] The above-mentioned offset ink was used to perform lithographic printing on high-quality paper to form a reversible thermochromic layer, thereby obtaining a reversible thermochromic sheet.

[0242] The sheet is rubbed with a friction tool made of SEBS to generate friction heat, and when heated to 32°C or higher, it turns blue.

[0243] After the reversible thermochromic sheet was cooled to 5° C., it was left to stand and the reversible thermochromic sheet turned white.

[0244] Application Example 9

[0245] 50.0 parts of the microcapsule pigment containing the reversible thermochromic composition prepared in Example 9 was uniformly dispersed and mixed in 50.0 parts of a linseed oil-based offset ink vehicle to prepare a reversible thermochromic offset ink.

[0246] The reversible thermochromic sheet was obtained by lithographic printing on high-quality paper using offset ink to form a reversible thermochromic layer.

[0247] If the sheet is heated to above 32°C using an electric heating tool, it will turn blue.

[0248] After the reversible thermochromic sheet is cooled to 24°C and left to stand for a while, the reversible thermochromic sheet turns white.

Claims

1. A reversible thermochromic microcapsule pigment, which contains a reversible thermochromic composition, wherein the reversible thermochromic composition comprises: (a) an electron-donating color-developing organic compound; (b) a hydroxyphenylacetic acid ester compound represented by the following general formula (1) as an electron-accepting compound; (c) a compound selected from the group consisting of chain hydrocarbons, alicyclic hydrocarbons and halogenated hydrocarbons, which is a reaction medium for reversibly causing the electron transfer reaction between the components (a) and (b); and (d) a styrene compound having a softening point of 5°C or higher and a weight average molecular weight of 200 to 100,000, The reversible thermochromic composition changes from a decolorizing state to a coloring state by heating, and changes from a coloring state to a decolorizing state by cooling, In the formula, R represents a linear alkyl group having 16 to 20 carbon atoms, X and Y are hydroxyl groups, and Z is hydrogen.

2. The microcapsule pigment according to claim 1, further comprising (e) a compound having a melting point of 50°C or higher and selected from alcohols, esters, ketones, ethers, acid amides, and aromatic hydrocarbons.

3. The microcapsule pigment according to claim 2, wherein the component (e) is a compound selected from esters, ethers and aromatic hydrocarbons. 4 . A reversible thermochromic liquid composition comprising the microcapsule pigment according to claim 1 , and a carrier. 5 . The composition according to claim 4 , wherein the content of the microcapsule pigment is 5 to 40% by mass based on the total mass of the liquid composition. 6 . A laminate comprising: a support and a reversible thermochromic layer, wherein the reversible thermochromic layer comprises the microcapsule pigment according to claim 1 .

7. A molded body comprising the microcapsule pigment according to any one of claims 1 to 3 in a support.

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