JP2001115153A - Reversibly thermochromic composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a reversibly thermochromic composition which is hardly colored brown in its colorless state. SOLUTION: This composition comprises (A) an electron-donating color- developing organic compound comprising a lactone derivative represented by formula 1 or 2, (B) an electron-accepting compound, and (C) a reaction medium which reversibly causes the electron-donating and -accepting reaction between the ingredients A and B in a specified temperature range. In the formulas, R1 is a 1-8C alkyl, phenyl or phenyl substituted by a 1-8C alkyl; R2 and R4 are each a 1-8C alkyl; and R3 is H, a 1-8C alkyl or alkoxy).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a reversible thermochromic composition. More specifically, the present invention relates to a reversible thermochromic composition which does not cause browning (coloring) in a decolored state caused by light irradiation.

[0002]

2. Description of the Related Art Heretofore, a reversible solution composed of a reaction medium having as an essential component a reaction medium which reversibly causes an electron transfer reaction between an electron-donating color-forming organic compound and an electron-accepting compound in a specific temperature range. Several proposals have been disclosed for thermochromic compositions (JP-B-51-44706, JP-B-51-44707, JP-B-44708, JP-B-1-29398, JP-B-4-17154, etc.). ).
Regarding the light fastness of the above-mentioned conventional reversible thermochromic composition, the addition of a light stabilizer can prevent a decrease in color density (color fading) at the time of color development caused by light irradiation. It is difficult to prevent browning (coloring) in the decolored state that occurs, and the reversible thermochromic composition, in which reversible color change is an important requirement, may greatly impair the contrast between color development and color erasing of the reversible thermochromic composition. There is.

[0003]

SUMMARY OF THE INVENTION The present invention can not be achieved by the above-mentioned conventional reversible thermochromic composition. It shows a good color density permanently at the time of color development, and has little residual color at the time of decolorization. In addition, it is an object of the present invention to provide a reversible thermochromic composition that prevents browning (coloring) deterioration during decoloring.

[0004]

As described above, high color density is exhibited at the time of color development, residual color is small at the time of color erasure, and
As a result of examining a reversible thermochromic composition that prevents browning (coloring) at the time of decoloring caused by light irradiation, the present inventors found that (a) an electron-donating color-forming organic As the compound, a specific lactone derivative having an indolyl group substituted by a phenyl group represented by the general formula (1) or (2), an (b) electron-accepting compound functioning as a color developer thereof, The present inventors have found that a system in which a reaction medium which causes the former color development and decoloration in a specific temperature range is compatible with the above requirements satisfies the above requirements, and completed the present invention. That is, the reversible thermochromic composition of the present invention comprises (a) a lactone derivative represented by the following general formula (1) or (2) as an electron-donating color-forming organic compound, (b) an electron-accepting compound, The present invention requires a reversible thermochromic composition comprising a reaction medium which reversibly causes an electron transfer reaction by the components (a) and (b) in a specific temperature range.

Embedded image (Wherein, R ₁ represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 8 carbon atoms, R ₂ represents an alkyl group having 1 to 8 carbon atoms, R ₃
Is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, 1 to 8 carbon atoms
And R ₄ represents an alkyl group having 1 to 8 carbon atoms.) Further, it is required that the reversible thermochromic composition is encapsulated in a microcapsule.

The components (a), (b) and (c) will be specifically described below. The (a) lactone derivative represented by the general formula (1) or (2) of the electron-donating color-forming organic compound exhibits a blue color tone. Among the substituents represented by R ₁ to R ₄ of the lactone derivative, R ₃ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms. To 8 alkoxy groups. The lactone derivative is exemplified below. 3- (4-dimethylaminophenyl) -3- (1-
Methyl-2-phenylindol-3-yl) -4-azaphthalide, 3- (4-diethylaminophenyl) -3
-(1-methyl-2-phenylindol-3-yl)
4-azaphthalide, 3- (4-di-n-butylaminophenyl) -3- (1-methyl-2-phenylindol-3-yl) -4-azaphthalide, 3- (4-di-n
-Amylaminophenyl) -3- (1-methyl-2-phenylindol-3-yl) -4-azaphthalide, 3
-(4-N-methyl-NN-hexylaminophenyl) -3- (1-methyl-2-phenylindole-3
-Yl) -4-azaphthalide, 3- (4-N-ethyl-
N-phenylaminophenyl) -3- (1-methyl-2
-Phenylindol-3-yl) -4-azaphthalide, 3- [4-N-ethyl-N- (4-n-butylphenyl) aminophenyl] -3- (1-methyl-2-phenylindole-3- Yl) -4-azaphthalide, 3-
(4-dimethylamino-2-ethylphenyl) -3-
(1-methyl-2-phenylindol-3-yl)-
4-azaphthalide, 3- (4-diethylamino-2-methylphenyl) -3- (1-methyl-2-phenylindol-3-yl) -4-azaphthalide, 3- (4-di-n-butylamino- 2-methylphenyl) -3- (1
-Methyl-2-phenylindol-3-yl) -4-
Azaphthalide, 3- (4-di-n-amylamino-2-
Ethylphenyl) -3- (1-methyl-2-phenylindol-3-yl) -4-azaphthalide, 3- (4-
N-methyl-NN-hexylamino-2-methylphenyl) -3- (1-methyl-2-phenylindole-
3-yl) -4-azaphthalide, 3- (4-N-ethyl-N-phenylamino-2-methylphenyl) -3-
(1-methyl-2-phenylindol-3-yl)-
4-azaphthalide, 3- [4-N-ethyl-N- (4-
n-butylphenyl) amino-2-methylphenyl]-
3- (1-methyl-2-phenylindol-3-yl) -4-azaphthalide, 3- (4-diethylamino-
2-methylphenyl) -3- (1-ethyl-2-phenylindol-3-yl) -4-azaphthalide, 3-
(4-diethylamino-2-methylphenyl) -3-
(1-n-butyl-2-phenylindol-3-yl) -4-azaphthalide, 3- (4-dimethylamino-
2-methoxyphenyl) -3- (1-methyl-2-phenylindol-3-yl) -4-azaphthalide, 3-
(4-dimethylamino-2-ethoxyphenyl) -3-
(1-methyl-2-phenylindol-3-yl)-
4-azaphthalide, 3- (4-dimethylamino-2-n
-Butoxyphenyl) -3- (1-methyl-2-phenylindol-3-yl) -4-azaphthalide, 3-
(4-Dimethylamino-2-n-hexyloxyphenyl) -3- (1-methyl-2-phenylindole-3
-Yl) -4-azaphthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-methyl-2-
Phenylindol-3-yl) -4-azaphthalide,
3- (4-diethylamino-2-n-butoxyphenyl) -3- (1-methyl-2-phenylindole-3
-Yl) -4-azaphthalide, 3- (4-diethylamino-2-n-hexyloxyphenyl) -3- (1-methyl-2-phenylindol-3-yl) -4-azaphthalide, 3- (4- Diethylamino-2-n-octyloxyphenyl) -3- (1-methyl-2-phenylindol-3-yl) -4-azaphthalide, 3- (4
-Di-n-butylamino-2-methoxyphenyl) -3
-(1-methyl-2-phenylindol-3-yl)
-4-azaphthalide, 3- (4-di-n-butylamino-2-ethoxyphenyl) -3- (1-methyl-2-phenylindol-3-yl) -4-azaphthalide,
-(4-di-n-butylamino-2-n-butoxyphenyl) -3- (1-methyl-2-phenylindole-
3-yl) -4-azaphthalide, 3- (4-di-n-butylamino-2-n-hexyloxyphenyl) -3-
(1-methyl-2-phenylindol-3-yl)-
4-azaphthalide, 3- (4-di-n-butylamino-
2-n-octyloxyphenyl) -3- (1-methyl-2-phenylindol-3-yl) -4-azaphthalide, 3- (4-di-n-amylamino-2-methoxyphenyl) -3- ( 1-methyl-2-phenylindol-3-yl) -4-azaphthalide, 3- (4-di-n
-Amylamino-2-ethoxyphenyl) -3- (1-
Methyl-2-phenylindol-3-yl) -4-azaphthalide, 3- (4-di-n-amylamino-2-n
-Butoxyphenyl) -3- (1-methyl-2-phenylindol-3-yl) -4-azaphthalide, 3-
(4-di-n-amylamino-2-n-amyloxyphenyl) -3- (1-methyl-2-phenylindol-3-yl) -4-azaphthalide, 3- (4-di-n-
Amylamino-2-n-hexyloxyphenyl) -3
-(1-methyl-2-phenylindol-3-yl)
4-azaphthalide, 3- (4-di-n-amylamino-2-n-octyloxyphenyl) -3- (1-methyl-2-phenylindol-3-yl) -4-azaphthalide, 3- (4 -Di-n-butylamino-2-methoxyphenyl) -3- (1-ethyl-2-phenylindol-3-yl) -4-azaphthalide, 3- (4-di-
n-butylamino-2-ethoxyphenyl) -3- (1
-Ethyl-2-phenylindol-3-yl) -4-
Azaphthalide, 3- (4-diethylamino-2-n-butoxyphenyl) -3- (1-n-butyl-2-phenylindol-3-yl) -4-azaphthalide, 3-
(4-Diethylamino-2-n-hexyloxyphenyl) -3- (1-n-hexyl-2-phenylindol-3-yl) -4-azaphthalide, 3- [4-N-ethyl-N- (4 -N-butylphenyl) amino-2-methylphenyl] -3- (1-ethyl-2-phenylindol-3-yl) -4-azaphthalide, 3- [4-N
-Ethyl-N- (4-n-butylphenyl) amino-2
-Methylphenyl] -3- (1-n-butyl-2-phenylindol-3-yl) -4-azaphthalide;

3- (4-dimethylaminophenyl) -3
-(1-methyl-2-phenylindol-3-yl)
-7-azaphthalide, 3- (4-diethylaminophenyl) -3- (1-methyl-2-phenylindole-3
-Yl) -7-azaphthalide, 3- (4-di-n-butylaminophenyl) -3- (1-methyl-2-phenylindol-3-yl) -7-azaphthalide, 3- (4
-Di-n-amylaminophenyl) -3- (1-methyl-2-phenylindol-3-yl) -7-azaphthalide, 3- (4-N-methyl-NN-hexylaminophenyl) -3 -(1-Methyl-2-phenylindol-3-yl) -7-azaphthalide, 3- (4-N-ethyl-N-phenylaminophenyl) -3- (1-methyl-2-phenylindol-3- Yl) -7-azaphthalide, 3- [4-N-ethyl-N- (4-n-butylphenyl) aminophenyl] -3- (1-methyl-2-
Phenylindol-3-yl) -7-azaphthalide,
3- (4-dimethylamino-2-ethylphenyl) -3
-(1-methyl-2-phenylindol-3-yl)
-7-azaphthalide, 3- (4-diethylamino-2-
Methylphenyl) -3- (1-methyl-2-phenylindol-3-yl) -7-azaphthalide, 3- (4-
Di-n-butylamino-2-methylphenyl) -3-
(1-methyl-2-phenylindol-3-yl)-
7-azaphthalide, 3- (4-di-n-amylamino-
2-ethylphenyl) -3- (1-methyl-2-phenylindol-3-yl) -7-azaphthalide, 3-
(4-N-methyl-NN-hexylamino-2-methylphenyl) -3- (1-methyl-2-phenylindol-3-yl) -7-azaphthalide, 3- (4-N-
Ethyl-N-phenylamino-2-methylphenyl)-
3- (1-methyl-2-phenylindol-3-yl) -7-azaphthalide, 3- [4-N-ethyl-N-
(4-n-butylphenyl) amino-2-methylphenyl] -3- (1-methyl-2-phenylindole-3
-Yl) -7-azaphthalide, 3- (4-diethylamino-2-methylphenyl) -3- (1-ethyl-2-phenylindol-3-yl) -7-azaphthalide,
-(4-diethylamino-2-methylphenyl) -3-
(1-n-butyl-2-phenylindol-3-yl) -7-azaphthalide, 3- (4-dimethylamino-
2-methoxyphenyl) -3- (1-methyl-2-phenylindol-3-yl) -7-azaphthalide, 3-
(4-dimethylamino-2-ethoxyphenyl) -3-
(1-methyl-2-phenylindol-3-yl)-
7-azaphthalide, 3- (4-dimethylamino-2-n
-Butoxyphenyl) -3- (1-methyl-2-phenylindol-3-yl) -7-azaphthalide, 3-
(4-Dimethylamino-2-n-hexyloxyphenyl) -3- (1-methyl-2-phenylindole-3
-Yl) -7-azaphthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-methyl-2-
Phenylindol-3-yl) -7-azaphthalide,
3- (4-diethylamino-2-n-butoxyphenyl) -3- (1-methyl-2-phenylindole-3
-Yl) -7-azaphthalide, 3- (4-diethylamino-2-n-hexyloxyphenyl) -3- (1-methyl-2-phenylindol-3-yl) -7-azaphthalide, 3- (4- Diethylamino-2-n-octyloxyphenyl) -3- (1-methyl-2-phenylindol-3-yl) -7-azaphthalide, 3- (4
-Di-n-butylamino-2-methoxyphenyl) -3
-(1-methyl-2-phenylindol-3-yl)
-7-azaphthalide, 3- (4-di-n-butylamino-2-ethoxyphenyl) -3- (1-methyl-2-phenylindol-3-yl) -7-azaphthalide,
-(4-di-n-butylamino-2-n-butoxyphenyl) -3- (1-methyl-2-phenylindole-
3-yl) -7-azaphthalide, 3- (4-di-n-butylamino-2-n-hexyloxyphenyl) -3-
(1-methyl-2-phenylindol-3-yl)-
7-azaphthalide, 3- (4-di-n-butylamino-
2-n-octyloxyphenyl) -3- (1-methyl-2-phenylindol-3-yl) -7-azaphthalide, 3- (4-di-n-amylamino-2-methoxyphenyl) -3- ( 1-methyl-2-phenylindol-3-yl) -7-azaphthalide, 3- (4-di-n
-Amylamino-2-ethoxyphenyl) -3- (1-
Methyl-2-phenylindol-3-yl) -7-azaphthalide, 3- (4-di-n-amylamino-2-n
-Butoxyphenyl) -3- (1-methyl-2-phenylindol-3-yl) -7-azaphthalide, 3-
(4-di-n-amylamino-2-n-amyloxyphenyl) -3- (1-methyl-2-phenylindol-3-yl) -7-azaphthalide, 3- (4-di-n-
Amylamino-2-n-hexyloxyphenyl) -3
-(1-methyl-2-phenylindol-3-yl)
-7-azaphthalide, 3- (4-di-n-amylamino-2-n-octyloxyphenyl) -3- (1-methyl-2-phenylindol-3-yl) -7-azaphthalide, 3- (4 -Di-n-butylamino-2-methoxyphenyl) -3- (1-ethyl-2-phenylindol-3-yl) -7-azaphthalide, 3- (4-di-
n-butylamino-2-ethoxyphenyl) -3- (1
-Ethyl-2-phenylindol-3-yl) -7-
Azaphthalide, 3- (4-diethylamino-2-n-butoxyphenyl) -3- (1-n-butyl-2-phenylindol-3-yl) -7-azaphthalide, 3-
(4-Diethylamino-2-n-hexyloxyphenyl) -3- (1-n-hexyl-2-phenylindol-3-yl) -7-azaphthalide, 3- [4-N-ethyl-N- (4 -N-butylphenyl) amino-2-methylphenyl] -3- (1-ethyl-2-phenylindol-3-yl) -7-azaphthalide, 3- [4-N
-Ethyl-N- (4-n-butylphenyl) amino-2
-Methylphenyl] -3- (1-n-butyl-2-phenylindol-3-yl) -7-azaphthalide;

The (b) electron-accepting compounds include compounds having an active proton and pseudo-acid compounds (compounds which are not acids but which act as acids in the composition to form the color of component (a)). And compounds having electron vacancies. When the compound having an active proton is exemplified, the compound having a phenolic hydroxyl group includes monophenols to polyphenols, and further, as a substituent thereof, an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, a carboxy group and an ester thereof. Or phenol-aldehyde condensed resins such as bis- and tris-type phenols having an amide group, a halogen group and the like. Further, a metal salt of the compound having a phenolic hydroxyl group may be used.

Specific examples will be described below. Phenol, o-
Cresol, tert-butylcatechol, nonylphenol, n-octylphenol, n-dodecylphenol, n-stearylphenol, p-chlorophenol, p-bromophenol, o-phenylphenol, 4- (4- (1-methylethoxyphenyl) Sulfonylphenol, 4- (4-butyloxyphenyl) sulfonylphenol, 4- (4-pentyloxyphenyl) sulfonylphenol, 4- (4-hexyloxyphenyl) sulfonylphenol, 4- (4-heptyloxyphenyl) sulfonylphenol , 4- (4-octyloxyphenyl) sulfonylphenol, n-butyl p-hydroxybenzoate, n-octyl p-hydroxybenzoate, resorcinol, dodecyl gallate, 2,2
-Bis (4'-hydroxyphenyl) propane, 4,4
-Dihydroxydiphenylsulfone, 1,1-bis (4'-hydroxyphenyl) ethane, 2,2-bis (4'-hydroxy-3-methylphenyl) propane,
Bis (4-hydroxyphenyl) sulfide, 1-phenyl-1,1-bis (4′-hydroxyphenyl) ethane, 1,1-bis (4′-hydroxyphenyl) -3-
Methylbutane, 1,1-bis (4′-hydroxyphenyl) -2-methylpropane, 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,
2,2-bis (4′-hydroxyphenyl) butane,
2,2-bis (4′-hydroxyphenyl) ethyl propionate, 2,2-bis (4′-hydroxyphenyl) -4-methylpentane, 2,2-bis (4′-hydroxyphenyl) hexafluoropropane 2,2-bis (4′-hydroxyphenyl) n-heptane, 2,2
-Bis (4'-hydroxyphenyl) n-nonane, and the like. Although the compound having a phenolic hydroxyl group can exhibit the most effective thermochromic properties, their metal salts, aromatic carboxylic acids and aliphatic carboxylic acids having 2 to 5 carbon atoms and their metal salts, It may be a compound selected from an acid metal salt, an acid phosphate ester and their metal salts, 1,2,3-triazole and derivatives thereof. Furthermore, a fluoroalcohol compound can also be used, and is exemplified below. 2-hydroxyhexafluoroisopropylbenzene, 1,3-bis (2-hydroxyhexafluoroisopropyl) benzene, 1,4-
Bis (2-hydroxyhexafluoroisopropyl) benzene, 1,3-bis (2-hydroxymethyl-hexafluoroisopropyl) benzene, 1,3-bis (3-
Hydroxy-1,1-bistrifluoromethylpropyl) benzene, 1,4-bis (2-hydroxymethyl-
Hexafluoroisopropyl) benzene, 1,4-bis (3-hydroxy-1,1-bistrifluoromethylpropyl) benzene, 2-hydroxymethyl-hexafluoroisopropylbenzene, 3-hydroxy-1,1-
Bistrifluoromethylpropylbenzene,

The component (c) of the reaction medium which causes the electron transfer reaction by the components (a) and (b) to reversibly occur in a specific temperature range will be described. Examples of the component (c) include alcohols, esters, ketones, ethers, and acid amides. When applied to microencapsulation and secondary processing, low molecular weight compounds evaporate out of the capsule system when subjected to high heat treatment, so that a compound having 10 or more carbon atoms should be stably retained in the capsule. It is preferably used. Alcohols have 1 carbon atom
An aliphatic monohydric saturated alcohol of 0 or more is effective. Specifically, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, heptadecyl alcohol, octadecyl Alcohol, eicosyl alcohol, docosyl alcohol and the like.

As the esters, esters having 10 or more carbon atoms are effective. The esters of a monovalent carboxylic acid having an aliphatic and alicyclic or aromatic ring and a monohydric alcohol having an aliphatic and alicyclic or aromatic ring are useful. Esters and aliphatics obtained from any combination of esters, aliphatic and alicyclic or aromatic polyhydric carboxylic acids and aliphatic and alicyclic or aromatic monohydric alcohols obtained from any combination And esters obtained from any combination of a monovalent carboxylic acid having an alicyclic or aromatic ring and a polyhydric alcohol having an aliphatic and an alicyclic or aromatic ring, and specifically, ethyl caprylate and caprylic acid. Octyl, stearyl caprylate, myristyl caprate,
Docosyl caprate, 2-ethylhexyl laurate,
N-decyl laurate, 3-methylbutyl myristate, cetyl myristate, isopropyl palmitate,
Neopentyl palmitate, nonyl palmitate, cyclohexyl palmitate, n-butyl stearate, 2-methylbutyl stearate, 3,5,5 stearate
-Trimethylhexyl, n-undecyl stearate,
Pentadecyl stearate, stearyl stearate,
Cyclohexylmethyl stearate, isopropyl behenate, hexyl behenate, lauryl behenate, behenyl behenate, cetyl benzoate, stearyl p-tert-butyl benzoate, dimyristyl phthalate, distearyl phthalate, dimyristyl oxalate, dicetyl oxalate ,
Dicetyl malonate, dilauryl succinate, dilauryl glutarate, diundecyl adipate, dilauryl azelate, di- (n-nonyl) sebacate, dineopentyl 1,18-octadecylmethylenedicarboxylate, ethylene glycol dimyristate, propylene glycol dilaurate, Propylene glycol distearate,
Hexylene glycol dipalmitate, 1,5-pentanediol distearate, 1,2,6-hexanetrioltrimyristate, 1,4-cyclohexanedioldidecyl, 1,4-cyclohexanedimethanol dimyristate, xylene Glycol dicaprinate, xylene glycol distearate and the like.

Esters of saturated fatty acids and branched aliphatic alcohols, unsaturated fatty acids or saturated or branched or substituted fatty acids of aliphatic alcohols having 16 or more carbon atoms, cetyl butyrate, Ester compounds selected from stearyl butyrate and behenyl butyrate are also effective. Specifically, 2-ethylhexyl butyrate, 2-ethylhexyl behenate, 2-ethylhexyl myristate, 2-ethylhexyl caprate, lauric acid 3,
5,5-trimethylhexyl, palmitic acid 3,5,5
-Trimethylhexyl, 3,5,5-trimethylhexyl stearate, 2-methylbutyl caproate, 2-methylbutyl caprylate, 2-methylbutyl caprate,
1-ethylpropyl palmitate, 1-ethylpropyl stearate, 1-ethylpropyl behenate, 1-ethylhexyl laurate, 1-ethylhexyl myristate, 1-ethylhexyl palmitate, 2-caproic acid
Methylpentyl, 2-methylpentyl caprylate, 2-methylpentyl caprate, 2-methylpentyl laurate, 2-methylbutyl stearate, 2 stearic acid
-Methylbutyl, 3-methylbutyl stearate, 1-methylheptyl stearate, 2-methylbutyl behenate, 3-methylbutyl behenate, 1-methylheptyl stearate, 1-methylheptyl behenate, 1-ethylpentyl caproate, palmitin 1-ethylpentyl acid, 1-methylpropyl stearate, 1 stearic acid
-Methyloctyl, 1-methylhexyl stearate,
1,1-dimethylpropyl laurate, 1-capric acid
Methylpentyl, 2-methylhexyl palmitate, 2-methylhexyl stearate, 2-methylhexyl behenate, 3,7-dimethyloctyl laurate, 3,7-dimethyloctyl myristate, 3,7 palmitate
-Dimethyloctyl, 3,7-dimethyloctyl stearate, 3,7-dimethyloctyl behenate, 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, 2
-Isostearyl ketomyristate, 2-ethylhexyl 2-fluoromyristate, cetyl butyrate, stearyl butyrate, behenyl butyrate and the like.

Further, regarding the color density-temperature curve, a large hysteresis characteristic (a curve plotting a change in color density due to a temperature change indicates a case where the temperature is changed from a low temperature to a high temperature and a case where the temperature is changed from a high temperature to a low temperature). Depends on the case)
In order to obtain a reversible thermochromic composition that exhibits color memory and changes color, the applicant of the present invention first disclosed in Japanese Patent Publication No. Hei 4-1715.
No. 4 discloses a carboxylic acid ester compound having a ΔT value (melting point−cloud point) of 5 ° C. or more and less than 50 ° C., for example, a carboxylic acid ester having a substituted aromatic ring in the molecule, containing an unsubstituted aromatic ring Esters of carboxylic acids 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, and fatty acids having 8 or more carbon atoms and branched Aliphatic alcohols or esters, esters of dicarboxylic acids with aromatic or branched aliphatic alcohols, dibenzyl cinnamate, heptyl stearate, didecyl adipate, dilauryl adipate, dimyristyl adipate, dicetyl adipate, distearyl adipate, Trilaurin, Trimyristin, Tristearin, Jimiri Chin distearate and the like are preferably used.

A fatty acid ester compound obtained from an odd aliphatic monohydric alcohol having 9 or more carbon atoms and an aliphatic carboxylic acid having an even carbon number, n-pentyl alcohol or n-heptyl alcohol, and an even aliphatic compound having 10 to 16 carbon atoms. Fatty acid ester compounds having a total of 17 to 23 carbon atoms obtained from aliphatic carboxylic acids 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-caprate
Heptyl, n-nonyl caprate, n-undecyl caprate, n-tridecyl caprate, n-pentadecyl caprate, n-pentyl laurate, n-laurate
Heptyl, n-nonyl laurate, n-undecyl laurate, n-tridecyl laurate, n-pentadecyl laurate, n-pentyl myristate, n-heptyl myristate, 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-stearate
-Nonyl, n-undecyl stearate, n-tridecyl stearate, n-pentadecyl stearate, n-nonyl eicosanoate, n-undecyl eicosanoate, n-tridecyl eicosanoate, n-pentadecyl eicosanoate, n-nonyl behenate , N-undecyl behenate, n-tridecyl behenate, n-pentadecyl behenate and the like.

As the ketones, aliphatic ketones having a total carbon number of 10 or more are effective, and 2-decanone, 3-decanone, 4-decanone, 2-undecanone, 3-undecanone, 4-undecanone, 5-undecanone, Undecanone, 2-dodecanone, 3-dodecanone, 4-dodecanone, 5-dodecanone, 2-tridecanone, 3-tridecanone, 2-tetradecanone, 2-pentadecanone, 8-pentadecanone, 2-hexadecanone, 3-hexadecanone, 9-heptacanone, 2-pentadecanone, 2-octadecanone, 2-nonadecanone, 10-nonadacanone, 2-eicosanone, 11-eicosanone, 2-heneicosanone, 2-docosanone, lauron, stearone, and the like. Further, arylalkyl 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-octyl acetophenone, n-nonanophenone, 4-n-heptyl acetophenone, n-
Octanophenone, 4-n-hexyl acetophenone,
4-n-cyclohexyl acetophenone, 4-tert
-Butylpropiophenone, n-heptaphenone, 4-
Examples thereof include n-pentyl acetophenone, cyclohexyl phenyl ketone, benzyl-n-butyl ketone, 4-n-butyl acetophenone, n-hexanophenone, 4-isobutyl acetophenone, 1-acetonaphthone, 2-acetonaphthone, and cyclopentyl phenyl ketone.

As ethers, aliphatic ethers having a total carbon number of 10 or more are effective, such as 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, decane Examples thereof include diol dimethyl ether, undecane diol dimethyl ether, dodecane diol dimethyl ether, tridecane diol dimethyl ether, decane diol diethyl ether, and undecane diol diethyl ether.

Examples of the acid amides include acetamide, propionamide, butyric amide, caproic amide, caprylic amide, capric amide, lauric amide,
Myristic amide, palmitic amide, stearic amide, behenic amide, oleic amide, erucamide, benzamide, caproic anilide, caprylic anilide, capric anilide, lauric anilide, myristic anilide, palmitic anilide,
Stearic acid anilide, behenic acid anilide, oleic acid anilide, erucic acid anilide, caproic acid N-methylamide, caprylic acid N-methylamide, capric acid N-
Methylamide, lauric acid N-methylamide, 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 ,
N-butylamide stearate, N-butylamide oleate, N-octylamide laurate, N-octylamide myristate, N-octylamide palmitate, N-octylamide stearate, N-oleate
Octylamide, lauric acid N-dodecylamide, myristic acid N-dodecylamide, palmitic acid N-dodecylamide, stearic acid N-dodecylamide, oleic acid N-dodecylamide, dilauric amide, dimyristic amide, dipalmitic acid Amide, distearic amide, dioleic amide, trilauric amide,
Trimyristic amide, tripalmitic amide, tristearic amide, trioleic amide, succinic amide, adipic amide, glutaric amide, malonamide, azelaic amide, maleic 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, adipic acid N-butylamide, glutaric acid N-butylamide, malonic acid N-butylamide, Adipic acid N-
Octylamide, adipic acid N-dodecylamide and the like.

The reversible thermochromic composition of the present invention is a compatibilizer containing the above-mentioned components (a), (b), and (c) as essential components. Although it depends on the type of each component and the components, generally, the component ratio at which desired characteristics can be obtained is as follows.
1 to 100, preferably 0.1 to 50, (c) component 5
100 (all of the above ratios are parts by weight).

Various light stabilizers can be added to the reversible thermochromic composition of the present invention, if necessary. The light stabilizer is contained in order to prevent light deterioration of the reversible thermochromic composition comprising the components (a), (b), and (c), and
It is contained in a proportion of 24% by weight, preferably 0.8 to 16% by weight. Among the light stabilizers, an ultraviolet absorber effectively blocks ultraviolet light contained in sunlight or the like and prevents light deterioration caused by an excited state due to a photoreaction of the component (a). Antioxidants, singlet oxygen quenchers, superoxide anion quenchers, ozone quenchers, and the like suppress oxidation reactions. The light stabilizers may be used alone or in combination of two or more.

Specific examples of the light stabilizer are described below.
Examples of the ultraviolet absorbent include 2,4-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone,
2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-octo Xybenzophenone, bis- (2-methoxy-4-hydroxy-5-benzoylphenyl) -methane, 2- [2 ′
-Hydroxy-3'-5'-di-t-amylphenyl]
-Benzophenone, 2-hydroxy-4-dodecyloxy-benzophenone [trade name: Seesorb 103, manufactured by Cipro Kasei Co., Ltd.], 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4-
Methoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2- [2′-hydroxy-
3'-5'-di-t-amylphenyl] -benzophenone and the like.

Phenyl salicylate, para-t salicylate
-Butylphenyl, paraoctylphenyl salicylate,
2-4-di-t-butylphenyl-4-hydroxybenzoate, 1-hydroxybenzoate, 1-hydroxy-3-t-butyl-benzoate, 1-hydroxy-
Salicylic acid UV absorbers such as 3-t-octyl benzoate and resorcinol monobenzoate.

Ethyl-2-cyano-3,3'-diphenylacrylate, 2-ethylhexyl-2-cyano-
Cyanoacrylate-based ultraviolet absorbers such as 3,3′-diphenylacrylate and 2-ethylhexyl-2-cyano-3-phenylcinnarate;

2- [5-t-butyl-2-hydroxyphenyl] -benzotriazole [trade name: Tinuvin-P
S, Ciba-Geigy], 2- [5-methyl-2-hydroxyphenyl] -benzotriazole, 2- [2, hydroxy-3,5-bis (a, a-dimethylbenzyl)]
Phenyl] -2H benzotriazole, 2- [3,5-
Di-tert-butyl-2-hydroxyphenyl] -benzotriazole, 2- [3-tert-butyl-5-methyl-2-
Hydroxyphenyl] -5-chlorobenzotriazole, 2- [3,5-di-t-butyl-2-hydroxyphenyl] -5-chlorobenzotriazole, 2- [3
5-Di-t-amyl-2-hydroxyphenyl] -benzotriazole (trade name: Tinuvin 328, manufactured by Ciba Geigy), methyl-3- [3-t-butyl-5- (2H
-Benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol molecular weight 300 (trade name: Tinuvin 1130, manufactured by Ciba Geigy), 2- [3-dodecyl-5-methyl-2-hydroxyphenyl] benzotriazole , Methyl-3- [3-
(2H-benzotriazol-2-yl) -5-t-butyl-4-hydroxyphenyl] propionate-polyethylene glycol molecular weight 300, 2- [3-t-butyl-5-propyloctylate-2-hydroxyphenyl]- 5-chlorobenzotriazole, 2- [2-hydroxyphenyl-3,5-di- (1,1′-dimethylbenzyl) phenyl] -2H-benzotriazole, 2-
[2-hydroxy-5-t-octylphenyl] -2H
-Benzotriazole, 2- [3-t-butyl-5-octyloxycarbonylylethyl-2-hydroxyphenyl] -benzotriazole [trade name: Tinuvin 384,
Ciba-Geigy], 2- [2-hydroxy-5-tetraoctylphenyl] -benzotriazole, 2- [2
-Hydroxy-4-octoxy-phenyl] -benzotriazole, 2- [2'-hydroxy-3 '-(3 "
4 "5" 6 "-tetrahydrophthalimidomethyl)-
5'-methylphenyl] -benzotriazole, 2-
Benzotriazole-based ultraviolet absorbers such as (2-hydroxy-5-t-butylphenyl) -benzotriazole.

Ethanediamide-N- (2-ethoxyphenyl) -N '-(4-isododecylphenyl), 2,
2,4,4-tetramethyl-20- (β-lauryl-oxycarbonyl) -ethyl-7-oxa-3,20-diazodispiro (5,1,11,2) heneicoic acid-21
And oxalic anilide type ultraviolet absorbers such as -one.

Examples of the antioxidant (antiaging agent) include dimethyl-1- (2, hydroxyethyl) -4-hydroxy-2,2,6,6, tetramethylpiperidine polycondensate of dimethyl succinate and poly [[6 -(1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2-cyyl "" (2,2,6,6-tetramethyl-4-piperidyl) imino "] , 2- (3,5-di-t-butyl-4)
-Hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentapetyl-4-piperidyl), N, N'-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,
2,6,6-pentapetyl-4-piperidyl) amino]
-6-chloro-1,3,5-triazine condensate, bis [1,2,2,6,6-pentamethyl-4-piperidylsebacic acid] 4-benzoyloxy-2,2,6,6-
Tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,
Hindered amine antioxidants such as 3,8-triazaspiro "4,5] decane-2,4-dione.

2,6, di-tert-butyl-4-methylphenol, 2-tert-butyl-4-methoxyphenol,
2,6-di-t-butyl-4-ethylphenol, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2-methylenebis (4-methyl-6-t -Butylphenol), 4,4-
Thiobis (2-methyl-6-t-butylphenol),
2,2-thiobis (4-methyl-6-t-butylphenol), 4,4-butylidenebis (3-methyl-6-t
-Butylphenol), 3,9-bis [1,1-dimethyl-2- [β- (3-t-butyl-4-hydroxy-5
-Methylphenyl) propionyloxy] ethyl] 2,
4,8,10-tetraoxaspiro [5,5] -undecane, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl- 2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]- Methane, 2,2-
Ethylene bis (4,6-di-t-butylphenol),
Bis [3,3′-bis- (4′-hydroxy-3′-t
-Butylphenyl) butyric acid] -glycol ester, 1,3,5-tris (3'5'-di-t-butyl-4'-hydroxybenzyl) -S-triazine-
2,4,6- (1H, 3H, 5H) -trione, tocophenol, 1,3,5-tris (4-t-butyl-3-
(Hydroxy-2,6-dimethylbenzyl) isocyanurate, pentaerythritol tetrakis (3-laurylthiopropionate), triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate ], 1,6-hexadiol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thioethylenebis [3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-t-butyl-4-hydroxy-hydrocinnamide), tris- (3,5-di-t-butyl) −
4-hydroxybenzyl) isocyanurate, 2,2
Phenolic antioxidants such as 4-trimethyl-1,2-hydroquinone, stylate phenol, 2,5-di-t-butyl-hydroquinone, bis (2,2,6,6-tetramethyl-4, piperidyl) sebacate Agent.

Dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate;
Sulfur-based antioxidants such as stearylthiopropylamide.

Tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, 3,
5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, triphenylphosphite, diphenylisodecylphosphite, phenylisodecylphosphite, 4,4'-butylidene-bis (3-methyl- 6-t-butylphenylditridecyl) phosphite, octadecylphosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol diphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene,
10- (3,5-di-tert-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9 -Oxa-10-phosphaphenanthrene, cyclic neopentatetraylbis (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2
6, -di-t-butyl-4-methylphenyl) phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, 2,4-bis-
(N-octylthio) -6- (4-hydroxy-3,5
-Di-t-butylanilino) -1,3,5-triazine, phosphoric acid-based antioxidants such as octylated diphenylamine, and the like.

As singlet oxygen quenchers, carotenes,
Examples include pigments, amines, phenols, nickel complexes, sulfides, and the like, for example, 1,4-diazabicyclo (2,2,2) octane (DABCO), β-carotene, 1,3-cyclohexadiene, 2-diethylaminomethylfuran, 2-phenylaminomethylfuran, 9
-Diethylaminomethylanthracene, 5-diethylaminomethyl-6-phenyl-3,4-dihydroxypyran, nickel dimethyldithiocarbamate, nickel 3
-5-di-t-butyl-4-hydroxybenzyl O-ethylphosphonate, nickel 3,5-di-t-butyl-
4-hydroxybenzyl O-butylphosphonate, nickel [2.2'-thiobis (4-t-octylphenolate)] (n-butylamine), nickel [2.2'-
Thio-bis (4-t-octylphenolate)] (2-
Ethylhexylamine), nickel bis [2.2'-thio-bis (4-t-octylphenolate)], nickel bis [2.2'-sulfone-bis (4-octylphenolate)], nickel bis [2 -Hydroxy-5-methoxyphenyl-NN-butylaldimine), nickel bis (dithiobenzyl), nickel bis (dithiobiacetyl) and the like.

Examples of the superoxide anion quencher include complexes of superoxide dismutase with cobalt and nickel.

Examples of the ozone quencher include 4,4'-thiobis (6-t-butyl-m-cresol), 2,4,6-
Tri-t-butylphenol, 1,4-diazabicyclo [2.2.2] octane, N-phenyl-β-naphthylamine, α-tocopherol, 4,4′-methylene-bis (2,6-di-t-butylphenol ), P, P'-
Diaminodiphenylmethane, 2,2'-methylene-bis (6-t-butyl-P-cresol), N, N'-diphenyl-P-phenylenediamine, N, N'-diphenylethylenediamine, N-isopropyl-N'- Phenyl-p-phenylenediamine and the like.

As the infrared absorbent, 700 to 2000
with a maximum absorption in the near infrared region of 400 nm
m is a compound having a property that does not have much absorption in the visible region, for example,

[0032]

Embedded image However, R ₁ , R ₂ , R ₃ and R ₄ in the formula are alkyl groups, X
Is either a halogen or a hydrogen atom, Me is nickel,
Indicates either palladium or platinum.

[0033]

Embedded image However, R ₁ , R ₂ , R ₃ and R ₄ in the formula are alkyl groups, X
Is either a halogen or a hydrogen atom, Me is nickel,
X represents any of palladium and platinum, and X represents any of carbon, oxygen and sulfur atoms.

[0034]

Embedded image However, R ₁ , R ₂ , R ₃ and R ₄ in the formula are alkyl groups, X
Is either a halogen or a hydrogen atom, Me is nickel,
X represents halogen or a hydrogen atom, either of palladium or platinum.

[0035]

Embedded image Here, R represents any one of a hydrogen atom, an alkoxy group, a phenyl group, an alkyl- or alkoxy-substituted phenyl group, and a thienyl group, and Me represents any one of nickel, palladium, and platinum.

[0036]

Embedded imageWhere R is an alkyl group and X is a perchlorate as an anion
(ClO_Four ^- ), Fluoborate (BF_Four ^- ),bird
Chloroacetic acid salt (Cl_Three COO^- ), Trifluoroacetate
(CF_Three COO^- ), Picrate [(NO_Three )_Three C₆ 
H_Two O^- ], Hexafluoroarsenate (AsF₆ ^- ), F
Xachloroantimonate, (SbCl₆ ^- ), Hex
Fluorantimonate (SbF₆ ^- ), Benzene sul
Fonate (C₆ H_Five SO_Three ^- ), Alkyl sulfonate
(RSO_Three ^- ), Phosphate (PO_Four ^{Three -} ), Sulfate (SO
_Four ^2- ), Chloride (Cl^- ), Bromide (Br)^- )
Indicates And the like.

The above-mentioned reversible thermochromic composition is effective even when applied as it is, but is preferably used as a microcapsule pigment encapsulated in microcapsules.
This is because the reversible thermochromic compositions can be maintained under the same composition under the various use conditions and can exert the same effect. By being encapsulated in the microcapsules, a chemically and physically stable pigment can be constituted, and the range of particle diameter of 0.1 to 100 μm, preferably 1 to 50 μm, more preferably 2 to 30 μm satisfies practicality.
The microencapsulation is carried out by a conventionally known interfacial polymerization method, in situ polymerization method, in-liquid curing coating method, phase separation method from aqueous solution, phase separation method from organic solvent, melting dispersion cooling method, air suspension. There are coating method, spray drying method, etc.
It is appropriately selected according to the application. Further, a secondary resin film may be further provided on the surface of the microcapsule according to the purpose to impart durability, or the surface characteristics may be modified for practical use. When the reversible thermochromic composition is encapsulated in the microcapsules, the light stabilizer may be encapsulated in the microcapsules together with the reversible thermochromic composition, or as a coloring material when not encapsulated in the microcapsules. It is added into the vehicle used when applied. or,
The light stabilizer can be included in a microcapsule and also added to a vehicle.

The reversible thermochromic composition is dispersed in a vehicle containing a resin binder to form a thermochromic layer.
Incidentally, the color change of the thermochromic layer can also be varied by mixing an appropriate amount of the non-thermochromic colored dye or pigment.

[0039]

BEST MODE FOR CARRYING OUT THE INVENTION The reversible thermochromic composition of the present invention comprises:
It can be dispersed or dispersed in various vehicles and printed or coated on a support such as paper, cloth, leather, plastic, or the like in the form of a printing ink or a spray paint to obtain a printed product or a coated product. In addition, characters and figures can be drawn on the support in the form of writing ink, solid writing tools such as crayons, paints, and the like. Further, after being dispersed in the resin, it can be molded to form various molded articles, films, sheets, filaments and the like. Thus, it is used in various fields such as toys, decorations, teaching materials, stationery, textiles, household goods, sports goods, indoor and outdoor equipment, clothing, and various printed materials.

[0040]

The following table shows the components (a), (b) and (c), the color change of the composition and the color change temperature. The numbers in parentheses in the table indicate parts by weight.

[0041]

[Table 1]

The following tables show comparative examples (a), (b),
The (c) component, the color change of the composition, and the color change temperature are shown (Comparative Examples 1 and 2 used a lactone derivative having an indolyl group not substituted with a phenyl group as the (a) component).

[0043]

[Table 2]

Light Resistance Test Preparation of Light Resistance Test Sample The reversible thermochromic composition 10 of Examples 1 to 3 and Comparative Example 1
The part was accommodated in a bottomed cylindrical glass tube to obtain a test sample.
For Examples 4 to 14 and Comparative Examples 2 and 3, microcapsule pigments containing each of the following compositions were used.
Parts were used as coloring agents, and 80 parts of the vehicle were added to form inks and printed on synthetic paper to obtain test samples.

A method for preparing a microcapsule pigment containing the reversible thermochromic composition will be described. Examples 4 to 1
10 parts of EPON 828 (epoxy resin, manufactured by Yuka Shell Epoxy Co., Ltd.) were added to 10 parts of 70 parts of the compositions of Comparative Example 2 and Comparative Example 2.
Heat and dissolve at 0 ° C.
Then, the mixture is stirred so as to become fine droplets. A solution prepared by dissolving 5 parts of a separately prepared curing agent (amine adduct of epoxy resin, manufactured by Yuka Shell Epoxy Co., Ltd.) in 45 parts of water was gradually added to the stirring solution, and the liquid temperature was raised to 80%. C. and kept stirring for about 5 hours to obtain a microcapsule suspension. The microcapsule pigment obtained by centrifuging the microcapsule suspension has the same color change temperature and color change as each composition.

Example 13 70 parts of the composition of Example 8 were used as light stabilizers, 2- (3,5
-Di-t-amyl-2-hydroxyphenyl) benzotriazole (2 parts) and Epon 828 (epoxy resin, Yuka Shell Epoxy Co., Ltd.) (10 parts) were heated and dissolved at 100 ° C, and this was dissolved in a 10% gelatin aqueous solution (100%). Dripping in the part,
Stir so that it becomes fine droplets. Curing agent prepared separately [Amine adduct of epoxy resin, Yuka Shell Epoxy Co., Ltd.
A solution prepared by dissolving 5 parts in 45 parts of water was gradually added to the stirring solution, and the solution was kept at 80 ° C., and stirring was continued for about 5 hours to obtain a microcapsule suspension. . The microcapsule pigment obtained by centrifuging the microcapsule suspension has the same color change temperature and color change as the composition comprising the components (a), (b), and (c).

Example 14 70 parts of the composition of Example 4 were used as light stabilizers with 2- (3-t
-Butyl-5-methyl-2-hydroxyphenyl) -5
-1.5 parts of chlorobenzotriazole, Epon 828
[Epoxy resin, manufactured by Yuka Shell Epoxy Co., Ltd.] 10 parts are heated and dissolved at 100 ° C., dropped into 100 parts of a 10% aqueous gelatin solution, and stirred so as to be fine droplets. A solution prepared by dissolving 5 parts of a separately prepared curing agent (amine adduct of epoxy resin, manufactured by Yuka Shell Epoxy Co., Ltd.) in 45 parts of water was gradually added to the stirring solution, and the liquid temperature was raised to 80%.
C. and kept stirring for about 5 hours to obtain a microcapsule suspension. The microcapsule pigment obtained by centrifuging the microcapsule suspension has the same color change temperature and color change as the composition comprising the components (a), (b), and (c).

Comparative Example 3 70 parts of the composition of Comparative Example 2 were used as light stabilizers, 2- (3,5
-Di-t-amyl-2-hydroxyphenyl) benzotriazole (2 parts) and Epon 828 (epoxy resin, Yuka Shell Epoxy Co., Ltd.) (10 parts) were heated and dissolved at 100 ° C, and this was dissolved in a 10% gelatin aqueous solution (100%). Dripping in the part,
Stir so that it becomes fine droplets. Curing agent prepared separately [Amine adduct of epoxy resin, Yuka Shell Epoxy Co., Ltd.
A solution prepared by dissolving 5 parts in 45 parts of water was gradually added to the stirring solution, and the solution was kept at 80 ° C., and stirring was continued for about 5 hours to obtain a microcapsule suspension. . The microcapsule pigment obtained by centrifuging the microcapsule suspension has the same color change temperature and color change as the composition comprising the components (a), (b), and (c).

Light resistance test method In each of the test samples before and after light irradiation of each of the above samples, a color difference meter [manufactured by Tokyo Denshoku Co., Ltd .; , TC-3600], and for Examples 1 to 12 and Comparative Examples 1 and 2, the change in lightness value when light was irradiated for 0, 10, and 20 hours was measured. Examples 13 and 14, and Comparative Example 3 0, 2 for
The change in lightness value when light was irradiated for 0 and 40 hours was measured. In this test, a carbon arc fade meter was used. The following table shows the light fastness test results.

[0050]

[Table 3]

From the above results, all of the samples using the reversible thermochromic composition of the present invention and the microcapsule pigment containing the same, not only maintain the color density at the time of light irradiation, but also brown at the time of decolorization (coloring). ) Excellent light fastness with almost no deterioration. On the other hand, the composition prepared in the comparative example and the sample using the microcapsule pigment containing the composition,
Even if the color density at the time of light irradiation is maintained, browning (coloring) deterioration at the time of decoloring occurs, and even if a light stabilizer is used in combination as shown in Comparative Example 3, it is completely prevented. Could not.

[0052]

According to the present invention, the use of a specific lactone derivative having an indolyl group substituted with a phenyl group as an electron-donating color-forming organic compound enables browning (coloring) at the time of decolorization caused by light irradiation. Deterioration can be prevented, and a reversible color-changing composition having a high color density at the time of coloring can be obtained. In addition, by adding a light stabilizer, browning (coloring) deterioration at the time of color erasing that occurs at the time of light irradiation can be further prevented, and the color development density at the time of light irradiation and browning (coloring) deterioration at the time of color erasing can be reduced. Prevention can be permanent.

Claims (2)

[Claims] (A) a lactone derivative represented by the following general formula (1) or (2), (b) an electron-accepting compound, (c) the (a):
(B) A reversible thermochromic composition comprising a reaction medium which reversibly causes an electron transfer reaction by a component in a specific temperature range. Embedded image (Wherein, R ₁ represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 8 carbon atoms, R ₂ represents an alkyl group having 1 to 8 carbon atoms, R ₃
Is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, 1 to 8 carbon atoms
R ₄ represents an alkyl group having 1 to 8 carbon atoms) 2. The method according to claim 1, wherein the microcapsules are included.
The reversible thermochromic composition according to the above.