JP2002129029A - Reversibly thermally color-changeable liquid composition and reversibly thermally color-changeable laminate using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a reversibly thermally color-changeable liquid composition having less browning (coloration) in its colorless state, and to provide a laminate using the composition. SOLUTION: The composition comprises (A) a specified lactone derivative as an electron-donating color-developing organic compound, (B) an electron- accepting compound, (C) a reaction medium which reversibly causes the electron- donating and -accepting reaction between the components A and B in a specified temperature range and a vehicle containing a resin. The laminate is obtained by forming a reversibly thermally color-changeable layer on a support using the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a reversible thermochromic liquid composition and a reversible thermochromic laminate using the same. More specifically, the present invention relates to a reversible thermochromic liquid composition in which browning (coloring) does not occur in a decolored state caused by light irradiation, and a laminate in which a reversible thermochromic layer is formed using the composition.

[0002]

2. Description of the Related Art Heretofore, (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound (c) the (a)
A liquid composition in which a reversible thermochromic composition comprising a compound which is a reaction medium for reversibly causing the electron transfer reaction according to (b) is dispersed in a vehicle is disclosed in JP-B-52-776.
No. 4 printing ink, JP-B-7-100769
Discloses a color-memorizable paint and the like described in Japanese Patent Application Laid-Open Publication No. H10-209,036. Regarding the light fastness of the conventional inks and paints described above, the addition of a light stabilizer can prevent a decrease in color density (fading) at the time of color development caused by light irradiation,
It is difficult to prevent browning (coloring) in the decolored state caused by light irradiation, and the reversible thermochromic composition, in which reversible color change is an important requirement, has a large contrast between coloration and decoloration. It may be damaged.

[0003]

The present inventors have made further studies on the reversible thermochromic liquid composition,
(A) a reversible heat composed of an electron-donating color-forming organic compound, (B) an electron-accepting compound, and (C) a compound that is a reaction medium for reversibly causing the electron transfer reaction according to (A) and (B). In a liquid composition comprising a reversible thermochromic microcapsule pigment containing a color-changing composition and a vehicle,
(A) By applying a specific lactone derivative to the component, a good color density is permanently exhibited at the time of color development, and there is little residual color at the time of color erasing, and browning at the time of color erasing (coloring)
A liquid composition in which deterioration is prevented is obtained, and by forming a reversible thermochromic layer using the composition on a support, a thermometer, toy field, decoration field, excellent practicality in the design field, etc. The inventors have found that a reversible thermochromic laminate can be obtained and completed the present invention.

[0004]

As described above, a liquid that exhibits a good color density permanently when coloring, has little residual color when decoloring, and prevents browning (coloring) deterioration during decoloring. As a result of examining the composition, the present inventors have found that, in a color forming system by an electron transfer reaction, (a) a phenyl group represented by the general formula (1) or (2) is substituted as an electron-donating color-forming organic compound. A specific lactone derivative having an indolyl group, a (b) electron-accepting compound that functions as a color developer, and (c) a reaction medium that causes the former to develop or discolor in a specific temperature range. The present inventors have found that a system comprising a microcapsule pigment containing a reversible thermochromic composition and a vehicle containing a resin satisfies the above requirements, and completed the present invention. That is, the present invention provides (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, (c)
A reversible heat composed of a microcapsule pigment containing a reversible thermochromic composition comprising a reaction medium for reversibly causing an electron transfer reaction by the components (a) and (b) in a specific temperature range, and a vehicle containing a resin. Require a discolorable liquid composition.

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.) Further, the reversible thermochromic liquid composition may be a paint, a printing ink, an ink for a writing implement, a cosmetic lacquer, a coloring liquid for a fiber. And a composition selected from paints.
Further, (a) a lactone derivative represented by the general formula (1) or (2) as an electron-donating color-forming organic compound;
(C) a microcapsule pigment containing a reversible thermochromic composition comprising a reaction medium that reversibly causes an electron transfer reaction by the components (a) and (b) in a specific temperature range. Microcapsule pigments,
A reversible thermochromic laminate formed by forming a reversible thermochromic layer on a support with a reversible thermochromic liquid composition composed of a vehicle containing a resin is required.

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-
Dihydroxydiphenyl sulfone, 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-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,
There are 2,2-bis (4-hydroxyphenyl) n-heptane, 2,2-bis (4-hydroxyphenyl) n-nonane, and the like. Although the compound having the phenolic hydroxyl group can exhibit the most effective thermochromic properties,
Their metal salts, aromatic carboxylic acids and C2-5
Aliphatic carboxylic acids and their metal salts, carboxylic acid metal salts, acidic phosphate esters and their metal salts,
It may be a compound selected from 2,3-triazole and its derivatives. 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-hexa) Fluoroisopropyl) 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-hexanetriol trimiristate, 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 include n-pentyl acetophenone, cyclohexyl phenyl ketone, benzyl-n-butyl ketone, 4-n-butyl acetophenone, n-hexanophenone, 4-isobutyl acetophenone, 1-acetonaphthone, 2-acetonaphthone, cyclopentyl phenyl ketone, and the like.

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 acid amide, dimyristic acid 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).

The above-mentioned reversible thermochromic composition is 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 particle diameter is 0.01 to 100 μm, preferably 0.1 to 100 μm.
The range of 50 μm, more preferably 0.1 to 30 μm satisfies the practicality. Incidentally, microencapsulation is 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,
There are a melting dispersion cooling method, an air suspension coating method, a spray drying method and the like, which are 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.

In the present invention, the microcapsule pigment is dispersed in a vehicle and used as a liquid composition such as a paint or printing ink. The vehicle used in the present invention is composed of components such as a resin, a solvent, and various additives.

Examples of the resin include an ionomer resin, isobutylene-maleic anhydride copolymer resin, acrylonitrile-acrylic styrene copolymer resin, acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer resin acrylonitrile-chlorinated polyethylene- Styrene copolymer resin, ethylene-vinyl chloride copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl acetate-vinyl chloride graft copolymer resin, vinyl acetate resin, vinyl chloride resin, chloride Vinylidene resin, chlorinated vinyl chloride resin, vinyl chloride-vinylidene chloride copolymer resin, chlorinated polyethylene resin, chlorinated polypropylene resin, polyamide resin, polycarbonate resin, polybutadiene, polyethylene tereph Rate resin, polybutylene terephthalate resin, polystyrene resin, high impact polystyrene resin, styrene-maleic acid copolymer resin, acryl-styrene copolymer resin, polypropylene resin, polymethylstyrene resin, acrylate resin, polymethylmethacrylate resin, epoxy Acrylate resin, alkylphenol resin, rosin-modified phenolic resin, rosin-modified alkyd resin, phenolic resin-modified alkyd resin, styrene-modified alkyd resin, epoxy resin-modified alkyd resin, acryl-modified alkyd resin, amino alkyd resin, butyral resin, polyurethane resin, vinyl chloride -Vinyl acetate copolymer resin, epoxy resin, alkyd resin, styrene-butadiene copolymer resin, unsaturated polyester resin, saturated polyester resin, Vinyl-acrylic copolymer resin, polyisobutylene, butyl rubber, cyclized rubber, chlorinated rubber, polyvinyl alkyl ether, fluororesin, silicon resin, phenol resin, petroleum hydrocarbon resin, ketone resin, toluene resin, xylene resin, melamine Resin, urea resin, benzoguanamine resin, polyethylene oxide, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymer resin, polyvinyl alcohol, modified polyvinyl alcohol, polyacrylate, polymethacrylate, acrylate copolymer emulsion, methacrylic acid Ester-based copolymer emulsion, vinyl acetate-acrylate copolymer emulsion,
Ethylene-vinyl acetate copolymer emulsion, styrene-acrylate copolymer emulsion, vinyl chloride copolymer emulsion, vinylidene chloride copolymer emulsion, polyvinyl acetate emulsion, polyolefin emulsion, rosin ester emulsion,
Synthetic resins such as epoxy resin emulsions, polyurethane emulsions, and synthetic rubber latex. Low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight polystyrene, cumarone plastic, polybutene, phenoxy plastic, liquid polybutadiene, liquid rubber, petroleum hydrocarbon resin, cyclopentadiene petroleum resin, etc. Cellulose derivatives, alginic acid derivatives,
Rosin derivatives, starches, polysaccharides, gums, natural rubber, shellac, agar, casein, glue, gelatin, polyterpenes, and other natural or semi-synthetic resins.

Since these resins are in a solid state at room temperature except for resin emulsions, some medium-molecular-weight polymers, and some reactive resins such as epoxy resins, water, aliphatic hydrocarbons, aromatic hydrocarbons, etc. By dissolving or dispersing in a solvent such as hydrogens, alcohols, glycols, glycol derivatives esters, ketones, etc., a liquid composition can be obtained, and a liquid composition is prepared by adding various additives as necessary. You. As the additive, a non-thermochromic colorant, a crosslinking agent, a curing agent, a drying agent, a plasticizer, a viscosity modifier, a dispersant,
UV absorbers, antioxidants, light stabilizers, antisettling agents, leveling agents, gelling agents, defoamers, matting agents, penetrants, pH adjusters, foaming agents, coupling agents, humectants, fungicides , An antiseptic, a rust inhibitor and the like.

Using the reversible thermochromic liquid composition, a conventionally known method, for example, printing means such as screen printing, offset printing, gravure printing, coater, tampo printing, transfer, brush coating, spray coating, static coating, etc. Paper, synthetic paper, thread, fabric, flocking or raised cloth, non-woven fabric, synthetic leather, leather, plastic, glass, ceramics, wood, etc., by means of electropainting, electrodeposition coating, flow coating, roller coating, dip coating, etc. A reversible thermochromic laminate can be obtained by forming a reversible thermochromic layer on a support such as a stone or metal. In addition,
The reversible thermochromic layer is a layer formed by evaporating the solvent in the liquid composition and other compounds, and the microcapsule pigment is fixed to the resin in a dispersed state. Examples of the form of the laminate include a form in which the reversible thermochromic layer is fixed in a layer form on the support surface, a form in which the microcapsule pigment is impregnated and fixed inside the support, and a part of the surface is exposed, such as plastic. Examples of various shaped articles made of non-permeable base materials, processed articles made of fibers and paper, and the like. Specific examples include clothing, footwear, precious metals, lighting equipment, toys, artificial flowers, stationery, daily necessities, kitchenware, and makeup tools. , Exercise equipment, printed matter such as books, vehicles, machines, indoor decorations, medical goods and the like.

Further, on the reversible thermochromic layer of the laminate,
Light resistance can be improved by laminating a layer containing a light stabilizer and / or a light-shielding pigment, or durability can be improved by providing a top coat layer. The light-shielding pigment is a metallic luster pigment, transparent titanium dioxide,
Pigments such as transparent iron oxide, transparent cesium oxide, and transparent zinc oxide are exemplified.

[0024]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The liquid composition in which the reversible thermochromic microcapsule pigment is dispersed in a vehicle is used as a paint, a printing ink, a writing ink, a paint or the like depending on the type of the vehicle. When a vehicle for forming a paint is used as the vehicle, a reversible thermochromic paint is obtained. Coating methods include brush coating, spray coating, electrostatic coating, dip coating, flow coating, roller coating, photopolymerization coating, etc.Evaporation drying type, penetration drying type, emulsion A paint selected from a mold, an oxidation polymerization type, a thermosetting resin type, a photocurable resin type, and the like is prepared. If a vehicle for a printing ink is used as a vehicle, a reversible thermochromic printing ink is prepared.
Printing methods include intaglio, letterpress, lithographic, stencil, and coater printing methods.Evaporation drying type, penetration drying type, emulsion type, oxidation polymerization type, thermosetting resin A printing ink selected from a mold, a photocurable resin mold and the like is prepared. If a vehicle for writing implement ink is used as a vehicle, a writing ink can be obtained. The flow characteristics such as viscosity and shear thinning viscosity are adjusted for the writing implement ink according to the writing mechanism, and various writing implement inks such as evaporative drying type and emulsion type are prepared according to the writing object. If a cosmetic lacquer is used as a vehicle, a nail polish cosmetic can be obtained. In cosmetics,
There are cosmetics for manicure, cosmetics for make-up, cosmetics for hair, and the like, and cosmetics of various compositions are prepared according to the makeup subject. If a fiber treatment binder is used as a vehicle, a fiber coloring liquid can be obtained. Examples of the fiber coloring method include immersion and spray coating, and a fiber coloring liquid having an appropriate composition is prepared according to the treatment method and the target material. A laminate is formed by providing a reversible thermochromic layer on a support of various materials and shapes using the liquid composition described above.

[0025]

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.

[0026]

[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).

[0028]

[Table 2]

The method for preparing the microcapsule pigment containing the reversible thermochromic composition is described below. In addition, the preparation method of the microcapsule pigment containing the reversible thermochromic compositions of Examples 2 to 9 and Comparative Examples 1 and 2 is the same as the method shown in Example 1.

Example 1 Preparation of a reversible thermochromic microcapsule pigment containing a reversible thermochromic composition 3- (4-di-n-butylaminophenyl) -3- (1
-Methyl-2-phenylindol-3-yl) -4-
1.5 parts by weight of azaphthalide, 6.0 parts by weight of 2,2-bis (4-hydroxyphenyl) propane, 25.0 parts by weight of myristyl alcohol, and 25.0 parts by weight of butyl stearate were heated and dissolved at 120 ° C. 10 parts of Epon 828 (epoxy resin, manufactured by Yuka Shell Epoxy Co., Ltd.) were heated and dissolved at 100 ° C. in 70 parts of the reversible thermochromic composition which had been made into a homogeneous solution by heating. 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%. ℃,
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 each composition.

Preparation of reversible thermochromic liquid composition 30.0 parts by weight of microcapsule pigment containing thermochromic composition 1 of Example 1 was mixed with 45.0 parts by weight of an acrylate resin emulsion and an antifoaming agent. 1.0 part by weight, uniformly dispersed in a vehicle consisting of 22.5 parts by weight of dilution water,
Filtration through a 180 mesh screen gave a reversible thermochromic aqueous spray paint.

Preparation of Reversible Thermochromic Laminate The above spray paint was filled into a spray gun (0.6 mm in diameter) and coated on the entire surface of a white fabric (support).
After drying, a reversible thermochromic layer was formed to obtain a reversible thermochromic fabric (reversible thermochromic laminate). Sewing the cloth,
A swimsuit for a doll was made. The doll swimsuit is colorless at room temperature (25 ° C.), but exhibits a blue color when cooled to 15 ° C. or less, and becomes colorless when the temperature exceeds 15 ° C. This change is caused by a temperature change. Could be repeated.

Example 2 Preparation of a reversible thermochromic liquid composition 15.0 parts by weight of a microcapsule pigment containing the reversible thermochromic composition of Example 2 was added to 40.0 parts by weight of an acrylic resin / xylene solution, and ultraviolet rays. 3.0 parts by weight of absorbent, 30.0 parts by weight of xylene, and 30 parts by weight of methyl isobutyl ketone.
A reversible thermochromic oil-based spray paint was obtained by stirring and mixing in a vehicle consisting of 0 parts by weight and 10.0 parts by weight of an isocyanate-based curing agent.

Preparation of Reversible Thermochromic Laminate The above spray paint was filled in a spray gun (0.6 mm in diameter), and the entire body of a white miniature of a car mold obtained by injection molding ABS resin was applied and dried. A reversible thermochromic miniature car (reversible thermochromic laminate) was obtained.
The reversible thermochromic miniature car exhibits a blue color at room temperature and becomes colorless when immersed in warm water at 50 ° C. or higher. When the miniature car is allowed to cool, it turns white again. This change could be made repeatedly by changing the temperature.

Example 3 Preparation of Reversible Thermochromic Liquid Composition 15.0 parts by weight of microcapsule pigment containing the reversible thermochromic composition of Example 3 was added to 20.0 parts by weight of a 50% acrylic resin / xylene solution. , Vinyl chloride-vinyl acetate copolymer resin 10.0
Parts by weight, methyl isobubutyl ketone, 30.0 parts by weight,
The mixture was stirred and mixed in a vehicle consisting of 30.0 parts by weight of cyclohexanone to obtain a reversible thermochromic oil-based spray paint.

Preparation of Reversible Thermochromic Laminate Using the above-mentioned spray paint, a butterfly pattern is painted on the feet of a polyvinyl chloride resin doll to obtain a reversible thermochromic doll (reversible thermochromic laminate). Was. A blue butterfly pattern appears on the feet of the doll at room temperature and becomes colorless when immersed in warm water of 30 ° C. or higher. When this doll is allowed to cool, a blue butterfly pattern appears again. This change could be made repeatedly by changing the temperature.

Example 4 Preparation of Reversible Thermochromic Liquid Composition 35.0 parts by weight of microcapsule pigment containing the reversible thermochromic composition of Example 4 was mixed with a soft epoxy resin 45.0.
Parts by weight, 20.0 parts by weight of a low-viscosity epoxy resin, 6.0 parts by weight of an ultraviolet absorber 2.0 parts by weight of a thixotropic agent, and 0.3 parts by weight of an antifoaming agent, after uniformly dispersed and mixed in a vehicle. Then, 40.0 parts by weight of a room temperature-curable aliphatic polyamine was added, and the mixture was uniformly stirred and mixed to obtain a reversible thermochromic soft epoxy ink.

Preparation of Reversible Thermochromic Laminate The reversible thermochromic epoxy ink was applied to the roof of a white miniature house molded product using a brush, and was heated and cured at 70 ° C. for 1 hour to obtain a reversible thermochromic miniature. A house (reversible thermochromic laminate) was obtained. When the reversible thermochromic miniature house is cooled to 15 ° C. or less, the roof turns blue,
This state was maintained at room temperature (25 ° C.). Also, 32
When heated above ℃, the roof turned white and was kept at room temperature. This change could be made repeatedly by changing the temperature.

Example 5 Preparation of a reversible thermochromic liquid composition 40.0 parts by weight of microcapsule pigment containing the reversible thermochromic composition of Example 5 and a fluorescent pink pigment 3.0
Parts by weight were uniformly dispersed and mixed in a vehicle consisting of 60.0 parts by weight of a hard liquid epoxy resin, 2.0 parts by weight of an ultraviolet absorber, 2.0 parts by weight of a thixotropic agent, and 0.5 parts by weight of an antifoaming agent. Thereafter, 35.0 parts by weight of a room temperature-curable aliphatic polyamine was added and uniformly dispersed and mixed to obtain a reversible thermochromic epoxy ink.

Preparation of Reversible Thermochromic Laminate The above-mentioned reversible thermochromic epoxy ink was used to print on the side of a mug made of white porcelain using a stainless steel screen plate with a floral pattern using a curved surface printing machine. The composition was cured by heating at 1 ° C. for 1 hour to obtain a reversible thermochromic mug (reversible thermochromic laminate). The reversible thermochromic mug is 10 ° C.
When cooled below, it changed to a purple floral pattern in which blue and pink were mixed, and this state was maintained at room temperature (25 ° C.). When heated above 36 ° C., the color changed to a pink flower pattern, and this state was maintained at room temperature. This change could be made repeatedly by changing the temperature.

Example 6 Preparation of Reversible Thermochromic Liquid Composition 40.0 parts by weight of a microcapsule pigment containing the reversible thermochromic composition of Example 6 and 8.0 parts by weight of a fluorescent yellow pigment were mixed with ethylene. Vinyl acetate copolymer resin emulsion 5
0.0 parts by weight, 3.0 parts by weight of an antifoaming agent, 1.0 part by weight of a thickener (sodium alginate), 3.0 parts by weight of a leveling agent, and 1.0 part by weight of a preservative are uniformly dispersed in a vehicle. After mixing, a reversible thermochromic screen ink was obtained.

Preparation of a Reversible Thermochromic Laminate A reversible thermochromic layer having a banana pattern was formed on a transparent support made of a soft vinyl chloride resin using the reversible thermochromic screen ink. A non-thermochromic layer having the same banana pattern as above was formed using a non-chromogenic yellow ink, and another transparent support was laminated on the non-color-changing layer to form a reversible thermochromic sheet ( A reversible thermochromic laminate) was obtained. The reversible thermochromic sheet has a room temperature (25
Under ℃), a yellow-green banana pattern with a mixture of blue and yellow is visible, but when heated above 30 ° C, it changes to a yellow banana pattern, and when left untreated, it becomes a yellow-green banana pattern again Become. This change could be made repeatedly by changing the temperature.

Example 7 Preparation of Reversible Thermochromic Liquid Composition Example 7 30.0 parts by weight of microcapsule pigment containing the reversible thermochromic composition was added to a carboxy-modified polyolefin-based self-emulsifying emulsion (solid content: 4 to 4%). 25%) 3
0.0 parts by weight, 5.0 parts by weight of a polyglyceryl acrylate-based wetting agent, 1.0 part by weight of triethanolamine, and 0.5 part by weight of methylcellulose. A reversible thermochromic marking pen ink was obtained by uniformly mixing in a vehicle consisting of 0.2 parts by weight of a preservative, 0.3 parts by weight of an antifoaming agent, and 32.0 parts by weight of water.

The marking pen ink was impregnated in an ink occluding body having a capillary channel, incorporated in a barrel, and a pen made of a plastic porous body was provided at the tip of the writing to obtain a reversible thermochromic marking pen.

Preparation of Reversible Thermochromic Laminate The above-mentioned marking pen was used to write on report paper. Note that the handwriting obtained by writing is colorless at room temperature (25 ° C.), but when cooled to 20 ° C. or lower, a blue handwriting appears, and when left to stand, it becomes colorless again. This change could be made repeatedly by changing the temperature.

Example 8 Preparation of Reversible Thermochromic Liquid Composition 15.0 parts by weight of microcapsule pigment containing the reversible thermochromic composition of Example 8 and 3.0 parts by weight of powdered fluorescent pink pigment were 50% acrylic resin / xylene solution 4
0.0 parts by weight, 1.0 part by weight of ultraviolet absorber, xylene 3
0.0 parts by weight, 30.0 parts by weight of methyl isobutyl ketone, and 10.0 parts by weight of an isocyanate-based curing agent were uniformly mixed in a vehicle to obtain a reversible thermochromic false oily spray ink for false nails.

Preparation of Reversible Thermochromic Laminate The oily spray ink for false nails was spray-coated on the surface of false nails (support) made of acetylcellulose resin using a spray gun (0.6 mm in diameter) and dried. Thus, a reversible thermochromic layer was provided, and a top coat layer was further provided thereon to obtain a reversible thermochromic false nail (reversible thermochromic laminate). In addition, as for the reversible thermochromic false nail, at room temperature (25 ° C.), a purple false nail in which blue and pink colors are mixed is visually recognized, but when heated to 35 ° C. or more, the pink false nail becomes a pink false nail. It changes, and when left untouched, it becomes a purple false nail again. This change could be made repeatedly by changing the temperature.

Example 9 Preparation of Reversible Thermochromic Liquid Composition 20.0 parts by weight of microcapsule pigment containing the reversible thermochromic composition of Example 9 was added to 80.0 parts by weight of an acrylate resin emulsion, water Dispersion type UV absorber 1.5
It was uniformly dispersed in a vehicle consisting of parts by weight to obtain a reversible thermochromic aqueous coating solution.

Preparation of Reversible Thermochromic Laminate In the reversible thermochromic aqueous coating solution, 70 mm
100.0 parts by weight of a 7 denier polyacrylonitrile raw cotton cut to a length of 10 cm are immersed, an excess coating solution is removed by centrifugation and dried at 90 ° C. for 10 minutes to obtain a reversible thermochromic polyacrylonitrile raw cotton. Was.

The reversible thermochromic polyacrylonitrile raw cotton was slivered over a card, knitted and sheared with a high pile knitting machine to obtain a reversible thermochromic high pile fabric having a pile length of 20 mm. Using the high pile fabric, a stuffed bear was sewn. The bear's stuffed toy turned into a blue bear when cooled below 15 ° C, and this state was maintained at room temperature (25 ° C). Further, when heated to 32 ° C. or higher, it turned white, and this state was maintained at room temperature. This change could be made repeatedly by changing the temperature.

Preparation of Reversible Thermochromic Liquid Composition 30.0 parts by weight of the microcapsule pigment containing the thermochromic composition of Comparative Example 1 was mixed with 45.0 parts by weight of an acrylate resin emulsion and 1. 0 parts by weight, dilution water 2
Disperse uniformly in 2.5 parts by weight of vehicle, 180
Filtration through a mesh screen gave a reversible thermochromic aqueous spray paint.

Preparation of a Reversible Thermochromic Laminate The spray paint was filled in a spray gun (0.6 mm in diameter), applied to the entire surface of a cloth (support), and dried to form a reversible thermochromic layer. Thus, a reversible thermochromic fabric (reversible thermochromic laminate) was obtained.

Preparation of Reversible Thermochromic Liquid Composition 30.0 parts by weight of the microcapsule pigment containing the thermochromic composition of Comparative Example 2 were mixed with 45.0 parts by weight of an acrylate resin emulsion, 0 parts by weight, dilution water 2
Disperse uniformly in 2.5 parts by weight of vehicle, 180
Filtration through a mesh screen gave a reversible thermochromic aqueous spray paint.

Preparation of Reversible Thermochromic Laminate The spray paint is filled in a spray gun (0.6 mm in diameter) to coat the entire surface of the fabric (support) and then dried to form a reversible thermochromic layer. Thus, a reversible thermochromic fabric (reversible thermochromic laminate) was obtained.

Light Resistance Test Preparation of Light Resistance Test Sample 20 parts of the microcapsule pigment containing the reversible thermochromic compositions of Examples 1 to 9 and Comparative Examples 1 and 2 were added to Vehicle 8
The test sample (reversible thermochromic laminate) was obtained by printing each of the inks in 0 part on a synthetic paper.

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 the change in the lightness value upon light irradiation for 0, 10, and 20 hours was measured. In this test, a carbon arc fade meter was used. The following table shows the light fastness test results.

[0057]

[Table 3]

[0058]

EFFECTS OF THE INVENTION The reversible thermochromic liquid composition of the present invention can prevent browning (coloring) deterioration at the time of decolorization caused by light irradiation, and has a high color density at the time of color development, and can be used for paints and printing. Ink, writing implement ink, cosmetic lacquer,
Excellent applicability in the field of coloring materials such as fiber coloring liquids and paints. Further, the laminate having a reversible thermochromic layer formed using the reversible thermochromic liquid composition has the same color-changing property, and has a temperature-indicating material, a temperature detection material, a forgery prevention, a training element, a toy, a decoration, and the like. Applied to various fields.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 5/26 C09D 5/26 7/12 7/12 11/02 11/02 11/16 11/16 201 / 00 201/00 F-term (reference) 4H056 BA02 BB01 BB16 BC01 BC04 BC05 BD03 BF04 BF26 BF28 4J002 AB011 AC011 AC021 AC121 BA011 BB061 BB241 BC031 BC061 BD031 BD061 BD081 BD101 BE021 BE041 BG041 BG061 CB061 CB061B011 EJ027 EJ037 EJ057 EP018 EU066 FB286 FB287 FB288 4J038 EA011 JA22 JA26 JA33 JA53 JA63 JB12 JB27 JC01 JC12 KA06 KA08 KA21 NA16 4J039 BC06 BC07 BC12 BC16 BC20 BC29 BC31 BC32 BC36 BC50 GA05 GA12 BE02 GA02

Claims (3)

[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 liquid composition comprising a microcapsule pigment containing a reversible thermochromic composition comprising a reaction medium that reversibly causes an electron transfer reaction by a component in a specific temperature range, and a vehicle containing a resin. . 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 reversible thermochromic composition according to claim 1, wherein the reversible thermochromic liquid composition is a composition selected from paints, printing inks, writing inks, cosmetic lacquers, textile coloring liquids, and paints. Liquid composition. 3. A lactone derivative represented by the general formula (1) or (2) as an electron-donating color-forming organic compound:
(B) an electron-accepting compound; and (c) a microcapsule pigment containing a reversible thermochromic composition comprising a reaction medium that reversibly causes an electron transfer reaction by the components (a) and (b) in a specific temperature range. And a reversible thermochromic layer formed on a support with a reversible thermochromic liquid composition comprising a vehicle containing a resin.