JP2020183466A - Multicolor discoloring ink composition for stamp and stamp using the same - Google Patents

Abstract

To provide a multicolor discoloring ink composition for stamp which can clearly visually recognize a color change between a plurality of colors, and a stamp using the same.SOLUTION: A multicolor discoloring ink composition for stamp is composed of a reversible thermochromic pigment A, a reversible thermochromic pigment B and a medium, in which the reversible thermochromic pigment A and the reversible thermochromic pigment B become completely colored states when the temperatures have reached a complete coloring temperature (t1), and become completely colorless states when the temperatures have reached a complete colorless temperature (t4), and the complete colorless temperature (t4) of the reversible thermochromic pigment B is on a higher temperature side than the complete colorless temperature (t4) of the reversible thermochromic pigment A or the complete coloring temperature (t1) of the reversible thermochromic pigment B is on a lower temperature side than the complete coloring temperature (t1) of the reversible thermochromic pigment A.SELECTED DRAWING: Figure 3

Description

The present invention relates to a multicolor discolorable ink composition for stamps and stamps using the same. More specifically, the present invention relates to a multicolor discolorable ink composition for stamps, which can obtain an image in which various color changes can be visually recognized by a temperature change, and a stamp using the same.

Conventionally, an ink composition for stamping for obtaining an image whose color changes with a temperature change has been disclosed (see, for example, Patent Document 1 or 2).
The image formed by using the ink composition shows a reversible color change from colored to colorless or from colored (1) to colored (2) due to a temperature change, and is excellent in decorativeness.

JP-A-2002-121427 JP-A-2015-209444

The present invention pursues the color change of the stamp image obtained by the stamp ink composition, and the color changes from colored to colored, and the color change is highly visible and has high commercial value. It is intended to provide a composition and a stamp using the composition.

The present invention reversibly performs an electron transfer reaction between (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) the above-mentioned (a) and (b) components in a specific temperature range. A reversible thermochromic pigment A containing a reversible thermochromic composition a composed of a reaction medium to be generated, (a) an electron-donating color-developing organic compound, (b) an electron-accepting compound, and (c). At least a reversible thermochromic pigment B containing a reversible thermochromic composition b comprising a reaction medium that reversibly causes an electron transfer reaction by the components (a) and (b) in a specific temperature range, and the medium. When the reversible thermochromic pigments A and B reach the complete color development temperature (t ₁ ) by lowering the temperature from the decolorized state, they are completely in the color development state, and the temperature rise from the color development state causes the complete decolorization temperature (t ₄ ). When it reaches become fully decolorized state are pigments, having a complete decoloring temperature of the reversible thermochromic pigment B (t ₄₎ to the high temperature side than the complete decoloring temperature (t ₄₎ of the thermochromic pigment a Alternatively, a multicolor discolorable ink composition for stamps having the complete color development temperature (t ₁ ) of the reversible thermochromic pigment B on the lower temperature side than the complete color development temperature (t ₁ ) of the reversible thermochromic pigment A is required. ..
Further, the reversible thermochromic pigment A has a complete decolorization temperature of 10 ° C. or more higher than the complete decolorization temperature of the reversible thermochromic pigment A, and the reversible thermochromic pigment A has a complete decolorization temperature. Having a complete decoloring temperature of the reversible thermochromic pigment B on the higher temperature side of 10 to 70 ° C., the complete decoloring temperature of the reversible thermochromic pigment A is 50 ° C. or higher, and the complete color development temperature is 0 ° C. or lower. Therefore, it is a requirement that the complete color development temperature of the reversible thermochromic pigment B is 0 ° C. or lower.
Further, the stamp is provided with a stamp material having continuous pores, the stamp material is impregnated with the ink composition for reversible thermochromic stamping, and the stamp is provided with a friction body.

The present invention has the complete decoloring temperature (t ₄ ) of the reversible thermochromic pigment B on the higher temperature side than the complete decoloring temperature (t ₄ ) of the reversible thermochromic pigment A, or the reversible thermochromic pigment A. By having the complete color development temperature (t ₁ ) of the reversible thermochromic pigment B on the lower temperature side than the complete color development temperature (t ₁ ), the color change from colored to colored can be clearly visually recognized, and the multicolor for stamps having high commercial value. A discolorable ink composition and a stamp using the same can be provided.

It is a graph explaining the hysteresis characteristic in the color density-temperature curve of a reversible thermochromic composition. It is a graph explaining the hysteresis characteristic in the color density-temperature curve of the reversible thermochromic composition having color memory. Color density-temperature curve of reversible thermochromic pigment A and reversible thermochromic pigment B contained in the multicolor discolorable ink composition for stamps according to an embodiment of the present invention (pigment A: thin line, pigment B: thick line) Is shown. Color density-temperature curve of reversible thermochromic pigment A and reversible thermochromic pigment B contained in the multicolor discolorable ink composition for stamps of another embodiment of the present invention (pigment A: thin line, pigment B: thick line) ) Is shown. Color density-temperature curve of reversible thermochromic pigment A and reversible thermochromic pigment B contained in the multicolor discolorable ink composition for stamps of another embodiment of the present invention (pigment A: thin line, pigment B: thick line) ) Is shown. Color density-temperature curve of reversible thermochromic pigment A and reversible thermochromic pigment B contained in the multicolor discolorable ink composition for stamps of another embodiment of the present invention (pigment A: thin line, pigment B: thick line) ) Is shown. It is a vertical cross-sectional explanatory view of the example of the stamp which incorporated the multicolor discoloration ink composition for a stamp of this invention.

The reversible thermochromic compositions a and b are (a) an electron-donating color-developing organic compound, (b) an electron-accepting compound, and (c) a reaction medium that determines the temperature at which the color reaction of both of them occurs. Examples thereof include a heat-decoloring type (decoloring by heating and developing color by cooling) reversible thermochromic composition containing at least three essential components.
The reversible thermochromic composition discolors before and after a predetermined temperature (discoloration point), and is decolorized in a temperature range above the high temperature side discoloration point and develops in a temperature range below the low temperature side discoloration point. Presented, only one of the two states exists in a specific temperature range, and the other state is maintained as long as the heat or cold required for the state to develop is applied. However, it has a characteristic that the hysteresis width (ΔH) is relatively small, which returns to the original state when the application of the heat or cold heat is removed (see FIG. 1).
In addition, the shape of the curve showing a large hysteresis characteristic, that is, plotting the change in coloring density due to temperature change, decreases from the higher temperature side than the discoloration temperature range, contrary to the case where the temperature is raised from the lower temperature side than the discoloration temperature range. The color changes by following a path that is significantly different from that of the case where the color is changed, and the color development state in the low temperature range below the complete color development temperature (t ₁ ) or the decolorization state in the high temperature range above the complete decolorization temperature (t ₄ ) , [temperature range between t ₂ ~t ₃ (substantially two-phase retaining temperature region)] specific temperature range in the heating decolorizable with color-memorizing (decolored by heating, develops color by cooling) the reversible thermal A discoloring composition can also be applied (see FIG. 2).

The components (a), (b), and (c) contained in the reversible thermochromic pigment will be specifically described below.
The component (a) of the present invention, that is, the electron-donating color-developing organic compound is a component that determines a color and is a compound that donates electrons to the component (b) that is a color developer to develop a color.
The component (a) of the present invention, that is, the electron-donating color-developing organic compound is a component that determines a color and is a compound that donates electrons to the component (b) that is a color developer to develop a color.
Examples of the electron-donating color-developing organic compound include phthalide compounds, fluorane compounds, stirinoquinolin compounds, diazarodamine lactone compounds, pyridine compounds, quinazoline compounds, bisquinazoline compounds, and the like, among which phthalide compounds and fluorane compounds preferable.
Examples of the phthalide compound include diphenylmethanephthalide compound, phenylindrillphthalide compound, indolylphthalide compound, diphenylmethaneazaphthalide compound, phenylindrillazaphthalide compound, and derivatives thereof. Of these, phenylindrill azaphthalide compounds and derivatives thereof are preferable.
In addition, examples of the fluorane compound include an aminofluorane compound, an alkoxyfluorane compound, and a derivative thereof.
Examples of these compounds are given below.
3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide,
3- (4-Diethylaminophenyl) -3- (1-ethyl-2-methylindole-3-yl) phthalide,
3,3-Bis (1-n-butyl-2-methylindole-3-yl) phthalide,
3,3-Bis (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide,
3- (2-ethoxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindole-3-yl) -4-azaphthalide,
3- (2-Hexyloxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindole-3-yl) -4-azaphthalide,
3- [2-ethoxy-4- (N-ethylanilino) phenyl] -3- (1-ethyl-2-methylindole-3-yl) -4-azaphthalide,
3- (2-Acetamide-4-diethylaminophenyl) -3- (1-propylindole-3-yl) -4-azaphthalide,
3,6-bis (diphenylamino) fluorane,
3,6-dimethoxyfluorane,
3,6-di-n-butoxyfluoran,
2-Methyl-6- (N-ethyl-N-p-trillamino) fluorane,
3-Chloro-6-cyclohexylaminofluorane,
2-Methyl-6-cyclohexylaminofluorane,
2- (2-Chloroamino) -6-dibutylaminofluorane,
2- (2-Chloroanilino) -6-di-n-butylaminofluorane,
2- (3-Trifluoromethylanilino) -6-diethylaminofluorane,
2- (3-Trifluoromethylanilino) -6-dipentylaminofluorane,
2- (Dibenzylamino) -6-diethylaminofluorane,
2- (N-Methylanilino) -6- (N-ethyl-N-p-trillamino) fluorane,
1,3-Dimethyl-6-diethylaminofluorane,
2-Chloro-3-methyl-6-diethylaminofluorane,
2-anilino-3-methyl-6-diethylaminofluorane,
2-anilino-3-methoxy-6-diethylaminofluorane,
2-anilino-3-methyl-6-di-n-butylaminofluorane,
2-anilino-3-methoxy-6-di-n-butylaminofluorane,
2-Xylidino-3-methyl-6-diethylaminofluorane,
2-Anilino-3-methyl-6- (N-ethyl-N-p-trillamino) fluorane,
1,2-Benz-6-diethylaminofluorane,
1,2-Benz-6- (N-ethyl-N-isobutylamino) fluorane,
1,2-Benz-6- (N-ethyl-N-isoamylamino) fluorane,
2- (3-Methoxy-4-dodecoxystilyl) quinoline,
Spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5,1'(3'H) isobenzofuran] -3'-on, 2- (diethylamino) -8- (diethylamino) -4-methyl ,
Spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5,1'(3'H) isobenzofuran] -3'-on, 2- (di-n-butylamino) -8- (di-n-butylamino) -N-Butylamino) -4-methyl,
Spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5,1'(3'H) isobenzofuran] -3'-on, 2- (di-n-butylamino) -8- (diethylamino) ) -4-Methyl,
Spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5,1'(3'H) isobenzofuran] -3'-on, 2- (di-n-butylamino) -8- (N) -Ethyl-N-i-amylamino) -4-methyl,
Spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5,1'(3'H) isobenzofuran] -3'-on, 2- (dibutylamino) -8- (dipentylamino) -4 -Methyl,
4,5,6,7-Tetrachloro-3- [4- (dimethylamino) -2-methoxyphenyl] -3- (1-butyl-2-methyl-1H-indole-3-yl) -1 (3H) ) -Isobenzofuranone,
4,5,6,7-Tetrachloro-3- [4- (diethylamino) -2-ethoxyphenyl] -3- (1-ethyl-2-methyl-1H-indole-3-yl) -1 (3H) -Isobenzofuranone,
4,5,6,7-Tetrachloro-3- [4- (diethylamino) -2-ethoxyphenyl] -3- (1-pentyl-2-methyl-1H-indole-3-yl) -1 (3H) -Isobenzofuranone,
4,5,6,7-Tetrachloro-3- [4- (diethylamino) -2-methylphenyl] -3- (1-ethyl-2-methyl-1H-indole-3-yl) -1 (3H) -Isobenzofuranone,
3', 6'-bis [phenyl (2-methylphenyl) amino] -spiro [isobenzofuran-1 (3H), 9'-[9H] xanthene] -3-one,
3', 6'-bis [phenyl (3-methylphenyl) amino] -spiro [isobenzofuran-1 (3H), 9'-[9H] xanthene] -3-one,
3', 6'-bis [phenyl (3-ethylphenyl) amino] -spiro [isobenzofuran-1 (3H), 9'-[9H] xanthene] -3-one,
2,6-bis (2'-ethyloxyphenyl) -4- (4'-dimethylaminophenyl) pyridine,
2,6-bis (2', 4'-diethyloxyphenyl) -4- (4'-dimethylaminophenyl) pyridine,
2- (4'-dimethylaminophenyl) -4-methoxy-quinazoline,
4,4'-(Ethylenedioxy) -bis [2- (4-diethylaminophenyl) quinazoline]
And so on.
As fluorans, in addition to the above-mentioned compound having a substituent on the phenyl group forming the xanthene ring, a substituent (for example,) on the phenyl group having the substituent on the phenyl group forming the xanthene ring and forming the lactone ring. , Alkyl group such as methyl group, halogen atom such as chloro group) may be a compound exhibiting blue or black color.

The component (b), that is, an electron-accepting compound is a compound that receives electrons from the component (a) and functions as a color developer of the component (a).
The electron-accepting compound includes a group of compounds having an active proton, a group of pseudo-acidic compounds [a group of compounds that are not acids but act as acids in the composition to develop color of component (a)], and have electron vacancies. There are compounds selected from the compound group and the like, and among these, the compound selected from the compound group having an active proton is preferable.
Examples of the compound group having an active proton include a compound having a phenolic hydroxyl group and its derivative, a carboxylic acid and its derivative, preferably an aromatic carboxylic acid and its derivative, an aliphatic carboxylic acid having 2 to 5 carbon atoms and its derivative. Derivatives, acidic phosphoric acid esters and their derivatives, azol compounds and their derivatives, 1,2,3-triazole and its derivatives, cyclic carbosulfoimides, halohydrins having 2 to 5 carbon atoms, sulfonic acids and their derivatives , Inorganic acids and the like.
Examples of the pseudoacid compound group include a metal salt of the compound having a phenolic hydroxyl group, the metal salt of the carboxylic acid, the metal salt of the acidic phosphoric acid ester, the metal salt of the sulfonic acid, an aromatic and an aliphatic carboxylic acid. Examples thereof include anhydrides, aromatic carboxylic acid-sulfonic acid anhydrides, cycloolefin dicarboxylic acid anhydrides, urea and its derivatives, thiourea and its derivatives, guanidine and its derivatives, halogenated alcohols and the like.
Examples of the compound group having electron vacancies include borates, boric acid esters, inorganic salts and the like.
Among these, a compound having a phenolic hydroxyl group is preferable because it can exhibit effective thermal discoloration characteristics.
The compounds having a phenolic hydroxyl group are widely included from monophenol compounds to polyphenol compounds, and further include bis-type, tris-type phenols and the like, phenol-aldehyde condensed resins and the like. Among the compounds having a phenolic hydroxyl group, those having at least two or more benzene rings are preferable. Further, these compounds may have a substituent, and examples of the substituent include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, a carboxyl group, and an ester or amide group thereof, a halogen group and the like.
Examples of the metal contained in the metal salt such as the compound having a phenolic hydroxyl group include sodium, potassium, calcium, zinc, zirconium, aluminum, magnesium, nickel, cobalt, tin, copper, iron, vanadium, titanium, lead, and Examples include molybdenum.

Examples of these compounds are given below.
Examples of the compound having one phenolic hydroxyl group include phenol, o-cresol, m-cresol, p-cresol, 4-ethylphenol, 4-n-propylphenol, 4-n-butylphenol, 2-tert-butylphenol, and 3 −tert-butylphenol, 4-tert-butylphenol, 4-n-pentylphenol, 4-tert-pentylphenol, 4-n-octylphenol, 4-tert-octylphenol, 4-n-nonylphenol, 4-n-dodecylphenol, 3-n-pentadecylphenol, 4-n-stearylphenol, 1- (4-hydroxyphenyl) decane-1-one, 4-chlorophenol, 4-bromophenol, 4-trifluoromethylphenol, 4-methylthiophenol , 4-Nitrophenol, 2-phenylphenol, 4-phenylphenol, 2-benzylphenol, 2-benzyl-4-chlorophenol, 4-cumylphenol, 4-hydroxybenzophenone, 4-chloro-4'-hydroxybenzophenone , 4-Fluoro-4'-hydroxybenzophenone, 4-cyclohexylphenol, 2-hydroxybenzyl alcohol, 3-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 4- (2-hydroxyethyl) phenol, 3-methoxyphenol, 4 -Ethoxyphenol, 4-n-propoxyphenol, 4-n-butoxyphenol, 4-n-heptyloxyphenol, 4- (2-methoxyethyl) phenol, α-naphthol, β-naphthol, 2,3-dimethylphenol , 2,4-Dimethylphenol, 2,6-dimethylphenol, 2,6-di-tert-butylphenol, 2,4-dichlorophenol, 2,4-difluorophenol, Timor, 3-methyl-4-methylthiophenol, 2-tert-butyl-5-methylphenol, 2,6-bis (hydroxymethyl) -4-methylphenol, 2,3,5-trimethylphenol, 2,6-bis (hydroxymethyl) -4-tert-octylphenol , 6-Hydroxy-1,3-benzooxathiol-2-one, 2,4-bis (phenylsulfonyl) phenol, 2,4-bis (phenylsulfonyl) -5-methylphenol, 2,4-bis (4) -Methylphenylsulfonyl) phenol, 2-phenylphenol, 4- Phenylphenol, 2,6-diphenylphenol, 3-benzylbiphenyl-2-ol, 3,5-dibenzylbiphenyl-4-ol, 4-cyano-4'-hydroxybiphenyl,
1-Hydroxybenzotriazole, 1-hydroxy-5-methylbenzotriazole, 1-hydroxy-5-chlorobenzotriazole, 1-hydroxy-5-methoxybenzotriazole, 1-hydroxy-4-benzoylaminobenzotriazole, 1-hydroxy -4,5,6,7-tetrachlorobenzotriazole, 1,4-hydroxybenzotriazole, 1-hydroxy-5-nitrobenzotriazole, 1-hydroxy-5-phenylbenzotriazole, 1-hydroxy-5-benzylbenzo Triazole, 1-hydroxy-5-ethylbenzotriazole, 1-hydroxy-5-n-octylbenzotriazole, 1-hydroxy-5-n-butylbenzotriazole,
4-Hydroxybenzoate n-butyl, 4-hydroxybenzoate n-octyl, 4-hydroxybenzoic acid 2-heptadecafluorooctylethane, 4-hydroxybenzoate benzyl, 4-hydroxybenzoic acid benzyl ester, 4-hydroxybenzoate Acid-o-methylbenzyl, 4-hydroxybenzoic acid-m-methylbenzyl, 4-hydroxybenzoic acid-p-methylbenzyl, 4-hydroxybenzoic acid-p-ethylbenzyl, 4-hydroxybenzoic acid-p-propylbenzyl , 4-Hydroxybenzoic acid-p-tert-butylbenzyl, 4-hydroxybenzoate phenylethyl, 4-hydroxybenzoic acid-o-methylphenylethyl, 4-hydroxybenzoic acid-m-methylphenylethyl, 4-hydroxybenzoate Examples thereof include acid-p-methylphenylethyl, 4-hydroxybenzoic acid-p-ethylphenylethyl, 4-hydroxybenzoic acid-p-propylphenylethyl, 4-hydroxybenzoic acid-p-tert-butylphenylethyl.

Examples of the compound having two phenolic hydroxyl groups include resorcin, 2-methylresorcin, 4-n-hexylresorcin, 4-n-octylresorcin, 4-tert-octylresorcin, 4-benzoylresorcin, 4-nitroresorcin, β. -Methyl resorcinol, benzyl β-resorcinol, 2-chloro-4-pentanoyl resorcinol, 6-chloro-4-pentanoyl resorcinol, 2-chloro-4-hexanoyl resorcinol, 6-chloro-4-hexanoyl resorcinol , 2-Chloro-4-propanoyl resorcinol, 6-chloro-4-propanoyl resorcinol, 2,6-dichloro-4-propanoyl resorcinol, 6-fluoro-4-propanoyl resorcinol, 2-chloro-4-phenyl Acetyl resorcinol, 6-chloro-4-phenylacetylresorcinol, 2-chloro-4-β-phenylpropanoylresorcinol, 6-chloro-4-β-phenylpropanoylresorcinol, 2-chloro-4-phenoxyacetylresorcinol, 6 −Chloro-4-phenoxyacetylresorcin, 4-benzoyl-2-chlororesorcin, 6-chloro-4-m-methylbenzoylresorcin, 4- [1', 3', 4', 9'a-tetrahydro-6' -Hydroxyspiro (cyclohexane-1,9'-[9H] -xanthene) -4'a- [2H] -yl] -1,3-benzenediol, hydroquinone, methylhydroquinone, trimethylhydroquinone, catechol, 4-tert- Butylcatechol, 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene,
2,4-Dihydroxybenzophenone, 4,4'-dihydroxybenzophenone, 2,4-dihydroxy-2'-methylbenzophenone, 2,4-dihydroxy-3'-methylbenzophenone, 2,4-dihydroxy-4'-methylbenzophenone , 2,4-Dihydroxy-4'-ethylbenzophenone, 2,4-dihydroxy-4'-n-propylbenzophenone, 2,4-dihydroxy-4'-isopropylbenzophenone, 2,4-dihydroxy-4'-n- Butylbenzophenone, 2,4-dihydroxy-4'-isobutylbenzophenone, 2,4-dihydroxy-4'-tert-butylbenzophenone, 2,4-dihydroxy-4'-n-pentylbenzophenone, 2,4-dihydroxy-4 ′ -N-Hexyl benzophenone, 2,4-dihydroxy-4'-n-heptyl benzophenone, 2,4-dihydroxy-4'-n-octyl benzophenone, 2,4-dihydroxy-4'-n-decylbenzophenone, 2 , 4-Dihydroxy-2', 3'-dimethylbenzophenone, 2,4-dihydroxy-2', 4'-dimethylbenzophenone, 2,4-dihydroxy-2', 5'-dimethylbenzophenone, 2,4-dihydroxy- 2', 6'-dimethylbenzophenone, 2,4-dihydroxy-3', 4'-dimethylbenzophenone, 2,4-dihydroxy-3', 5'-dimethylbenzophenone, 2,4-dihydroxy-2', 4' , 6'-trimethylbenzophenone, 2,4-dihydroxy-2'-methoxybenzophenone, 2,4-dihydroxy-3'-methoxybenzophenone, 2,4-dihydroxy-4'-methoxybenzophenone, 2,4-dihydroxy-2 ′ -Ethoxybenzophenone, 2,4-dihydroxy-4 ′-ethoxybenzophenone, 2,4-dihydroxy-4'-n-propoxybenzophenone, 2,4-dihydroxy-4'-isopropoxybenzophenone, 2,4-dihydroxy- 4'-n-butoxybenzophenone, 2,4-dihydroxy-4'-isobutoxybenzophenone, 2,4-dihydroxy-4'-n-pentyloxybenzophenone, 2,4-dihydroxy-4'-n-hexyloxybenzophenone , 2,4-Dihydroxy-4'-n-heptyloxybenzophenone, 2,4-dihydroxy-4'-n-octyloxybenzophenone, 2,4-dihydroki Si-4'-n-nonyloxybenzophenone, 2,4-dihydroxy-2', 3'-dimethoxybenzophenone, 2,4-dihydroxy-2', 4'-dimethoxybenzophenone, 2,4-dihydroxy-2', 5'-dimethoxybenzophenone, 2,4-dihydroxy-2', 6'-dimethoxybenzophenone, 2,4-dihydroxy-3', 4'-dimethoxybenzophenone, 2,4-dihydroxy-3', 5'-dimethoxybenzophenone , 2,4-Dihydroxy-3', 4'-diethoxybenzophenone, 2,4-dihydroxy-2', 3', 4'-trimethoxybenzophenone, 2,4-dihydroxy-2', 3', 6' Examples thereof include -trimethoxybenzophenone, 2,4-dihydroxy-3', 4', 5'-trimethoxybenzophenone, 2,4-dihydroxy-3', 4', 5'-triethoxybenzophenone and the like.

Further, as the compound of bis-type phenol, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) n-butane, 1,1-bis (4-hydroxyphenyl) n-pentane, 1,1-bis (4-hydroxyphenyl) n-hexane, 1,1-bis (4-hydroxyphenyl) n-heptane, 1,1-bis (4-Hydroxyphenyl) n-octane, 1,1-bis (4-hydroxyphenyl) n-nonane, 1,1-bis (4-hydroxyphenyl) n-decane, 1,1-bis (4-hydroxy-) 3-Methylphenyl) decane, 1,1-bis (4-hydroxyphenyl) n-dodecane, 1,1-bis (4-hydroxyphenyl) -2-methylpropane, 1,1-bis (4-hydroxyphenyl) -3-Methylbutane, 1,1-bis (4-hydroxyphenyl) -3-methylpentane, 1,1-bis (4-hydroxyphenyl) -2,3-dimethylpentane, 1,1-bis (4-hydroxy) Phenyl) -2-ethylbutane, 1,1-bis (4-hydroxyphenyl) -2-ethylhexane, 1,1-bis (4-hydroxyphenyl) -3,7-dimethyloctane, 1,1-bis (4) -Hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxy-3-methyl) cyclohexane, diphenolic acid, 1-phenyl -1,1-bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) n-butane, 2,2-bis (4-hydroxyphenyl) Hydroxyphenyl) n-pentane, 2,2-bis (4-hydroxyphenyl) n-hexane, 2,2-bis (4-hydroxyphenyl) n-heptane, 2,2-bis (4-hydroxyphenyl) n -Octane, 2,2-bis (4-hydroxyphenyl) n-nonane, 2,2-bis (4-hydroxyphenyl) n-decane, 2,2-bis (4-hydroxyphenyl) n-dodecane, 2, 2-Bis (4-hydroxyphenyl) -6,10,14-trimethylpentadecane, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) methylpropio Nate, 2,2-bis (4-hydroxyphenyl) butyl pro Pionate, 2,2-bis (4-hydroxy-3-methylphenyl) methylpropionate, 2,2-bis (4-hydroxyphenyl) ethylpropionate, 2,2-bis (4-hydroxyphenyl)- 4-Methylpentane, 2,2-bis (4-hydroxyphenyl) -4-methylhexane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,2-bis (3,5-dihydroxymethyl-) 4-Hydroxyphenyl) hexafluoropropane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) butane, 2,2-bis (4) -Hydroxy-3-isopropylphenyl) propane, 2,2-bis (3-sec-butylphenyl-4-hydroxy) propane, 2,2-bis (4-hydroxy-3-phenylphenyl) propane, 2,2- Bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dihydroxymethyl-4-hydroxyphenyl) Propane, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene, 1,4-bis [2- (4) -Hydroxyphenyl) -2-propyl] benzene, 3,3-bis (4-hydroxyphenyl) oxyindole, 3,3-bis (4-hydroxy-3-methylphenyl) oxyindole, bis (2-hydroxyphenyl) Methan, bis (2-hydroxy-5-methylphenyl) methane, bis (2-hydroxy-3-hydroxymethyl-5-methyl) methane, 4,4'-[1,4-phenylenebis (1-methylethylidene)) ] Bis (2-methylphenol), 1,1-bis (4-hydroxy-3-phenylphenyl) cyclohexane, 3,3-ethyleneoxydiphenol, 1,4-bis (4-hydroxybenzoart) -3- Methylbenzene, 4,4 ″ -dihydroxy-3 ″ -methyl-p-terphenyl, 4,4 ″ -dihydroxy-3 ″ -isopropyl-p-terphenyl, 2,2-dimethyl-1,3-bis (4) -Hydroxybenzoyloxy) propane, 2,2'-biphenol, 4,4'"-dihydroxy-p-quaterphenyl,
4,4-Dihydroxydiphenyl ether, bis (4-hydroxyphenylthioethyl) ether bis (4-hydroxyphenyl) sulfone, 4-benzyloxy-4'-hydroxydiphenylsulfone, 4- (4-methylbenzyloxy) -4' -Hydroxydiphenylsulfone, 4- (4-ethylbenzyloxy) -4'-hydroxydiphenylsulfone, 4- (4-n-propylbenzyloxy) -4'-hydroxydiphenylsulfone, 4- (4-isopropylbenzyloxy) -4'-Hydroxydiphenylsulfone, 4- (4-n-butylbenzyloxy) -4'-hydroxydiphenylsulfone, 4- (4-isobutylbenzyloxy) -4'-hydroxydiphenylsulfone, 4- (4-sec -Butylbenzyloxy) -4'-hydroxydiphenylsulfone, 4- (4-tert-butylbenzyloxy) -4'-hydroxydiphenylsulfone, 4- (3-methylbenzyloxy) -4'-hydroxydiphenylsulfone, 4 -(3-Ethylbenzyloxy) -4'-hydroxydiphenylsulfone, 4- (3-n-propylbenzyloxy) -4′-hydroxydiphenylsulfone, 4- (3-isopropylbenzyloxy) -4′-dihydroxyphenyl Sulfone, 4- (3-n-butylbenzyloxy) -4'-hydroxydiphenylsulfone, 4- (3-isobutylbenzyloxy) -4'-hydroxydiphenylsulfone, 4- (3-sec-butylbenzyloxy)- 4'-Hydroxydiphenylsulfone, 4- (3-tert-butylbenzyloxy) -4'-hydroxydiphenylsulfone, 4- (2-methylbenzyloxy) -4′-hydroxydiphenylsulfone, 4- (2-ethylbenzyl) Oxy) -4'-hydroxydiphenyl sulfone, 4- (2-n-propylbenzyloxy) -4'-hydroxydiphenylsulfone, 4- (2-isopropylbenzyloxy) -4'-hydroxydiphenylsulfone, 4- (2) -N-Butylbenzyloxy) -4'-Hydroxydiphenylsulfone, 4- (2-isobutylbenzyloxy) -4'-hydroxydiphenylsulfone, 4- (2-sec-butylbenzyloxy) -4'-hydroxydiphenylsulfone , 4- (2-tert-Butylbenzyloxy) -4'-hydroxydiphenylsulfone, 2,4'-dihydroki Sidiphenyl sulfone, 3,4'-dihydroxydiphenyl sulfone, 4-hydroxydiphenyl sulfone, 4-methyl-4'-hydroxidiphenyl sulfone, 4-ethyl-4'-hydroxydiphenyl sulfone, 4-n-propyl-4' -Hydroxydiphenyl sulfone, 4-isopropyl-4'-hydroxydiphenyl sulfone, 4-chloro-4'-hydroxydiphenyl sulfone, 4-fluoro-4'-hydroxydiphenyl sulfone, 4-chloro-2-methyl-4'-hydroxy Diphenyl sulfone, 4-methoxy-4'-hydroxydiphenyl sulfone, 4-ethoxy-4'-hydroxydiphenyl sulfone, 4-n-propoxy-4'-hydroxydiphenyl sulfone, 4-isopropoxy-4'-hydroxydiphenyl sulfone, 4-n-Butoxy-4'-Hydroxydiphenyl Sulfone, 4-Isobutoxy-4'-Hydroxydiphenyl Sulfone, 4-sec-Butoxy-4'-Hydroxydiphenyl Sulfone, 4-tert-Butoxy-4'-Hydroxydiphenyl Sulfone, 4-n-Pentyloxy-4'-Hydroxydiphenylsulfone, 4-Isopentyloxy-4'-hydroxydiphenylsulfone, 4- (1-propenyloxy) -4'-hydroxydiphenylsulfone, 4- (2-propenyloxy) ) -4'-Hydroxydiphenyl sulfone, 4-benzyloxy-4'-hydroxydiphenyl sulfone, 4- (β-phenoxyethoxy) -4'-hydroxydiphenyl sulfone, 4- (β-phenoxypropoxyl) -4'- Hydroxydiphenyl sulfone, bis (2-allyl-4-hydroxydiphenyl) sulfone, bis [4-hydroxy-3- (2-propenyl) phenyl] sulfone, bis (3,5-dibromo-4-hydroxyphenyl) sulfone, bis (3,5-dichloro-4-hydroxyphenyl) sulfone, bis (3-phenyl-4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-n-propylphenyl) sulfone, bis (4-hydroxy-3-3) Methylphenyl) sulfone, 3,4-dihydroxydiphenyl sulfone, 3', 4'-dihydroxy-4-methyldiphenyl sulfone, 3,4,4'-trihydroxydiphenyl sulfone, bis (3,4-dihydroxyphenyl) sulfone, 2,3,4-trihydroxydiphenylsulfone, 4-isopropoxy- 4'-Hydroxydiphenyl sulfide, 4-n-propoxy-4'-hydroxydiphenyl sulfide, 4-allyloxy-4'-hydroxydiphenyl sulfide, 4-benzyloxy-4'-hydroxydiphenyl sulfide, 4- (2-prope Nyloxy) -4'-hydroxydiphenyl sulfide, 3-benzyl-4-benzyloxy-4'-hydroxydiphenyl sulfide, 3-phenethyl-4-phenethyloxy-4'-hydroxydiphenyl sulfide, 3-methylbenzyl-4-methyl Benzyloxy-4'-hydroxydiphenylsulfone, 4-benzyloxy-3'-benzyl-4'-hydroxydiphenylsulfone, 4-phenethyloxy-3'-phenethyl-4'-hydroxydiphenylsulfone, 4-methylbenzyloxy- 3'-methylbenzyl-4'-hydroxydiphenylsulfone, α, α'-bis {4- (p-hydroxyphenylsulfone) phenoxy} -p-xylene, 4,4'-{oxybis (ethylene oxide-p-phenylene sulfonyl) )} Diphenol bis (4-hydroxyphenyl) sulfide, bis (4-hydroxy-3-methylphenyl) sulfide, bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, bis (3-ethyl-4-hydroxy) Phenyl) sulfide, bis (3,5-diethyl-4-hydroxyphenyl) sulfide, bis (4-hydroxy-3-n-propylphenyl) sulfide, bis (3,5-di-n-propyl-4-hydroxyphenyl) ) Sulfide, bis (3-tert-butyl-4-hydroxyphenyl) sulfide, bis (3,5-di-tert-butyl-4-hydroxyphenyl) sulfide, bis (4-hydroxy-3-n-pentylphenyl) Sulfide, bis (3-n-hexyl-4-hydroxyphenyl) sulfide, bis (3-n-heptyl-4-hydroxyphenyl) sulfide, bis (5-tert-octyl-2-hydroxyphenyl) sulfide, bis (2) -Hydroxy-3-tert-octylphenyl) sulfide, bis (2-hydroxy-5-n-octyl-phenyl) sulfide, bis (5-chloro-2-hydroxyphenyl) sulfide, bis (3-cyclohexyl-4-hydroxy) Phenyl) sulfide, bis (4-hydroxyphenylthioethoxy) methane, 1,5- (4-hydroxyphenylthi) E) Examples thereof include -3-oxypentane and 1,8-bis (4-hydroxyphenylthio) -3,6-dioxaoctane.

Examples of the compound having three phenolic hydroxyl groups include pyrogallol, phloroglucinol, phloroglucinolcarboxylic acid, gallate, octyl gallate, and dodecyl gallate.

Furthermore, as a tris-type phenol compound,
4,4', 4 "-Methyllysine trisphenol,
4,4', 4 "-methylidinetris (2-methylphenol),
4,4'-[(2-Hydroxyphenyl) methylene] bis (2,3,5-trimethylphenol),
4,4'-[(4-Hydroxyphenyl) methylene] bis (2-methylphenol),
4,4'-[(4-Hydroxyphenyl) methylene] bis (2,6-dimethylphenol),
4,4'-[(4-Hydroxy-3-methoxyphenyl) methylene] bisphenol,
4,4'-[(4-Hydroxyphenyl) methylene] bis (2-cyclohexyl-5-methylphenol),
4,4', 4 "-ethylysine trisphenol,
4,4', 4 "-ethylysintris (2-methylphenol),
4,4'-[(2-Hydroxyphenyl) methylene] bis (2-cyclohexyl-5-methylphenol),
2,6-bis [(2-Hydroxy-5-methylphenyl) methyl] -4-methylphenol,
2,4-Bis [(2-Hydroxy-5-methylphenyl) methyl] -6-cyclohexylphenol,
4,4'-[1- {4- [1- (4-Hydroxyphenyl) -1-methylethyl] phenyl} methylidene] bisphenol,
4,4'-[1- {4- [1- (4-Hydroxyphenyl) -1-methylethyl] phenyl} ethylidene] bisphenol,
4,4'-[1- {4- [1- (4-Hydroxyphenyl) -1-methylethyl] phenyl} propylidene] bisphenol,
4,4'-[1- {4- [1- (4-Hydroxyphenyl) -1-methylethyl] phenyl} butylidene] bisphenol,
4,4'-[1- {4- [1- (4-Hydroxyphenyl) -1-methylethyl] phenyl} pentylidene] bisphenol,
4,4'-[1- {4- [1- (4-Hydroxyphenyl) -1-methylethyl] phenyl} hexylidene] bisphenol,
4,4'-[1- {4- [1- (4-Hydroxyphenyl) -1-methylethyl] phenyl} heptylidene] bisphenol,
4,4'-[1- {4- [1- (4-Hydroxyphenyl) -1-methylethyl] phenyl} isobutylidene] bisphenol,
4,4'-[1- {4- [1- (4-Hydroxyphenyl) -1-methylethyl] phenyl} neopentylidene] bisphenol,
2,2'-[1- {4- [1- (2-Hydroxyphenyl) -1-methylethyl] phenyl} ethylidene] bisphenol,
3,3'-[1- {4- [1- (3-Hydroxyphenyl) -1-methylethyl] phenyl} ethylidene] bisphenol,
4,4'-[1- {4- [1- (3-Fluoro-4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bis (2-fluorophenol),
4,4'-[1- {4- [1- (3-Chloro-4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bis (2-chlorophenol),
4,4'-[1- {4- [1- (3-Bromo-4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bis (2-bromophenol),
4,4'-[1- {4- [1- (4-Hydroxy-3-methylphenyl) -1-methylethyl] phenyl} etylidene] bis (2-methylphenol),
4,4'-[1- {4- [1- (3-ethyl-4-hydroxyphenyl) -1-methylethyl] phenyl} etylden] bis (2-ethylphenol),
4,4'-[1- {4- [1- (3-tert-butyl-4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bis (2-tert-butylphenol),
4,4'-[1- {4- [1- (4-Hydroxy-3-trifluoromethylphenyl) -1-methylethyl] phenyl} etylidene] bis (2-trifluoromethylphenol),
1,1-bis (4-hydroxyphenyl) -4- (4-hydroxy-α-ethyl) benzylcyclohexane,
4,4'-[(3-ethoxy-4-hydroxycyphenyl) methylene] bisphenol,
4,4'-[(3-Hydroxyphenyl) methylene] bis (2,6-dimethylphenol),
2,2'-[(4-Hydroxyphenyl) methylene] bis (3,5-dimethylphenol),
4,4'-[(4-Hydroxy-3-methoxyphenyl) methylene] bis (2,6-dimethylphenol),
2,2'-[(2-Hydroxyphenyl) methylene] bis (3,5,6-trimethylphenol),
4,4'-[(3-Hydroxyphenyl) methylene] bis (2,3,6-trimethylphenol),
4,4'-[(4-Hydroxyphenyl) methylene] bis (2,3,6-trimethylphenol),
4,4'-[(3-Hydroxyphenyl) methylene] bis (2-cyclohexyl-5-methylphenol),
4,4'-[(4-Hydroxyphenyl-3-methoxy) methylene] bis (2-cyclohexyl-5-methylphenol),
1,1-bis (4-hydroxyphenyl) -4-hydroxyphenylcyclohexane,
4,4'-[3- (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-phenyl) propylidene] bis (2-cyclohexyl-5-methylphenol),
4,4'-[(2-Hydroxyphenyl) methylene] bis (2-methylphenol),
2,4', 4 "-methylysine trisphenol,
4,4'-[(2-Hydroxyphenyl) methylene] bis (3-methylphenol),
4,4'-[4- (4-Hydroxyphenyl) -sec-butylidene] bis (4-hydroxyphenol),
2,2'-[(3-Hydroxyphenyl) methylene] bis (3,5-dimethylphenol),
4,4'-[(2-Hydroxy-3-methoxyphenyl) methylene] bis (2,5-dimethylphenol),
4,4'-[(2-Hydroxy-3-methoxyphenyl) methylene] bis (2,6-dimethylphenol),
2,2'-[(2-Hydroxy-3-methoxyphenyl) methylene] bis (3,5-dimethylphenol),
2,2'-[(3-Hydroxy-4-methoxyphenyl) methylene] bis (3,5-dimethylphenol),
2,2'-[(4-Hydroxy-3-methoxyphenyl) methylene] bis (3,5-dimethylphenol),
4,4'-[(2-Hydroxyphenyl) methylene] bis (2-isopropylphenol),
4,4'-[(3-Hydroxyphenyl) methylene] bis (2-isopropylphenol),
4,4'-[(4-Hydroxyphenyl) methylene] bis (2-isopropylphenol),
2,2'-[(3-Hydroxyphenyl) methylene] bis (3,5,6-trimethylphenol),
2,2'-[(4-Hydroxyphenyl) methylene] bis (3,5,6-trimethylphenol),
2,2'-[(4-3-ethoxy-4-hydroxyphenyl) methylene] bis (3,5-dimethylphenol),
1,1-bis (4-hydroxy-3-methylphenyl) -4- (4-hydroxyphenyl) cyclohexane,
4,4'-[(2-Hydroxy-3-methoxyphenyl) methylene] bis (2-isopropylphenol),
4,4'-[(3-Hydroxy-4-methoxyphenyl) methylene] bis (2-isopropylphenol),
4,4'-[(4-Hydroxy-3-methoxyphenyl) methylene] bis (2-isopropylphenol),
2,2'-[(2-Hydroxy-3-methoxyphenyl) methylene] bis (3,5,6-trimethylphenol,
2,2'-[(3-Hydroxy-4-methoxyphenyl) methylene] bis (3,5,6-trimethylphenol),
2,2'-[(4-Hydroxy-3-methoxyphenyl) methylene] bis (3,5,6-trimethylphenol),
4,4'-[(3-ethoxy-4-hydroxyphenyl) methylene] bis (2-isopropylphenol),
2,2'-[(3-ethoxy-4-hydroxyphenyl) methylene] bis (3,5,6-trimethylphenol),
4,4'-[(3-ethoxy-4-hydroxyphenyl) methylene] bis (2,3,6-trimethylphenol),
1,1-bis (3,5-dimethyl-4-hydroxyphenyl) -4- (4-hydroxyphenyl) cyclohexane,
4,4'-[(4-Hydroxy-3-methoxyphenyl) methylene] bis (2-tert-butyl-5-methylphenol),
4,4'-[(2-Hydroxyphenyl) methylene] bis (2-cyclohexylphenol),
4,4'-[(3-Hydroxyphenyl) methylene] bis (2-cyclohexylphenol),
4,4'-[(3-ethoxy-4-hydroxyphenyl) methylene] bis (2-tert-butyl-6-methylphenol),
4,4'-[(3-Methoxy-2-hydroxyphenyl) methylene] bis (2-cyclohexylphenol),
4,4'-[(3-Hydroxy-4-methoxyphenyl) methylene] bis (2-cyclohexylphenol),
4,4'-[1- {4- [1- (3-Fluoro-4-hydroxylophenyl) -1-methylethyl] phenyl} etylidene] bis (2-tert-butylphenol),
4,4'-[1- {4- [1- (3,5-dimethyl-4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bis (2,6-dimethylphenol),
4,4'-[(3-ethoxy-4-hydroxyphenyl) methylene] bis (2-cyclohexyl-5-methylphenol),
4,4'-[(3-cyclohexyl-4-hydroxyphenyl) ethylidene] bis (2-cyclohexylphenol),
4,4'-[(5-cyclohexyl-4-hydroxy-2-methoxyphenyl) ethylidene] bis (2-cyclohexyl-5-methylphenol),
4,4'-[1- {4- [1- (3-Cyclohexyl-4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bis (2-cyclohexylphenol),
4,4'-[1- {4- [1- (3-Fluoro-4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bisphenol,
4,4'-[1- {4- [1- (3-Fluoro-4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bis (2-methylphenol),
4,4'-[1- {4- [1- (3-Fluoro-4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bis (2,6-dimethylphenol),
2,6-bis [(5-fluoro-2-hydroxyphenyl) methyl] -4-methylphenol,
2,6-bis [(3,5-dimethyl-4-hydroxyphenyl) methyl] -4-methylphenol,
2,6-bis [(4-hydroxyphenyl) methyl] -4-methylphenol, 2,6-bis [(4-hydroxyphenyl) methyl] -4-ethylphenol,
2,4-Bis [(4-Hydroxy-3-methylphenyl) methyl] -6-methylphenol,
2,6-bis [(4-Hydroxy-3-methylphenyl) methyl] -4-methylphenol,
2,6-bis [(4-hydroxy-3-methylphenyl) methyl] -4-ethylphenol,
2,6-bis [(2-Hydroxy-5-methylphenyl) methyl] -4-ethylphenol,
2,6-bis [(3,5-dimethyl-2-hydroxyphenyl) methyl] -4-methylphenol,
2,6-bis [(2,4-dimethyl-6-hydroxyphenyl) methyl] -4-methylphenol,
2,4-Bis [(4-Hydroxyphenyl) methyl] -6-cyclohexylphenol,
2,6-bis [(2,5-dimethyl-4-hydroxyphenyl) methyl] -3,4-dimethylphenol,
2,6-bis [(2,5-dimethyl-4-hydroxyphenyl) methyl] -4-ethylphenol,
2,6-bis [(4-hydroxy-2,3,6-trimethylphenyl) methyl] -4-methylphenol,
2,4-Bis [(4-Hydroxy-3-methylphenyl) methyl] -6-cyclohexylphenol,
2,6-bis [(4-Hydroxy-3-methylphenyl) methyl] -4-cyclohexylphenol,
2,6-bis [(2-Hydroxy-5-methylphenyl) methyl] -4-cyclohexylphenol,
2,6-bis [(4-hydroxy-2,3,5-trimethylphenyl) methyl] -4-ethylphenol,
2,4-Bis [(2,5-dimethyl-4-hydroxyphenyl) methyl] -6-cyclohexylphenol,
4,4', 4 "-methyridintris (2,6-dimethylphenol),
α- (4-Hydroxy-3-methylphenyl) -α, α'-bis (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene,
α'-(4-Hydroxy-3-methylphenyl) -α, α-bis (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene,
α, α-bis (4-hydroxy-3-methylphenyl) -α'-(4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene,
α, α'-bis (4-hydroxy-3-methylphenyl) -α- (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene,
1,1-bis (4-hydroxyphenyl) -4- [1- (4-hydroxyphenyl) -1-methylpropyl] cyclohexane,
2,6-bis [(3,5-dimethyl-4-hydroxyphenyl) methyl] -4-ethylphenol,
1,1'-bis (4-hydroxyphenyl) -4- [1- (4-hydroxyphenyl) propyl] cyclohexane,
1,1'-bis (4-hydroxy-3-methylphenyl) -4- [1- (4-hydroxyphenyl) propyl] cyclohexane,
1,1'-bis (3,5-dimethyl-4-hydroxyphenyl) -4- [1- (4-hydroxyphenyl) propyl] cyclohexane,
1- (4-Hydroxyphenyl) -1- [4,4-bis (4-hydroxyphenyl) cyclohexyl] -4-isopropylcyclohexane,
4,4'-[3- (2,5-dimethyl-4-hydroxyphenyl) butylene] bis (2,5-dimethylphenol),
1,3,5-tri (4-hydroxy-3-phenylphenyl) adamantane,
1,3,5-tri (3-cyclohexyl-4-hydroxyphenyl) adamantane,
2,4-Bis [(3,5-dimethyl-4-hydroxyphenyl) methyl] -6-cyclohexylphenol,
2,6-bis [(2,5-dimethyl-4-hydroxyphenyl) methyl] -4-cyclohexylphenol,
2,4-Bis [(3-cyclohexyl-4-hydroxyphenyl) methyl] -6-methylphenol,
2,4-Bis [(4-Hydroxy-2,3,5-trimethylphenyl) methyl] -6-cyclohexylphenol,
2,6-bis [(5-fluoro-2-hydroxyphenyl) methyl] -4-fluorophenol,
2,6-bis [(3-fluoro-4-hydroxyphenyl) methyl] -4-fluorophenol,
2,4-Bis [(3-fluoro-4-hydroxyphenyl) methyl] -6-methylphenol,
4,4'-[3- (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-biphenylpropylidene] bis (5-cyclohexyl-2-methylphenol),
4,4'-[3- (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropylidene] bis (2,5-dimethylphenol),
2,4-Bis [(2,5-dimethyl-4-hydroxyphenyl) methyl] -6-methylphenol, 1,1,2-tris (4-hydroxyphenyl) ethane,
1,1,3-Tris (4-hydroxyphenyl) propane, 1,1,4-Tris (4-hydroxyphenyl) butane,
1,2,2-tris (4-hydroxyphenyl) propane, 1,2,2-tris (4-hydroxyphenyl) butane,
1,2,2-tris (4-hydroxyphenyl) pentane, 1,2,2-tris (4-hydroxyphenyl) hexane,
1,2,2-tris (4-hydroxyphenyl) heptane, 1,2,2-tris (4-hydroxyphenyl) octane,
1,2,2-Tris (4-hydroxyphenyl) -3-methylbutane 1,2,2-Tris (4-hydroxyphenyl) -3,3-dimethylbutane,
1,2,2-tris (4-hydroxyphenyl) -4,4-dimethylpentane, 1,3,3-tris (4-hydroxyphenyl) butane,
1,3,3-Tris (4-hydroxyphenyl) pentane, 1,3,3-Tris (4-hydroxyphenyl) hexane,
1,3,3-tris (4-hydroxyphenyl) heptane, 1,3,3-tris (4-hydroxyphenyl) octane,
1,3,3-Tris (4-hydroxyphenyl) nonane, 1,4,4-Tris (4-hydroxyphenyl) pentane,
1,4,4-Tris (4-hydroxyphenyl) hexane, 1,4,4-Tris (4-hydroxyphenyl) heptane,
1,4,4-Tris (4-hydroxyphenyl) octane, 1,4,4-Tris (4-hydroxyphenyl) nonane,
1,4,4-Tris (4-hydroxyphenyl) decane, 1,2,2-Tris (2-hydroxyphenyl) propane,
1,1,2-Tris (3-hydroxyphenyl) propane,
1- (4-Hydroxyphenyl) -2,2-bis (2-hydroxyphenyl) propane,
1,2,2-Tris (3-fluoro-4-hydroxyphenyl) propane,
1,2,2-Tris (3-chloro-4-hydroxyphenyl) propane,
1,2,2-Tris (3-bromo-4-hydroxyphenyl) propane,
2,2-Bis (3-ethyl-4-hydroxyphenyl) -1- (4-hydroxyphenyl) propane,
2,2-Bis (3-tert-butyl-4-hydroxyphenyl) -1- (4-hydroxyphenyl) propane,
2,2-Bis (2-hydroxy-3-biphenylyl) -1- (4-hydroxyphenyl) propane,
2,2-Bis (3-trifluoromethyl-4-hydroxyphenyl) -1- (4-hydroxyphenyl) propane,
2- (3-Methyl-4-hydroxyphenyl) -1,2-bis (4-hydroxyphenyl) propane,
1- (3-Methyl-4-hydroxyphenyl) -2,2-bis (4-hydroxyphenyl) propane,
3- (3-Methyl-4-hydroxyphenyl) -1,3-bis (4-hydroxyphenyl) butane,
1- (3-Methyl-4-hydroxyphenyl) -3,3-bis (4-hydroxyphenyl) butane,
4- (3-Methyl-4-hydroxyphenyl) -1,4-bis (4-hydroxyphenyl) pentane,
1- (3-Methyl-4-hydroxyphenyl) -4,4-bis (4-hydroxyphenyl) pentane,
1,2-bis (3-methyl-4-hydroxyphenyl) -2- (4-hydroxyphenyl) propane,
3,3-Bis (3-methyl-4-hydroxyphenyl) -1- (4-hydroxyphenyl) butane,
1,3-bis (3-methyl-4-hydroxyphenyl) -3- (4-hydroxyphenyl) butane,
4,4-Bis (3-methyl-4-hydroxyphenyl) -1- (4-hydroxyphenyl) pentane,
1,4-Bis (3-methyl-4-hydroxyphenyl) -4- (4-hydroxyphenyl) pentane,
1,1,2-Tris (3-methyl-4-hydroxyphenyl) ethane,
1,2,2-Tris (3-methyl-4-hydroxyphenyl) propane,
1,1,3-Tris (3-methyl-4-hydroxyphenyl) propane,
1,3,3-Tris (3-methyl-4-hydroxyphenyl) butane,
1,1,4-Tris (3-methyl-4-hydroxyphenyl) butane,
1,4,4-Tris (3-methyl-4-hydroxyphenyl) pentane,
4,4'-[4- (4-Hydroxyphenyl) -sec-butylidene] bis (2-methylphenol)
And so on.

As a compound having four or more phenolic hydroxyl groups,
Bis [2-hydroxy-3- (2-hydroxy-5-methylbenzyl) -5-methylphenyl] methane,
4,6-bis [(4-Hydroxyphenyl) methyl) -1,3-benzenediol,
4,4'-[(3,4-dihydroxyphenyl) methylene] bis (2,6-dimethylphenol),
4,4'-[(3,4-dihydroxyphenyl) methylene] bis (2-cyclohexyl-5-methylphenol),
4,4'-[(3,4-dihydroxyphenyl) methylene] bis (2-methylphenol),
4,4'-[(3,4-dihydroxyphenyl) methylene] bis (2,3,6-trimethylphenol),
1,1,2,2-tetrakis (4-hydroxyphenyl) ethane,
1,1,2,2-tetrakis (4-hydroxy-3-methylphenyl) ethane,
1,1,2,2-tetrakis (3,5-dimethyl-4-hydroxyphenyl) ethane,
1,1,4,4-tetrakis (3,5-dimethyl-4-hydroxyphenyl) benzene,
2,2'-bis [4,4- (4-hydroxy-3-methylphenyl) cyclohexyl] propane,
2,2'-[(3,4-dihydroxyphenyl) methylene] bis (3,5-dimethylphenol),
3,6-bis [(3,5-dimethyl-4-hydroxyphenyl) methyl) catechol,
4,6-bis [(3,5-dimethyl-4-hydroxyphenyl) methyl) -1,3-benzenediol,
2,2'-[(3,4-dihydroxyphenyl) methylene] bis (3,5,6-trimethylphenol),
4,4'-[(3,4-dihydroxyphenyl) methylene] bis (2-cyclohexylphenol),
Bis [3- (2-hydroxybenzyl) -4-hydroxy-5-methylphenyl] methane,
Bis [3- (3-hydroxybenzyl) -4-hydroxy-5-methylphenyl] methane,
Bis [3- (4-hydroxybenzyl) -4-hydroxy-5-methylphenyl] methane,
Bis [3- (2-hydroxybenzyl) -2-hydroxy-5-methylphenyl] methane,
Bis [3- (2-hydroxybenzyl) -3-hydroxy-5-methylphenyl] methane,
Bis [3- (2-hydroxybenzyl) -4-hydroxy-5-methylphenyl] methane,
Bis [3- (3-Hydroxy-2-methylbenzyl) -2-hydroxy-5-methylphenyl] methane,
Bis [3- (4-Hydroxy-3-methylbenzyl) -2-hydroxy-5-methylphenyl] methane,
Bis [3- (3-hydroxy-4-methylbenzyl) -2-hydroxy-5-methylphenyl] methane,
Bis [3- (2-hydroxy-3-methylbenzyl) -2-hydroxy-5-methylphenyl] methane,
α, α', α ", α'"-tetrakis (4-hydroxyphenyl) benzene,
Bis [3- (3,6-dimethyl-2-hydroxybenzyl) -2-hydroxy-5-methylphenyl] methane,
[3- (3,6-Dimethyl-2-hydroxybenzyl) -2-hydroxy-5-methylphenyl],
[3- (2,5-dimethyl-4-hydroxybenzyl) -2-hydroxy-5-methylphenyl] methane,
Bis [3- (2,5-dimethyl-4-hydroxybenzyl) -2-hydroxy-5-methylphenyl] methane,
Bis [3- (3,5-dimethyl-4-hydroxybenzyl) -2-hydroxy-5-methylphenyl] methane,
Bis [3- (2-hydroxy-3,4,6-trimethylbenzyl) -2-hydroxy-5-methylphenyl] methane,
Bis [2-hydroxy-3- (4-hydroxy-2,3,5-trimethylbenzyl) -5-methylphenyl] methane,
4,4', 4 ", 4'"-Tetrakis (4-hydroxyphenyl) -1,1'-bicyclohexyl,
2,2'-bis [4,54-bis (4-hydroxyphenyl) cyclohexyl] propane,
4,4', 4 ", 4'"-Tetrakis (4-hydroxy-3-methylphenyl) -1,1'-bicyclohexyl,
Bis [3- (5-cyclohexyl-4-hydroxy-2-methylbenzyl) -4-hydroxy-5-methylphenyl] methane,
4,4', 4 ", 4'"-Tetrakis (3,5-dimethyl-4-hydroxyphenyl) -1,1'-bicyclohexyl,
1,1-bis [3- (2-hydroxy-5-methylbenzyl) -5-cyclohexyl-4-hydroxyphenyl] cyclohexane,
1,1-bis [3- (3,5-dimethyl-4-hydroxybenzyl) -5-cyclohexyl-4-hydroxyphenyl] cyclohexane,
1,1-bis [3- (5-cyclohexyl-4-hydroxy-2-methylbenzyl) -5-cyclohexyl-4-hydroxyphenyl] cyclohexane,
4,6-bis [α-methyl- (4-hydroxyphenyl) benzyl-1,3-benzenediol,
2,2-Bis [3- (4-Hydroxy-3-methylbenzyl) -4-hydroxy-5-methylphenyl] propane,
2,6-bis [(3,5-dimethyl-4-hydroxyphenyl) benzyl] -4- [α-methyl- (3,5-dimethyl-4-hydroxyphenyl) benzyl] phenol,
4,4', 4 ", 4'"-Tetrakis (4-hydroxy-3-isopropylphenyl) -1,1'-bicyclohexyl,
4,4'-bis [(3,4-dihydroxyphenyl) methylene] bis (2-isopropylphenol)
2,4,6-tris (4-hydroxybenzyl) -1,3-benzenediol,
4,6-bis (3,5-dimethyl-4-hydroxybenzyl) pyrogallol,
3,3'-[(2-Hydroxyphenyl) methylene] bis (5-methylcatechol),
2,6-bis (2,4-dihydroxybenzyl) -4-ethylphenol,
2,4-Bis (2,4-dihydroxybenzyl) -6-cyclohexylphenol,
2,6-bis (5-tert-butyl-2,3-dihydroxybenzyl) -4-methylphenol,
2,4,6-tris (3,5-dimethyl-4-hydroxybenzyl) resorcin,
2,4,6-tris (3,5-dimethyl-2-hydroxybenzyl) resorcin,
2,6-bis (2,4-dihydroxybenzyl) -3,4-dimethylphenol,
2,6-bis [3- (2-hydroxy-5-methylbenzyl) -2,5-dimethyl-4-hydroxybenzyl] -3,4-dimethylphenol,
4,6-bis (α-methyl-4-hydroxybenzyl) pyrogallol,
4,4'-[1- {4- [1- (3,5-bis (4-hydroxybenzyl) -4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bis [2,6-bis (2,6-bis) 4-Hydroxybenzyl) phenol],
4,4'-[1- {4- [1- (3,5-bis (4-hydroxy-3-methylbenzyl) -4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bis [2 6-bis (4-hydroxy-3-methylbenzyl) phenol],
4,4'-[1- {4- [1- (3,5-bis (3,5-dimethyl-4-hydroxybenzyl) -4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bis [ 2,6-bis (3,5-dimethyl-4-hydroxybenzyl) phenol],
4,4'-[1- {4- [1- (3,5-bis (4-hydroxy-2,3,6-trimethylbenzyl) -4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] Bis [2,6-bis (4-hydroxy-2,3,6-trimethylbenzyl) phenol],
Bis [5- (2,4-dihydroxybenzyl) -4-hydroxy-3-methylphenyl] methane, bis [3- (2,4-dihydroxybenzyl) -2,5-dimethyl-4-hydroxyphenyl] methane,
Bis [3- (2,4-dihydroxy-3-methylbenzyl) -2,5-dimethyl-4-hydroxyphenyl] methane,
Bis [5- (4-hydroxybenzyl) -2,3,4-trihydroxyphenyl] methane,
1,1-bis [5- (4-hydroxybenzoyl) -2,3,4-trihydroxyphenyl] ethane,
3,3', 5,5'-tetrakis (4-hydroxybenzyl) -4,4'-dihydroxybiphenyl,
3,3', 5,5'-tetrakis (4-hydroxy-3-methylbenzyl) -4,4'-dihydroxybiphenyl,
3,3', 5,5'-tetrakis (2-hydroxy-5-methylbenzyl) -4,4'-dihydroxybiphenyl,
3,3', 5,5'-Tetrakis (3,5-dimethyl-4-hydroxybenzyl) -4,4'-dihydroxybiphenyl,
Bis [3- (α, α-bis (4-hydroxy-3-methylphenyl) methyl-4-hydroxyphenyl] methane,
Bis [3,5-bis (2-hydroxy-5-methylbenzyl) -4-hydroxyphenyl] methane,
4,4', 4 "-ethylidinetris {[2- (2-hydroxy-5-methyl) benzyl] -6-methylphenol},
2,2-bis [3,5-bis (2-hydroxy-5-methylphenylmethyl) phenyl] propane,
Bis [3- (α, α-bis (2,5-dimethyl-4-hydroxyphenyl) methyl-4-hydroxyphenyl] methane,
Bis [5- (3,5-dimethyl-4-hydroxybenzyl) -2,3,4-trihydroxyphenyl] methane,
Bis [3- (2,3,4-trihydroxybenzyl) -2,5-dimethyl-4-hydroxyphenyl] methane,
1,1-bis [3- (2,3,4-trihydroxybenzyl) -5-cyclohexyl-4-hydroxyphenyl] cyclohexane,
1,8,15,22-Tetranonyl-3,5,10,12,17,19,24,26-Octahydroxy [1,1,1,1] -metacyclophane,
4,4'-[1- {4- [1- (3,5-bis (4-hydroxy-2-methylbenzyl) -4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bis [2 6-Bis (4-hydroxy-2-methylbenzyl) phenol],
4,4'-[1- {4- [1- (3,5-bis (2-hydroxy-5-methylbenzyl) -4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bis [2 6-bis (2-hydroxy-5-methylbenzyl) phenol],
4,4'-[1- {4- [1- (3,5-bis (3-ethyl-4-hydroxybenzyl) -4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bis [2 6-Bis (3-ethyl-4-hydroxybenzyl) phenol],
4,4'-[1- {4- [1- (3,5-bis (3,5-dimethyl-2-hydroxyphenyl) -4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bis [ 2,6-bis (3,5-dimethyl-2-hydroxyphenyl) phenol],
4,4'-[1- {4- [1- (3,5-bis (4-hydroxy-3-isopropylphenyl) -4-hydroxyphenyl) -1-methylethyl] phenyl} ethylidene] bis [2 6-Bis (4-hydroxy-3-isopropylphenyl) phenol],
Bis [3- (α, α-bis (3,5-dimethyl-4-hydroxyphenyl) methyl-4-hydroxyphenyl] methane,
Bis [3- (α, α-bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) methyl-4-hydroxyphenyl] methane,
4,4'-[4-Hydroxy-3,5-bis (2-hydroxybenzyl) methylene] bis [2,6-bis (2-hydroxybenzyl)] phenol,
4,4'-[4-Hydroxy-3,5-bis (4-hydroxybenzyl) methylene] bis [2,6-bis (4-hydroxybenzyl)] phenol,
4,4', 4 "-ethylidinetris [2,6-bis (2-hydroxybenzyl) phenol],
4,4', 4 "-ethylidinetris [2,6-bis (4-hydroxybenzyl) phenol],
2,2-bis [3,5-bis (4-hydroxy-3-methylbenzyl) -4-hydroxyphenyl] propane,
1,8,15,22-Tetraethyl-3,5,10,12,17,19,24,26-Octahydroxy [1,1,1,1] -metacyclophane,
α, α', α ", α'"-tetrakis (3,5-dimethyl-4-hydroxyphenyl) -1,4-dimethylbenzene,
4,4'-[1- {4- [1- (3,5-bis (2-hydroxy-5-isopropylphenyl) -4-hydroxyphenyl) -1-methylethyl] phenyl} ethylidene] bis [2 6-bis (2-hydroxy-5-isopropylphenyl) phenol],
4,4'-[1- {4- [1- (3,5-bis (4-hydroxy-2,3,5-trimethylphenyl) -4-hydroxyphenyl) -1-methylethyl] phenyl} ethylidene] Bis [2,6-bis (4-hydroxy-2,3,5-trimethylphenyl) phenol],
4,4'-[1- {4- [1- (3,5-bis (3-sec-butyl-4-hydroxyphenyl) -4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bis [ 2,6-bis (3-sec-butyl-4-hydroxyphenyl) phenol],
4,4'-[1- {4- [1- (3,5-bis (3-tert-butyl-4-hydroxyphenyl) -4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bis [ 2,6-bis (3-tert-butyl-4-hydroxyphenyl) phenol],
2,6-bis {[3- (2,4-dihydroxybenzyl) -2,5-dimethyl-4-hydroxy] benzyl} -4-methylphenol,
1,1-bis [5- (2,4-dihydroxybenzyl) -3-cyclohexyl-4-hydroxyphenyl] cyclohexane,
1,1-bis [5- (2,3,4-trihydroxybenzyl) -3-cyclohexyl-4-hydroxyphenyl] cyclohexane,
Examples thereof include 2,2-bis [4,4', 4 ", 4'"-tetrakis (3,5-dihydroxymethyl-4-hydroxyphenyl) cyclohexyl] propane.

Examples of the carboxylic acid and its derivatives include 3,5-di (α-methylbenzyl) salicylic acid and its zinc salt, 4- (2-p-methoxyphenyloxyethoxy) salicylic acid and its zinc salt, 4-hydroxyphenylbenzoic acid, and the like. Zinc 4-chlorobenzoate, 4- [2- (p-methoxyphenoxy) ethyloxy] zinc salicylate, 4- [3- (p-tolylsulfonyl) propyloxy] zinc salicylate, 5- [p- (2-p-) Methoxyphenoxyethoxy) cumyl] zinc salicylate, zinc 4-octyloxycarbonylaminosalicylate, 3,5-distyrene salicylic acid, N- (p-toluenesulfonyl) -glycine, N- (p-toluenesulfonyl) -alanine, N- (P-Toluenesulfonyl) -β-alanine, N-phenylaminocarbonyl-glycine, N-phenylaminocarbonyl-valine, N- (m-tolylaminocarbonyl) -phenylalanine, N- (m-tolylaminocarbonyl) -cysteine -S-benzyl, N- (m-trillaminocarbonyl) -methionine, N- (m-trillaminocarbonyl) -tyrosine, N- (p-trillaminocarbonyl) -phenylalanine, N- (p-trillaminocarbonyl) -Cysteine-S-benzyl, N- (p-tolylaminocarbonyl) -methionine, N- (p-tolylaminocarbonyl) -methionine, N- (phenylaminocarbonyl) -methionine, N- (p-tolylaminocarbonyl) -Tyrosine, 2-O- (phenylaminocarbonyl) -mandelic acid, 2-O- (p-tolylaminocarbonyl) -mandelic acid, 2-O- (m-trillaminocarbonyl) -mandelic acid, 2-O- (O-trillaminocarbonyl) -mandelic acid, 2-O- (1-naphthylaminocarbonyl) -mandelic acid, 2-O- (3-isopropenyl-α, α-dimethylbenzylaminocarbonyl) -mandelic acid, 2 -O- (benzylaminocarbonyl) -mandelic acid, 2-O- (phenethylaminocarbonyl) -mandelic acid, 2-O- (phenylaminocarbonyl) -lactic acid, 2-O- (p-tolylaminocarbonyl) -lactic acid , 2-O- (m-tolylaminocarbonyl) -lactic acid, 2-O- (o-tolylaminocarbonyl) -lactic acid, 2-O- (1-naphthylaminocarbonyl) -lactic acid, 2-O- (3-) Isopropenyl-α, α-dimethylbenzylaminocarbonyl) -lactic acid, 2-O- (ben Dylaminocarbonyl) -lactic acid, 2-O- (phenethylaminocarbonyl) -lactic acid and the like can be mentioned.

Examples of the acidic phosphoric acid ester compound include methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, isodecyl acid phosphate, isotridecyl acid phosphate, oleyl acid phosphate, and tetracosyl. Examples thereof include acid phosphate, monobutyl phosphate, dibutyl phosphate, monoisodecyl phosphate, bis (2-ethylhexyl) phosphate and the like.

The compound having a phenolic hydroxyl group can exhibit the most effective thermal discoloration property, but is an aromatic carboxylic acid and an aliphatic carboxylic acid having 2 to 5 carbon atoms, a carboxylic acid metal salt, an acidic phosphoric acid ester and a metal thereof. It may be a compound selected from a salt, 1,2,3-triazole and a derivative thereof.

The component (c) of the reaction medium that reversibly causes the electron transfer reaction by the components (a) and (b) in a specific temperature range will be described.
Examples of the component (c) include alcohols, esters, ketones, ethers, and acid amides.
When the compound is applied to microencapsulation and secondary processing, low molecular weight compounds easily evaporate to the outside of the capsule when subjected to high heat treatment, so the number of carbon atoms is 10 or more in order to stably retain the compound in the capsule. Compound is preferably used.
As alcohols, aliphatic monohydric saturated alcohols having 10 or more carbon atoms are effective. Specifically, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl. Examples thereof include alcohols, heptadecyl alcohols, octadecyl alcohols, eicosyl alcohols and docosyl alcohols.

As the esters, esters having 10 or more carbon atoms are effective, and any combination of a monovalent carboxylic acid having an aliphatic and an alicyclic or aromatic ring and a monovalent alcohol having an aliphatic and an alicyclic or aromatic ring is effective. Esters, aliphatic and alicyclics obtained from any combination of a polycarboxylic acid having an aliphatic and alicyclic or aromatic ring and a monovalent alcohol having an aliphatic and alicyclic or aromatic ring. Alternatively, esters obtained from any combination of a monovalent carboxylic acid having an aromatic ring and an aliphatic and a polyvalent alcohol having an alicyclic or aromatic ring can be mentioned, and specific examples thereof include ethyl caprylate, octyl caprylate, and capryl. Stearyl acid, myristyl caprate, docosyl caprate, 2-ethylhexyl laurate, n-decyl laurate, 3-methylbutyl myristate, cetyl myristate, isopropyl palmitate, neopentyl palmitate, nonyl palmitate, cyclohexyl palmitate, stearic acid N-butyl acid acid, 2-methylbutyl stearate, 3,5,5-trimethylhexyl stearate, n-undecyl stearate, pentadecyl stearate, stearyl stearate, cyclohexylmethyl stearate, isopropyl behenate, hexyl behenate, behen Lauryl acid, behenyl behenyl, cetyl benzoate, p-tert-butyl stearyl benzoate, dimyristyl phthalate, distearyl phthalate, dimyristyl oxalate, disetyl oxalate, disetyl malonate, dilauryl succinate, dilauryl glutarate, adipine Diundecyl acid, dilauryl azelaate, di- (n-nonyl) sebacate, dineopentil 1,18-octadecylmethylene dicarboxylic acid, ethylene glycol dimylstate, propylene glycol dilaurate, propylene glycol distearate, hexylene glycol dipalmitate, 1,5-Pentanediol distearate, 1,2,6-hexanetriol trimilistate, 1,4-cyclohexanediol didecyl, 1,4-cyclohexanedimethanol dimystate, xylene glycol dicaprine, xylene glycol Examples include distearate.

Also, esters of saturated fatty acids and branched fatty alcohols, esters of unsaturated fatty acids or fatty alcohols branched or branched from saturated fatty acids having branches or substituents, or esters of aliphatic alcohols having 16 or more carbon atoms, cetyl butyrate, stearyl butyrate and Ester compounds selected from behenyl butyrate are also effective.
Specifically, 2-ethylhexyl butyrate, 2-ethylhexyl behenate, 2-ethylhexyl myristate, 2-ethylhexyl capric acid, 3,5,5-trimethylhexyl laurate, 3,5,5-trimethylhexyl palmitate, 3,5,5-trimethylhexyl stearate, 2-methylbutyl caproate, 2-methylbutyl caprylate, 2-methylbutyl capriate, 1-ethylpropyl palmitate, 1-ethylpropyl stearate, 1-ethylpropyl behenate, 1-ethylhexyl laurate, 1-ethylhexyl myristate, 1-ethylhexyl palmitate, 2-methylpentyl caproate, 2-methylpentyl caprylate, 2-methylpentyl caprate, 2-methylpentyl laurate, 2-stearate Methylbutyl, 2-methylbutyl stearate, 3-methylbutyl stearate, 1-methylheptyl stearate, 2-methylbutyl behenate, 3-methylbutyl behenate, 1-methylheptyl stearate, 1-methylheptyl behenate, caproic acid 1 -Ethylpentyl, 1-ethylpentyl palmitate, 1-methylpropyl stearate, 1-methyloctyl stearate, 1-methylhexyl stearate, 1,1-dimethylpropyl laurate, 1-methylpentyl capricate, palmitic acid 2-Methylhexyl, 2-methylhexyl stearate, 2-methylhexyl behenate, 3,7-dimethyloctyl laurate, 3,7-dimethyloctyl myristate, 3,7-dimethyloctyl palmitate, 3, stearate 7-Dimethyloctyl, 3,7-dimethyloctyl behenate, stearyl oleate, behenyl oleate, stearyl linoleic acid, behenyl linoleate, 3,7-dimethyloctyl erucate, stearyl erucate, isostearic erucate, isostearic acid Cetyl, stearyl isostearate, 2-methylpentyl 12-hydroxystearate, 2-ethylhexyl 18-bromostearate, isostearyl 2-ketomyristate, 2-ethylhexyl 2-fluoromyristate, cetyl butyrate, stearyl butyrate, behenyl butyrate And so on.

Further, in order to discolor by showing a large hysteresis characteristic with respect to the color density-temperature curve and to give color memory depending on the temperature change, it is described in Japanese Patent Publication No. 4-17154 and has a temperature of 5 ° C. or higher and lower than 50 ° C. A carboxylic acid ester compound showing a ΔT value (melting point-cloud point), for example, a carboxylic acid ester containing a substituted aromatic ring in the molecule, an ester of a carboxylic acid containing an unsubstituted aromatic ring and an aliphatic alcohol having 10 or more carbon atoms. , A carboxylic acid ester containing a cyclohexyl group in the molecule, a fatty acid having 6 or more carbon atoms and an unsubstituted aromatic alcohol or phenol ester, a fatty acid having 8 or more carbon atoms and a branched aliphatic alcohol or ester, a dicarboxylic acid and an aromatic alcohol or Esters of branched aliphatic alcohols, dibenzyl silicate, heptyl stearate, didecyl adipate, dilauryl adipate, dimyristyl adipate, disetyl adipate, distearyl adipate, trilaurin, trimyristin, tristeare, dimyristin, distearate, etc. Can be mentioned.

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 number of carbon atoms, n-pentyl alcohol or n-heptyl alcohol and an even aliphatic carboxylic acid having 10 to 16 carbon atoms. Aliphatic ester compounds having a total carbon number of 17 to 23 obtained from an acid are also effective.
Specifically, n-pentadecyl acetate, n-tridecyl butyrate, n-pentadecyl butyrate, n-undecyl caproate, n-tridecyl caproate, n-pentadecyl caproate, n-nonyl caprylate, n-undecyl caprylate, N-tridecyl caprylate, n-pentadecyl caprylate, n-heptyl caprate, n-nonyl caprate, n-undecyl caprate, n-tridecyl caprate, n-pentadecyl caprate, n-pentyl laurate, laurate n-heptyl, n-nonyl laurate, n-undecyl laurate, n-tridecyl laurate, n-pentadecyl laurate, n-pentyl myristate, n-heptyl myristate, n-nonyl myristate, n-myristate Undecyl, n-tridecyl myristate, n-pentadecyl myristate, n-pentyl palmitate, n-heptyl palmitate, n-nonyl palmitate, n-undecyl palmitate, n-tridecyl palmitate, n-pentadecyl palmitate, N-nonyl stearate, n-undecyl stearate, n-tridecyl stearate, n-pentadecyl stearate, n-nonyl eicosanoate, n-undersi eicosanoate, n-tridecyl eicosanoate, n-pentadecyl eicosanoate, behenic acid Examples thereof include n-nonyl, n-undecyl behenate, n-tridecyl behenate, and n-pentadecyl behenate.

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, 2 -Dodecanone, 3-Dodecanone, 4-Dodecanone, 5-Dodecanone, 2-Tridecanone, 3-Tridecanone, 2-Tetradecanone, 2-Pentadecanone, 8-Pentadecanone, 2-Hexadecanone, 3-Hexadecanone, 9-Heptadecanone, 2-Pentadecanone , 2-Octadecanone, 2-Nonadecanone, 10-Nonadecanone, 2-Eicosanone, 11-Eicosanone, 2-Heneikosanone, 2-Docosanone, Lauron, Stealon and the like.
Furthermore, arylalkylketones having a total carbon number of 12 to 24, such as n-octadecanophenone, n-heptadecanophenone, n-hexadecanophenone, n-pentadecanophenone, n-tetradeca Nophenone, 4-n-dodecaacetophenone, n-tridecanophenone, 4-n-undecanoacetophenone, n-laurofenone, 4-n-decanoacetophenone, n-undecanophenone, 4-n-nonylacetophenone, n-decanophenone, 4-n-octylacetophenone, n-nonanophenone, 4-n-heptylacetophenone, n-octanophenone, 4-n-hexylacetophenone, 4-n-cyclohexylacetophenone, 4-tert-butylpropiophenone , N-Heptaphenone, 4-n-pentylacetophenone, cyclohexylphenylketone, benzyl-n-butylketone, 4-n-butylacetophenone, n-hexanophenone, 4-isobutylacetophenone, 1-acetonafton, 2-acetonafton, cyclopentylphenyl Examples include ketones.

As the ethers, aliphatic ethers having a total carbon number of 10 or more are effective, and dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, dinonyl ether, didecyl ether, diundecyl ether, didodecyl ether, and ditri. Decyl ether, ditetradecyl ether, dipentadecyl ether, dihexadecyl ether, dioctadecyl ether, decanediol dimethyl ether, undecanediol dimethyl ether, dodecanediol dimethyl ether, tridecanediol dimethyl ether, decanediol diethyl ether, undecanediol diethyl ether, etc. Can be mentioned.

Acid amides include acetamide, propionic acid amide, butyric acid amide, caproic acid amide, capric acid amide, capric acid amide, lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, and oleic acid amide. , Elcaic acid amide, benzamide, caproic acid anilide, capric acid anilide, capric acid anilide, laurate anilide, myristic acid anilide, palmitate anilide, stearate anilide, behenic acid anilide, oleic acid anilide, erucate anilide -Methylamide, capric acid N-methylamide, capric acid N-methylamide, lauric acid N-methylamide, myristic acid N-methylamide, palmitic acid N-methylamide, stearate N-methylamide, behenic acid N-methylamide, oleic acid N-methylamide , Elcaic 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, palmitin Acid N-butylamide, stearate N-butylamide, oleic acid N-butylamide, laurate N-octylamide, myristic acid N-octylamide, palmitate N-octylamide, stearate N-octylamide, oleate N-octylamide Amide, lauric acid N-dodecylamide, myristic acid N-dodecylamide, palmitate N-dodecylamide, stearate N-dodecylamide, oleic acid N-dodecylamide, dilauric acid amide, dimyristic acid amide, dipalmitic acid amide , Distearic acid amide, Dioleic acid amide, Trilaurate amide, Trimyristic acid amide, Tripalmitic acid amide, Tristearic acid amide, Trioleic acid amide, Succinic acid amide, Adipic acid amide, Gluteric acid amide, Malonic acid amide, Azeline Acid amide, maleic acid amide, succinic acid N-methylamide, adipic acid N-methylamide, glutaric acid N-methylamide, malonic acid N-methylamide, azelaic acid N-methylamide, succinic acid N-ethylamide, adipate N-ethylamide, glutaru Acid N-ethylamide, malonic acid N-ethylamide, azelaic acid N-ethylamide, succinic acid N-butylamide, adipic acid N- Butyramide, glutaric acid N-butylamide, malonic acid N-butylamide, adipic acid N-octylamide, adipic acid N-dodecylamide and the like can be mentioned.

〔式中、Ｒ_１は水素原子又はメチル基を示し、ｍは０〜２の整数を示し、Ｘ_１、Ｘ_２のいずれか一方は−（ＣＨ_２）_ｎＯＣＯＲ_２又は−（ＣＨ_２）_ｎＣＯＯＲ_２、他方は水素原子を示し、ｎは０〜２の整数を示し、Ｒ_２は炭素数４以上のアルキル基又はアルケニル基を示し、Ｙ_１及びＹ_２は水素原子、炭素数１〜４のアルキル基、メトキシ基、又は、ハロゲンを示し、ｒ及びｐは１〜３の整数を示す。〕
前記式（１）で示される化合物のうち、Ｒ_１が水素原子の場合、より広いヒステリシス幅を有する可逆熱変色性組成物が得られるため好適であり、更にＲ_１が水素原子であり、且つ、ｍが０の場合がより好適である。
なお、式（１）で示される化合物のうち、より好ましくは下記一般式（２）で示される化合物が用いられる。

式中のＲは炭素数８以上のアルキル基又はアルケニル基を示すが、好ましくは炭素数１０〜２４のアルキル基、更に好ましくは炭素数１２〜２２のアルキル基である。
前記化合物として具体的には、オクタン酸−４−ベンジルオキシフェニルエチル、ノナン酸−４−ベンジルオキシフェニルエチル、デカン酸−４−ベンジルオキシフェニルエチル、ウンデカン酸−４−ベンジルオキシフェニルエチル、ドデカン酸−４−ベンジルオキシフェニルエチル、トリデカン酸−４−ベンジルオキシフェニルエチル、テトラデカン酸−４−ベンジルオキシフェニルエチル、ペンタデカン酸−４−ベンジルオキシフェニルエチル、ヘキサデカン酸−４−ベンジルオキシフェニルエチル、ヘプタデカン酸−４−ベンジルオキシフェニルエチル、オクタデカン酸−４−ベンジルオキシフェニルエチルを例示できる。 Further, as the component (c), a compound represented by the following general formula (1) can also be used.

[In the formula, R ₁ represents a hydrogen atom or a methyl group, m represents an integer of 0 to ₂ , and either X ₁ or X ₂ is − (CH ₂ ) _n OCOR ₂ or − (CH ₂ ) _n. COOR ₂ , the other represents a hydrogen atom, n represents an integer of 0 to 2, R ₂ represents an alkyl or alkenyl group having 4 or more carbon atoms, Y ₁ and Y ₂ represent a hydrogen atom and 1 to 4 carbon atoms. Indicates an alkyl group, a methoxy group, or a halogen, and r and p represent integers of 1 to 3. ]
Among the compounds represented by the formula (1), when R ₁ is a hydrogen atom, it is suitable because a reversible thermochromic composition having a wider hysteresis width can be obtained, and further, R ₁ is a hydrogen atom and , M is more preferably 0.
Of the compounds represented by the formula (1), the compound represented by the following general formula (2) is more preferably used.

R in the formula represents an alkyl group or an alkenyl group having 8 or more carbon atoms, preferably an alkyl group having 10 to 24 carbon atoms, and more preferably an alkyl group having 12 to 22 carbon atoms.
Specifically, the compounds include -4-benzyloxyphenylethyl octanoate, -4-benzyloxyphenylethyl nonanoate, -4-benzyloxyphenylethyl decanoate, -4-benzyloxyphenylethyl undecanoate, and dodecanoic acid. -4-benzyloxyphenylethyl, 4-benzyloxyphenylethyl tridecanoate, -4-benzyloxyphenylethyl tetradecanoate, -4-benzyloxyphenylethyl pentadecanoic acid, -4-benzyloxyphenylethyl hexadecanoic acid, heptadecanoic acid Examples thereof include -4-benzyloxyphenylethyl and -4-benzyloxyphenylethyl octadecanoic acid.

（式中、Ｒは炭素数８以上のアルキル基又はアルケニル基を示し、ｍ及びｎはそれぞれ１〜３の整数を示し、Ｘ及びＹはそれぞれ水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、ハロゲンを示す。）
前記化合物として具体的には、オクタン酸１,１−ジフェニルメチル、ノナン酸１,１−ジフェニルメチル、デカン酸１,１−ジフェニルメチル、ウンデカン酸１,１−ジフェニルメチル、ドデカン酸１,１−ジフェニルメチル、トリデカン酸１,１−ジフェニルメチル、テトラデカン酸１,１−ジフェニルメチル、ペンタデカン酸１,１−ジフェニルメチル、ヘキサデカン酸１,１−ジフェニルメチル、ヘプタデカン酸１,１−ジフェニルメチル、オクタデカン酸１,１−ジフェニルメチルを例示できる。 Further, as the component (c), a compound represented by the following general formula (3) can also be used.

(In the formula, R represents an alkyl group or an alkoxy group having 8 or more carbon atoms, m and n represent integers of 1 to 3 respectively, and X and Y represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and carbon, respectively. Indicates the number 1 to 4 alkoxy groups and halogens.)
Specifically, the compounds include octanoic acid 1,1-diphenylmethyl, nonanoic acid 1,1-diphenylmethyl, decanoic acid 1,1-diphenylmethyl, undecanoic acid 1,1-diphenylmethyl, and dodecanoic acid 1,1-. Diphenylmethyl, tridecanoic acid 1,1-diphenylmethyl, tetradecanoic acid 1,1-diphenylmethyl, pentadecaneic acid 1,1-diphenylmethyl, hexadecanoic acid 1,1-diphenylmethyl, heptadecanoic acid 1,1-diphenylmethyl, octadecanoic acid 1,1-Diphenylmethyl can be exemplified.

（式中、Ｘは水素原子、炭素数１乃至４のアルキル基、メトキシ基、ハロゲン原子のいずれかを示し、ｍは１乃至３の整数を示し、ｎは１乃至２０の整数を示す。）
前記化合物としては、マロン酸と２−〔４−(４−クロロベンジルオキシ）フェニル）〕エタノールとのジエステル、こはく酸と２−（４−ベンジルオキシフェニル）エタノールとのジエステル、こはく酸と２−〔４−(３−メチルベンジルオキシ）フェニル）〕エタノールとのジエステル、グルタル酸と２−（４−ベンジルオキシフェニル）エタノールとのジエステル、グルタル酸と２−〔４−(４−クロロベンジルオキシ）フェニル）〕エタノールとのジエステル、アジピン酸と２−（４−ベンジルオキシフェニル）エタノールとのジエステル、ピメリン酸と２−（４−ベンジルオキシフェニル）エタノールとのジエステル、スベリン酸と２−（４−ベンジルオキシフェニル）エタノールとのジエステル、スベリン酸と２−〔４−(３−メチルベンジルオキシ）フェニル）〕エタノールとのジエステル、スベリン酸と２−〔４−(４−クロロベンジルオキシ）フェニル）〕エタノールとのジエステル、スベリン酸と２−〔４−(２，４−ジクロロベンジルオキシ）フェニル）〕エタノールとのジエステル、アゼライン酸と２−（４−ベンジルオキシフェニル）エタノールとのジエステル、セバシン酸と２−（４−ベンジルオキシフェニル）エタノールとのジエステル、１，１０−デカンジカルボン酸と２−（４−ベンジルオキシフェニル）エタノールとのジエステル、１，１８-オクタデカンジカルボン酸と２−（４−ベンジルオキシフェニル）エタノールとのジエステル、１，１８-オクタデカンジカルボン酸と２−〔４−(２−メチルベンジルオキシ）フェニル）〕エタノールとのジエステルを例示できる。 Further, as the component (c), a compound represented by the following general formula (4) can also be used.

(In the formula, X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, or a halogen atom, m represents an integer of 1 to 3, and n represents an integer of 1 to 20.)
Examples of the compound include a diester of malonic acid and 2- [4- (4-chlorobenzyloxy) phenyl)] ethanol, a diester of oxalic acid and 2- (4-benzyloxyphenyl) ethanol, and a diester of oxalic acid and 2-. [4- (3-Methylbenzyloxy) phenyl)] Diester with ethanol, Diester with glutaric acid and 2- (4-benzyloxyphenyl) ethanol, Diester with glutaric acid and 2- [4- (4-chlorobenzyloxy) Phenyl)] Diester with ethanol, diester with adipic acid and 2- (4-benzyloxyphenyl) ethanol, diester with pimeric acid and 2- (4-benzyloxyphenyl) ethanol, suberic acid and 2- (4-benzyloxyphenyl) ethanol Diester with benzyloxyphenyl) ethanol, diester with suberic acid and 2- [4- (3-methylbenzyloxy) phenyl)] Diester with ethanol, diester with suberic acid and 2- [4- (4-chlorobenzyloxy) phenyl)] Diester with ethanol, diester with suberic acid and 2- [4- (2,4-dichlorobenzyloxy) phenyl)] ethanol, diester with azelaic acid and 2- (4-benzyloxyphenyl) ethanol, with sebacic acid Diester with 2- (4-benzyloxyphenyl) ethanol, diester with 1,10-decandicarboxylic acid and 2- (4-benzyloxyphenyl) ethanol, 1,18-octadecanedicarboxylic acid and 2- (4-benzyl) Examples thereof include a diester with oxyphenyl) ethanol, and a diester with 1,18-octadecanedicarboxylic acid and 2- [4- (2-methylbenzyloxy) phenyl)] ethanol.

（式中、Ｒは炭素数１乃至２１のアルキル基又はアルケニル基を示し、ｎは１乃至３の整数を示す。）
前記化合物としては、１，３−ビス（２−ヒドロキシエトキシ）ベンゼンとカプリン酸とのジエステル、１，３−ビス（２−ヒドロキシエトキシ）ベンゼンとウンデカン酸とのジエステル、１，３−ビス（２−ヒドロキシエトキシ）ベンゼンとラウリン酸とのジエステル、１，３−ビス（２−ヒドロキシエトキシ）ベンゼンとミリスチン酸とのジエステル、１，４−ビス（ヒドロキシメトキシ）ベンゼンと酪酸とのジエステル、１，４−ビス（ヒドロキシメトキシ）ベンゼンとイソ吉草酸とのジエステル、１，４−ビス（２−ヒドロキシエトキシ）ベンゼンと酢酸とのジエステル、１，４−ビス（２−ヒドロキシエトキシ）ベンゼンとプロピオン酸とのジエステル、１，４−ビス（２−ヒドロキシエトキシ）ベンゼンと吉草酸とのジエステル、１，４−ビス（２−ヒドロキシエトキシ）ベンゼンとカプロン酸とのジエステル、１，４−ビス（２−ヒドロキシエトキシ）ベンゼンとカプリル酸とのジエステル、１，４−ビス（２−ヒドロキシエトキシ）ベンゼンとカプリン酸とのジエステル、１，４−ビス（２−ヒドロキシエトキシ）ベンゼンとラウリン酸とのジエステル、１，４−ビス（２−ヒドロキシエトキシ）ベンゼンとミリスチン酸とのジエステルを例示できる。 Further, as the component (c), a compound represented by the following general formula (5) can also be used.

(In the formula, R represents an alkyl group or an alkenyl group having 1 to 21 carbon atoms, and n represents an integer of 1 to 3).
Examples of the compound include a diester of 1,3-bis (2-hydroxyethoxy) benzene and capric acid, a diester of 1,3-bis (2-hydroxyethoxy) benzene and undecanoic acid, and 1,3-bis (2). Diester of -hydroxyethoxy) benzene and lauric acid, diester of 1,3-bis (2-hydroxyethoxy) benzene and myristic acid, diester of 1,4-bis (hydroxymethoxy) benzene and butyric acid, 1,4 -Diester of bis (hydroxymethoxy) benzene and isovaleric acid, diester of 1,4-bis (2-hydroxyethoxy) benzene and acetic acid, 1,4-bis (2-hydroxyethoxy) benzene and propionic acid Diester, diester of 1,4-bis (2-hydroxyethoxy) benzene and valerate, diester of 1,4-bis (2-hydroxyethoxy) benzene and caproic acid, 1,4-bis (2-hydroxyethoxy) ) Diester of benzene and capric acid, diester of 1,4-bis (2-hydroxyethoxy) benzene and capric acid, diester of 1,4-bis (2-hydroxyethoxy) benzene and lauric acid, 1,4 An example is an example of a diester of −bis (2-hydroxyethoxy) benzene and myristic acid.

（式中、Ｘは水素原子、炭素数１乃至４のアルキル基、炭素数１乃至４のアルコキシ基、ハロゲン原子のいずれかを示し、ｍは１乃至３の整数を示し、ｎは１乃至２０の整数を示す。）
前記化合物としては、こはく酸と２−フェノキシエタノールとのジエステル、スベリン酸と２−フェノキシエタノールとのジエステル、セバシン酸と２−フェノキシエタノールとのジエステル、１，１０-デカンジカルボン酸と２−フェノキシエタノールとのジエステル、１，１８-オクタデカンジカルボン酸と２−フェノキシエタノールとのジエステルを例示できる。 Further, as the component (c), a compound represented by the following general formula (6) can also be used.

(In the formula, X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, m represents an integer of 1 to 3, and n represents 1 to 20. Indicates an integer of.)
Examples of the compound include a diester of succinic acid and 2-phenoxyethanol, a diester of suberic acid and 2-phenoxyethanol, a diester of sebacic acid and 2-phenoxyethanol, and a diester of 1,10-decandicarboxylic acid and 2-phenoxyethanol. Examples thereof include a diester of 1,18-octadecanedicarboxylic acid and 2-phenoxyethanol.

（式中、Ｒは炭素数４乃至２２のアルキル基、シクロアルキルアルキル基、シクロアルキル基、炭素数４乃至２２のアルケニル基のいずれかを示し、Ｘは水素原子、炭素数１乃至４のアルキル基、炭素数１乃至４のアルコキシ基、ハロゲン原子のいずれかを示し、ｎは０又は１を示す。）
前記化合物としては、４−フェニル安息香酸デシル、４−フェニル安息香酸ラウリル、４−フェニル安息香酸ミリスチル、４−フェニル安息香酸シクロヘキシルエチル、４−ビフェニル酢酸オクチル、４−ビフェニル酢酸ノニル、４−ビフェニル酢酸デシル、４−ビフェニル酢酸ラウリル、４−ビフェニル酢酸ミリスチル、４−ビフェニル酢酸トリデシル、４−ビフェニル酢酸ペンタデシル、４−ビフェニル酢酸セチル、４−ビフェニル酢酸シクロペンチル、４−ビフェニル酢酸シクロヘキシルメチル、４−ビフェニル酢酸ヘキシル、４−ビフェニル酢酸シクロヘキシルメチルを例示できる。 Further, as the component (c), a compound represented by the following general formula (7) can also be used.

(In the formula, R represents any of an alkyl group having 4 to 22 carbon atoms, a cycloalkylalkyl group, a cycloalkyl group, and an alkoxy group having 4 to 22 carbon atoms, and X is a hydrogen atom and an alkyl having 1 to 4 carbon atoms. Indicates a group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and n indicates 0 or 1).
Examples of the compound include decyl 4-phenylbenzoate, lauryl 4-phenylbenzoate, myristyl 4-phenylbenzoate, cyclohexylethyl 4-phenylbenzoate, octyl 4-biphenylacetate, nonyl 4-biphenylacetate, and 4-biphenylacetic acid. Decyl, 4-biphenylacetate lauryl, 4-biphenylacetate myristyl, 4-biphenylacetate tridecyl, 4-biphenylacetate pentadecyl, 4-biphenylacetate cetyl, 4-biphenylacetate cyclopentyl, 4-biphenylacetate cyclohexylmethyl, 4-biphenylacetate hexyl , 4-Cyclohexylmethyl biphenylacetate can be exemplified.

（式中、Ｒは炭素数３乃至１８のアルキル基、炭素数３乃至１８の脂肪族アシル基のいずれかを示し、Ｘは水素原子、炭素数１乃至３のアルキル基、炭素数１又は２のアルコキシ基、ハロゲン原子のいずれかを示し、Ｙは水素原子、メチル基のいずれかを示し、Ｚは水素原子、炭素数１乃至４のアルキル基、炭素数１又は２のアルコキシ基、ハロゲン原子のいずれかを示す。）
前記化合物としては、４−ブトキシ安息香酸フェノキシエチル、４−ペンチルオキシ安息香酸フェノキシエチル、４−テトラデシルオキシ安息香酸フェノキシエチル、４−ヒドロキシ安息香酸フェノキシエチルとドデカン酸とのエステル、バニリン酸フェノキシエチルのドデシルエーテルを例示できる。 Further, as the component (c), a compound represented by the following general formula (8) can also be used.

(In the formula, R represents any of an alkyl group having 3 to 18 carbon atoms and an aliphatic acyl group having 3 to 18 carbon atoms, and X is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and 1 or 2 carbon atoms. Indicates either an alkoxy group or a halogen atom, Y indicates either a hydrogen atom or a methyl group, Z is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 or 2 carbon atoms, or a halogen atom. Indicates one of.)
Examples of the compound include phenoxyethyl 4-butoxybenzoate, phenoxyethyl 4-pentyloxybenzoate, phenoxyethyl 4-tetradecyloxybenzoate, an ester of phenoxyethyl 4-hydroxybenzoate and dodecanoic acid, and phenoxyethyl vanirate. Dodecyl ether can be exemplified.

（式中、Ｒは炭素数４乃至２２のアルキル基、炭素数４乃至２２のアルケニル基、シクロアルキルアルキル基、シクロアルキル基のいずれかを示し、Ｘは水素原子、アルキル基、アルコキシ基、ハロゲン原子のいずれかを示し、Ｙは水素原子、アルキル基、アルコキシ基、ハロゲン原子のいずれかを示し、ｎは０又は１を示す。）
前記化合物としては、ｐ−ヒドロキシ安息香酸オクチルの安息香酸エステル、ｐ−ヒドロキシ安息香酸デシルの安息香酸エステル、ｐ−ヒドロキシ安息香酸ヘプチルのｐ−メトキシ安息香酸エステル、ｐ−ヒドロキシ安息香酸ドデシルのo-メトキシ安息香酸エステル、ｐ−ヒドロキシ安息香酸シクロヘキシルメチルの安息香酸エステルを例示できる。 Further, as the component (c), a compound represented by the following general formula (9) can also be used.

(In the formula, R represents any of an alkyl group having 4 to 22 carbon atoms, an alkenyl group having 4 to 22 carbon atoms, a cycloalkylalkyl group, and a cycloalkyl group, and X is a hydrogen atom, an alkyl group, an alkoxy group, and a halogen. Indicates any of the atoms, Y indicates any of a hydrogen atom, an alkyl group, an alkoxy group, and a halogen atom, and n indicates 0 or 1).
Examples of the compound include benzoic acid ester of octyl p-hydroxybenzoate, benzoic acid ester of decyl p-hydroxybenzoate, p-methoxybenzoic acid ester of heptyl p-hydroxybenzoate, and o-decyl of dodecyl p-hydroxybenzoate. Examples thereof include methoxybenzoic acid ester and benzoic acid ester of cyclomethylmethyl p-hydroxybenzoate.

（式中、（式中、Ｒは炭素数３乃至１８のアルキル基、炭素数６乃至１１のシクロアルキルアルキル基、炭素数５乃至７のシクロアルキル基、炭素数３乃至１８のアルケニル基のいずれかを示し、Ｘは水素原子、炭素数１乃至４のアルキル基、炭素数１乃至３のアルコキシ基、ハロゲン原子のいずれかを示し、Ｙは水素原子、炭素数１乃至４のアルキル基、メトキシ基、エトキシ基、ハロゲン原子のいずれかを示す。）
前記化合物としては、ｐ−ヒドロキシ安息香酸ノニルのフェノキシエチルエーテル、ｐ−ヒドロキシ安息香酸デシルのフェノキシエチルエーテル、ｐ−ヒドロキシ安息香酸ウンデシルのフェノキシエチルエーテル、バニリン酸ドデシルのフェノキシエチルエーテルを例示できる。 Further, as the component (c), a compound represented by the following general formula (10) can also be used.

In the formula, (in the formula, R is any of an alkyl group having 3 to 18 carbon atoms, a cycloalkylalkyl group having 6 to 11 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, and an alkoxy group having 3 to 18 carbon atoms. X indicates a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a halogen atom, and Y indicates a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or methoxy. Indicates a group, an ethoxy group, or a halogen atom.)
Examples of the compound include phenoxyethyl ether of nonyl p-hydroxybenzoate, phenoxyethyl ether of decyl p-hydroxybenzoate, phenoxyethyl ether of undecyl p-hydroxybenzoate, and phenoxyethyl ether of dodecyl vanirate.

（式中、Ｒは炭素数３乃至８のシクロアルキル基又は炭素数４乃至９のシクロアルキルアルキル基を示し、ｎは１乃至３の整数を示す。）
前記化合物としては、１，３−ビス（２−ヒドロキシエトキシ）ベンゼンとシクロヘキサンカルボン酸とのジエステル、１，４−ビス（２−ヒドロキシエトキシ）ベンゼンとシクロヘキサンプロピオン酸とのジエステル、１，３−ビス（２−ヒドロキシエトキシ）ベンゼンとシクロヘキサンプロピオン酸とのジエステルを例示できる。 Further, as the component (c), a compound represented by the following general formula (11) can also be used.

(In the formula, R represents a cycloalkyl group having 3 to 8 carbon atoms or a cycloalkylalkyl group having 4 to 9 carbon atoms, and n represents an integer of 1 to 3).
Examples of the compound include a diester of 1,3-bis (2-hydroxyethoxy) benzene and cyclohexanecarboxylic acid, a diester of 1,4-bis (2-hydroxyethoxy) benzene and cyclohexanepropionic acid, and 1,3-bis. Examples thereof include a diester of (2-hydroxyethoxy) benzene and cyclohexanepropionic acid.

（式中、Ｒは炭素数３乃至１７のアルキル基、炭素数３乃至８のシクロアルキル基、炭素数５乃至８のシクロアルキルアルキル基を示し、Ｘは水素原子、炭素数１乃至５のアルキル基、メトキシ基、エトキシ基、ハロゲン原子を示し、ｎは１乃至３の整数を示す。）
前記化合物としては、４−フェニルフェノールエチレングリコールエーテルとシクロヘキサンカルボン酸とのジエステル、４−フェニルフェノールジエチレングリコールエーテルとラウリン酸とのジエステル、４−フェニルフェノールトリエチレングリコールエーテルとシクロヘキサンカルボン酸とのジエステル、４−フェニルフェノールエチレングリコールエーテルとオクタン酸とのジエステル、４−フェニルフェノールエチレングリコールエーテルとノナン酸とのジエステル、４−フェニルフェノールエチレングリコールエーテルとデカン酸とのジエステル、４−フェニルフェノールエチレングリコールエーテルとミリスチン酸とのジエステルを例示できる。 Further, as the component (c), a compound represented by the following general formula (12) can also be used.

(In the formula, R represents an alkyl group having 3 to 17 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and a cycloalkylalkyl group having 5 to 8 carbon atoms, and X is a hydrogen atom and an alkyl having 1 to 5 carbon atoms. A group, a methoxy group, an ethoxy group, and a halogen atom are indicated, and n represents an integer of 1 to 3).
Examples of the compound include a diester of 4-phenylphenol ethylene glycol ether and cyclohexanecarboxylic acid, a diester of 4-phenylphenol diethylene glycol ether and lauric acid, a diester of 4-phenylphenol triethylene glycol ether and cyclohexanecarboxylic acid, and 4 -Diester of phenylphenol ethylene glycol ether and octanoic acid, diester of 4-phenylphenol ethylene glycol ether and nonanoic acid, diester of 4-phenylphenol ethylene glycol ether and decanoic acid, 4-phenylphenol ethylene glycol ether and myristine Examples thereof include diesters with acids.

The reversible thermochromic composition is a companion containing the components (a), (b), and (c) as essential components, and the ratio of each component is the concentration, discoloration temperature, discoloration form, and type of each component. However, in general, the component ratio at which the desired characteristics are obtained is (a) component 1, (b) component 0.1 to 100, preferably 0.1 to 50, and more preferably 0. It is in the range of 5 to 20, (c) component 5 to 200, preferably 5 to 100, and more preferably 10 to 100 (all of the above ratios are parts by mass).

Further, various light stabilizers can be added as needed.
The light stabilizer is contained in order to prevent photodegradation of the reversible thermochromic composition composed of the components (a), (b) and (c), and is 0.3 with respect to 1% by mass of the component (a). It is contained in an amount of ~ 24% by mass, preferably 0.3 to 16% by mass. Further, among the above-mentioned light stabilizers, the ultraviolet absorber effectively blocks ultraviolet rays contained in sunlight and the like, and prevents photodegradation caused by an excited state due to a photoreaction of the component (a). Further, antioxidants, singlet oxygen quenchers, superoxide anion quenchers, ozone quenchers and the like suppress the oxidation reaction caused by light.
The light stabilizer may be used alone or in combination of two or more.

The reversible thermochromic composition is used as a reversible thermosetting pigment by being dispersed in a thermoplastic resin or a thermosetting resin, or by being encapsulated in microcapsules.
In addition, microencapsulation is conventionally known as an interfacial polymerization method, an in-Situ polymerization method, an in-liquid curing coating method, a phase separation method from an aqueous solution, a phase separation method from an organic solvent, a melting dispersion cooling method, and an air suspension. There are a coating method, a spray drying method, etc., which are appropriately selected according to the application. Further, a secondary resin film may be further provided on the surface of the microcapsules depending on the purpose to impart durability, or the surface characteristics may be modified for practical use.
The microcapsule pigment is preferably in the range of inclusions / wall film = 7/1 to 1/1 (mass ratio), and when the ratio of the wall film is within the above range, the color density at the time of color development and It is possible to prevent a decrease in sharpness, and more preferably, inclusions / wall film = 6/1 to 1/1 (mass ratio).
By encapsulating in the microcapsules, a chemically and physically stable pigment can be formed, and a particle size of 0.1 to 15 μm, preferably 0.5 to 10 μm, more preferably 0.5 to 5 μm is practical. Satisfy sex.
To measure the particle size and average particle size, the particle area is determined using the image analysis type particle size distribution measurement software "MacView" manufactured by Mountech, and the projected area circle equivalent diameter (Heywood) is determined from the area of the particle area. (Diameter) is calculated, and it is a value measured as the particle diameter and the average particle diameter of particles corresponding to equal volume spheres based on the calculated values. When the particle size of all or most of the particles exceeds 0.2 μm, an isovolume sphere is used by the Coulter method using a particle size distribution measuring device (manufactured by Beckman Coulter, Inc., product name: Multisizer 4e). It is also possible to measure as the particle size and average particle size of the corresponding particles.
Furthermore, using a laser diffraction / scattering type particle size distribution measuring device (device name: LA-300, manufactured by Horiba Seisakusho Co., Ltd.) calibrated based on the numerical values measured using the measuring device by the Coulter method, volume-based. The particle size and the average particle size (median size) of the above may be measured.

The discoloration of the reversible thermochromic pigment will be described.
When the reversible thermochromic pigments A and B reach the complete color development temperature (t ₁ ) by lowering the temperature from the decolorized state, they are completely in the color development state, and when the temperature rises from the color development state, they reach the complete decolorization temperature (t ₄ ). It is a pigment that completely fades when it reaches it, and it is preferable that each pigment exhibits a different color.
By having one complete decoloring temperature of the reversible thermochromic pigment A (t ₄₎ from the hot side to the other of the complete decoloring temperature of the reversible thermochromic pigment B (t _4), a plurality of thermochromic at Atsushi Nobori The color change between colors due to the sex pigment can be clearly visually recognized.
The hysteresis characteristics of the reversible thermochromic pigment in the color concentration-temperature curve will be described below with reference to the graph of FIG.
In FIG. 2, the vertical axis represents the color density and the horizontal axis represents the temperature. The change in color density due to temperature change progresses along the arrow. Here, A is a point indicating the concentration at a temperature t ₄ (hereinafter, referred to as a complete decolorization temperature) at which a completely decolorized state is reached, and B is a temperature t ₃ (hereinafter, a decolorization start temperature) at which decolorization begins. It is a point indicating the density at (referred to as), C is a point indicating the density at the temperature t ₂ at which color development starts (hereinafter referred to as the color development start temperature), and D is the temperature t ₁ (hereinafter referred to as) at which the color reaches a completely developed state. , Called the complete color development temperature).
Further, the length of the line segment EF is a measure indicating the contrast of discoloration, and the length of the line segment HG is a temperature width indicating the degree of hysteresis (hereinafter, referred to as a hysteresis width ΔH), and the larger this ΔH value is, the more. , It is easy to maintain each state before and after discoloration.
Here, the difference between t ₄ and t ₃ or the difference between t ₂ and t ₁ (Δt) is a measure of the sensitivity of discoloration.

As an example, to be specifically described by the color density-temperature curve of FIG. 3, the complete decolorization of one reversible thermochromic pigment A is on the higher temperature side than the complete decoloring temperature (t ₄ ) of the other reversible thermochromic pigment B. 'to satisfy ₍₄ [hereinafter, the reversible thermochromic pigment B to be distinguished from the reversible thermochromic pigment a (t temperature _t)' to as)], the reversible thermochromic pigments a, B color developed together When the temperature rises from the colored (1) state, the reversible thermochromic pigment A is decolorized and becomes colored (2) when the temperature reaches the complete decoloring temperature (t ₄ ), and becomes colored (1). The color change of the colored (2) can be clearly visually recognized.
Moreover, upon reaching the temperature of complete decoloring temperature (t _'4) is reversible thermochromic pigment B for decoloring a color change from colored (2) to colorless is visually recognized.
When the temperature reaches the complete color development temperature (t ₁ = t ' ₁ ) due to the temperature decrease, the reversible thermochromic pigment A and the reversible thermochromic pigment B develop color and return to colored (1).
Furthermore, by adding a non-color changing colorant, the color change of colored (1), colored (2), and colored (3) is visually recognized, and the color change of colored (1) and colored (2) is clearly defined. It can be visually recognized.

Further, as another example, specifically described by the color density-temperature curve of FIG. 4, the reversible thermochromic pigment B is completely on the higher temperature side than the complete decoloring temperature (t ₄ ) of one of the reversible thermochromic pigments A. to meet the decoloring temperature (t _'4), a reversible thermochromic pigment a, the B is gradually heated from both the state of the color was colored (1), reach the temperature of the complete decoloring temperature (t ₄₎ Then, the reversible thermochromic pigment A is decolorized and becomes colored (2), and the color change between the colored (1) and the colored (2) can be clearly visually recognized.
Moreover, upon reaching the temperature of complete decoloring temperature (t _'4) is reversible thermochromic pigment B for decoloring a color change from colored (2) to colorless is visually recognized.
When the temperature reaches the perfect color development temperature (t ' ₁ ) by lowering the temperature, the reversible thermochromic pigment B develops color and returns to colored (2), and when the temperature is further lowered to reach the perfect color development temperature (t ₁ ). The reversible thermochromic pigment A develops color and returns to colored (1).
Furthermore, by adding a non-color changing colorant, clear color changes of colored (1), colored (2), and colored (3) are visually recognized, and the color changes of colored (1) and colored (2) are observed. It can be clearly seen.

Further, as another example, specifically described by the color density-temperature curve of FIG. 5, one reversible thermochromic pigment A is on the higher temperature side than the complete decoloring temperature (t ₄ ) of the other reversible thermochromic pigment B. to meet the complete decoloring temperature (t _'4), the temperature of the reversible thermochromic pigment a, the B is gradually heated from the state of the color was colored (1) together, complete decoloring temperature (t ₄₎ When the temperature reaches, the reversible thermochromic pigment A is decolorized and becomes colored (2), and the color change between the colored (1) and the colored (2) can be clearly visually recognized.
Moreover, upon reaching the temperature of complete decoloring temperature (t _'4) is reversible thermochromic pigment B for decoloring a color change from colored (2) to colorless is visually recognized.
When the temperature reaches the perfect color development temperature (t ' ₁ ) by lowering the temperature, the reversible thermochromic pigment B develops color and returns to colored (2), and when the temperature is further lowered to reach the perfect color development temperature (t ₁ ). The reversible thermochromic pigment A develops color and returns to colored (1).
Furthermore, by adding a non-color changing colorant, the color change of colored (1), colored (2), and colored (3) is visually recognized, and the color change of colored (1) and colored (2) is clearly defined. It can be visually recognized.

Further, as another example, specifically described by the color density-temperature curve of FIG. 6, the reversible thermochromic pigment B of one reversible thermochromic pigment A is on the higher temperature side than the complete decoloring temperature (t ₄ ) of the other reversible thermochromic pigment B. to meet the complete decoloring temperature (t _'4), the temperature of the reversible thermochromic pigment a, the B is gradually heated from the state of the color was colored (1) together, complete decoloring temperature (t ₄₎ When the temperature reaches, the reversible thermochromic pigment A is decolorized and becomes colored (2), and the color change between the colored (1) and the colored (2) can be clearly visually recognized.
Moreover, upon reaching the temperature of complete decoloring temperature (t _'4) is reversible thermochromic pigment B for decoloring a color change from colored (2) to colorless is visually recognized.
Note that become colored (3) reaches the temperature thermochromic pigments A and color development of complete coloring temperature (t1) by cooling and further by lowering reaches a temperature of complete coloring temperature (t _'1) reversible The thermochromic pigment B develops color and returns to colored (1).
Further, by adding a non-color-changing colorant, color changes of colored (1), colored (2), colored (3), and colored (4) are visually recognized, and the colored (1) and colored (2) can be visually recognized. The color change is clearly visible.

By having a complete decoloring temperature (t _'4) of the reversible thermochromic pigment B to the high temperature side 10 ° C. or higher than the complete decoloring temperature (t ₄₎ of said reversible thermochromic pigments A, more thermochromic pigments The color change between the colors can be clearly visually recognized, and the temperature is preferably 15 ° C. or higher, more preferably 20 ° C. or higher.
Furthermore, by having a complete decoloring temperature (t _'4) of the reversible thermochromic pigment B to 10 to 70 ° C. higher temperature side than the complete decoloring temperature (t ₄₎ of said reversible thermochromic pigments A, color change Is easily expressed, preferably 15 to 60 ° C., more preferably 20 to 50 ° C.
When the color is changed by the frictional heat generated by the friction body described later, the reversible heat is 15 to 40 ° C., preferably 20 to 35 ° C. higher than the complete decoloring temperature (t ₄ ) of the reversible thermochromic pigment A. by having a complete decoloring temperature (t _'4) of discoloring pigment B, it tends to express the color change in friction heat.
Further, the reversible thermochromic pigment A has a complete decoloring temperature (t ₄ ) of 50 ° C. or higher, preferably 55 ° C. or higher, more preferably 60 ° C. or higher, and a complete color development temperature (t ₁ ) of 0 ° C. or lower, preferably 0 ° C. or higher. Is -5 ° C or lower, more preferably -10 ° C or lower, and the complete color development temperature (t ₁ ) of the reversible thermochromic pigment B is 0 ° C or lower, preferably -5 ° C or lower, more preferably -10 ° C or lower. This makes it easier to maintain the discolored state at room temperature.

Apart from this, by having the complete decolorization temperature (t ₁ ) of the other reversible thermochromic pigment B on the lower temperature side than the complete color development temperature (t ₁ ) of _one reversible thermochromic pigment A, a plurality of reversible thermochromic pigments B are provided at the time of temperature decrease. The color change between colored pigments due to the heat-changing pigment can be clearly visually recognized.
By having the complete color development temperature (t ' ₁ ) of the reversible thermochromic pigment B on the lower temperature side of 10 ° C. or more lower than the complete color development temperature (t ₁ ) of the reversible thermochromic pigment A, the thermochromic pigment is further used. The color change between the colored colors can be clearly visually recognized, and the temperature is preferably 15 ° C. or higher, more preferably 20 ° C. or higher.
Furthermore, by having a complete coloring temperature (t _'1) of the reversible thermochromic pigment B to 10 to 70 ° C. lower temperature side than the complete coloring temperature (t ₁₎ of the reversible thermochromic pigment A, expressing a color change It is easy to heat, preferably 15 to 60 ° C, more preferably 20 to 50 ° C.

Next, an ink composition containing the reversible thermochromic pigment will be described.
The blending ratio of the reversible thermochromic pigment is 10 to 40% by mass, preferably 10 to 35% by mass, and more preferably 10 to 30% by mass with respect to the total amount of the ink composition.
If it is less than 10% by mass, the color development density tends to decrease, and if it exceeds 40% by mass, the dispersion stability becomes poor in the ink composition.

The reversible thermochromic pigments include antioxidants, ultraviolet absorbers, infrared absorbers, dissolution aids, preservatives / fungicides, non-thermally discoloring dyes, pigments, etc., as long as they do not affect their functions. Various additives can be added.

As the medium, water and, if necessary, a water-soluble organic solvent are used.
Examples of the water-soluble organic solvent include glycols such as glycerin, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,3-butylene glycol and ethylene glycol monomethyl ether, and their lower alkyl ethers, 2-pyrrolidone and N-. Examples thereof include vinylpyrrolidone and urea, and examples of the pigment include (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) the electron transfer reaction by the components (a) and (b) at a specific temperature. When a reversible thermochromic microcapsule pigment containing a reversible thermochromic composition comprising a reaction medium that reversibly occurs in the region is used, glycerin and propylene glycol are preferably used as the water-soluble organic solvent.

Examples of the thickener include xanthan gum, welan gum, succinoglycan (average molecular weight of about 1 to 8 million) in which the constituent monosaccharides are organic acid-modified heteropolysaccharides of glucose and galactose, guar gum, locust bean gum and its derivatives, and hydroxy. Polymers with a molecular weight of 100,000 to 150,000 containing ethyl cellulose, alkyl esters of alginate, and alkyl esters of methacrylic acid as main components, and thickening polysaccharides with gelling ability extracted from seaweeds such as glycomannan, agar, and caragenin. Benzilidene sorbitol and benziliden xylitol or derivatives thereof, crosslinkable acrylic acid polymer, inorganic fine particles, polyglycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene lanolin / lanolin alcohol -Examples of nonionic surfactants having an HLB value of 8 to 12, such as beeswax derivatives, polyoxyethylene alkyl ethers, polyoxypropylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, fatty acid amides, and salts of dialkyl or dialkenyl sulfosuccinic acid. It can be used alone or in combination.
And so on.
An alkali-soluble acrylic emulsion is preferably used as the thickener.
When an alkali-soluble acrylic emulsion is used as the thickener, the pH of the ink composition is adjusted to 6 to 11, preferably 7 to 11, and more preferably 7 to 10.

Further, a binder resin can be added for fixing the image and adjusting the viscosity.
The binder resin is selected from resin emulsions, alkali-soluble resins, and water-soluble resins.
Examples of the resin emulsion include polyacrylic acid ester, styrene-acrylic acid copolymer, polyvinyl acetate, ethylene-vinyl acetate copolymer, ethylene-vinyl chloride copolymer, methacrylic acid-maleic acid copolymer, and ethylene-. Examples thereof include aqueous dispersions of methacrylic acid copolymers, α-olefin-maleic acid copolymers, polyesters, polyurethanes and the like, and examples of the alkali-soluble resin include styrene-maleic acid copolymers and ethylene-maleic acid copolymers. , Styrene-acrylic acid copolymer and the like, and examples of the water-soluble resin include polyvinyl alcohol and polyvinyl butyral, and one kind or a mixture of two or more kinds can be used.

In addition, additives such as pH adjusters, preservatives and fungicides can be added as needed.
Examples of the pH adjuster include inorganic salts such as ammonia, sodium carbonate, sodium phosphate, sodium hydroxide and sodium acetate, and organic basic compounds such as water-soluble amine compounds such as triethanolamine and diethanolamine.
Examples of the preservative or fungicide include phenolic acid, a sodium salt of 1,2-benzisothiazolin-3-one, sodium benzoate, sodium dehydroacetate, potassium sorbate, propyl paraoxybenzoate, 2,3,5,6. -Tetrachloro-4- (methylsulfonyl) pyridine and the like can be mentioned.
In addition, a fluorine-based surfactant that improves the permeability of the solvent and a defoaming agent such as nonionic, anionic, cationic surfactant, and dimethylpolysiloxane can also be added.
A non-thermally discoloring dye or pigment is blended in the ink composition, and tautomerizes from colored (1) to colored (2) and from colored (2) to colored (3) by changing the temperature. It can also be configured to form a thermochromic image.

The ink composition preferably has an ink viscosity of 3000 to 10000 mPa · s, more preferably 3500 to 7000 mPa · s, and even more preferably 4000 to 6000 mPa · s, as measured at 25 ° C. using a BL type viscometer at 6 rpm. -S, and the degree of fluctuation (ink viscosity measured at 6 rpm / ink viscosity measured at 60 rpm) is preferably 1.1 to 2.5, more preferably 1.2 to 2.0.
If the ink viscosity is less than 3000 mPa · s, the stamp image formed on the paper surface using the ink composition tends to bleed. If it exceeds 10000 mPa · s, the fluidity of the reversible thermochromic pigment is insufficient in the continuous pores, the smooth flow of the ink composition on the printing surface cannot be ensured, and an unclear printing image is formed by the continuous printing operation. Will be done.
If the degree of fluctuation is less than 1.1, the image formed on the paper surface using the ink composition tends to bleed, and if it exceeds 2.5, the fluidity of the reversible thermochromic pigment is insufficient in continuous pores. , The smooth flow of the ink composition on the stamp surface cannot be ensured, and an unclear stamp image is formed by the continuous stamping operation.

The ink composition is used as an ink composition for a stamp pad and an ink composition for a stamp provided with a stamp material having continuous pores.
The stamp pad is impregnated with the ink composition for a stamp pad to obtain a stamp pad that supplies the ink composition to the stamp surface of the stamp to be contacted, or the ink composition for a stamp provided with a stamp material having continuous pores is continuously pored. A stamp can be obtained by impregnating a stamp material having a stamp material with the stamp material.
A stamp provided with a stamp material having continuous pores is obtained by impregnating a rubber-like elastic body having continuous pores, which is a stamp material, with an ink composition, and when this is pressed against a target surface, the ink composition is targeted from the opening of the continuous pores. It moves to the surface and the surface shape of the stamp is transferred. The portion where transfer is not desired is a recess, or the opening thereof is closed to prevent the ink composition from adhering to the target surface.
It is preferable that the stamp material having continuous pores is housed in the stamp base material so that the stamp surface is exposed, and the exposed surface is provided with a cap to prevent the ink composition from drying or being contaminated by accidental contact when not in use.
An ink storage portion for supplying an ink composition to the stamp material may be provided at the rear portion of the stamp material having continuous pores.

The image formed by the ink composition can be discolored by rubbing with a finger or applying a heating tool or a cooling tool.
Examples of the heating tool include an energization heating discoloring tool equipped with a resistance heating element, a heating discoloring tool filled with hot water, and a hair dryer. However, a friction member is preferably used as a means for discoloring by a simple method. Used.
As the friction member, an elastic body such as an elastomer or a plastic foam, which is rich in elasticity and can generate appropriate friction at the time of rubbing to generate frictional heat, is suitable.
An eraser can be used to rub the image, but since erasing residue is generated during rubbing, the above-mentioned friction member that hardly generates erasing residue is preferably used.
As the material of the friction member, a silicone resin, a SEBS resin (styrene ethylene butylene styrene block copolymer), a polyester resin, a polyester elastomer, or the like is used.
As the friction member, a stamp set can be obtained by combining a stamp and a friction body which is a separate member having an arbitrary shape, but by providing the friction member on the stamp, the stamp becomes excellent in portability.
Examples of the cooling device include a cold discoloring tool using a Peltier element, a cold discoloring tool filled with a refrigerant such as cold water and ice pieces, and an application of a refrigerator or a freezer.

Examples are described below. The part in the embodiment is a mass part.
Example 1
Preparation of reversible thermochromic pigment (a) 9-Ethyl (3-methylbutyl) amino-spiro [12H-benzo (a) xanthen-12,1'(3'H) isobenzofuran] -3'-on 1 as a component Part, 8 parts of bis (3-methyl-4-hydroxyphenyl) sulfide as component (b), 5 parts of 1,1-bis (4'-hydroxyphenyl) hexafluoropropane, 4-benzyl capricate as component (c) A reversible thermochromic composition a composed of 50 parts of oxyphenyl ethyl was encapsulated in microcapsules to prepare a reversible thermochromic pigment A.
The average particle size of the reversible thermochromic pigment A is 2.0 μm, the complete decolorization temperature (t ₄ ) is 64 ° C., the complete color development temperature (t ₁ ) is -14 ° C., and the color changes from pink due to temperature changes. It turns colorless.
(A) Part 1,6-bis (2-ethyloxyphenyl) -4- (4-bis (4-methylphenyl) aminophenyl) pyridine as a component, and 2,2-bis (4') as a component (b) A reversible thermochromic composition b consisting of 5 parts of -hydroxyphenyl) hexafluoropropane and 50 parts of a diester of pimeric acid and 2- (4-benzyloxyphenyl) ethanol as a component (c) is encapsulated in a microcapsule and reversible. A thermochromic pigment B was prepared.
The average particle diameter is 2.0μm in the microcapsules B, complete decoloring temperature (t _'4) is 78 ° C., complete coloring temperature (t' ₁₎ a is -11 ° C., from orange to colorless by a temperature change Discolor.

Preparation of Multicolor Discoloring Ink Composition for Stamps 10.0 parts of the reversible thermochromic pigment A (previously cooled to -14 ° C or lower to develop a pink color), the reversible thermochromic pigment B (previously (Cooled to -11 ° C or lower to develop an orange color) 10.0 parts, glycerin 50.0 parts, alkali-soluble acrylic emulsion [Rome & Haas Japan Co., Ltd., trade name: Primal DR73] 1 .5 parts, triethanolamine 0.9 parts, polyvinylpyrrolidone 50% aqueous solution 10.0 parts, silicon-based defoaming agent 0.2 parts, permeation leveling agent 0.5 parts, preservative 0.2 parts, water 16.7 parts were mixed to obtain a multicolor discolorable ink composition for stamping.

Making stamps (see Fig. 4)
The ink composition was impregnated into the stamp material 2 having continuous pores, fixed to the stamp base material 3 so that the stamp surface of the stamp material was exposed, and the cap 5 was fitted to obtain a stamp.
A friction member 4 made of SEBS resin is provided at the rear end of the stamp base material.
When the stamp was repeatedly pressed against the target surface (paper), the ink composition smoothly flowed out from the stamp surface of the stamp material and moved to the target surface, and a stamp image could be formed.
The image has a vermilion color in which pigment A and pigment B are mixed at room temperature (25 ° C.), and when rubbed with a friction body provided on the stamp base material, pigment A is completely formed at 64 ° C. impression orange by pigment B was decolored (t ₄₎ is clearly visible, further warmed 78 ° C. to become the pigment B colorless completely decolorized (t _'4) to.
The state then cooled becomes -11 ° C. and the pigment B is completely colored (t _'1) and impression orange are visually recognized, further comprising the pigment A is completely colored -14 ℃ (t ₁₎ to , A vermilion image in which pigment A and pigment B were mixed was visually recognized.
The change of state in which the color changes reversibly to colorless, vermilion and orange, can be clearly discriminated, and the visibility of the stepwise color change is excellent.
The stamp is used to form a vermilion "homework" stamp on the notebook, and after the homework is finished, it is rubbed with a friction body to change the color to an orange "homework" stamp, and then rubbed. The image of "homework" could be made colorless, and it was ideal for checking whether the homework was completed, erasing it when it was not needed, and stamping it again.

Example 2
Preparation of reversible thermochromic pigment (a) As a component, 3- (4-diethylamino-2-hexyloxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, (2 parts, ( (B) 8 parts of bis (3-methyl-4-hydroxyphenyl) sulfide as a component, 5 parts of 1,1-bis (4'-hydroxyphenyl) hexafluoropropane as a component, and (c) 4-benzyloxyphenylethyl capricate as a component. A reversible thermochromic composition a composed of 50 parts was encapsulated in microcapsules to prepare a reversible thermochromic pigment A.
The average particle size of the reversible thermochromic pigment A is 2.0 μm, the complete decolorization temperature (t4) is 64 ° C., the complete color development temperature (t1) is -14 ° C., and the color changes from blue to colorless due to a temperature change. To do.
(A) 1.5 parts of 2,6-bis (2-ethyloxyphenyl) -4- (4-dimethylaminophenyl) -pyridine as a component, and 2,2-bis (4'-hydroxyphenyl) as a component (b) ) Hexafluoropropane 5 parts, (c) Reversible thermal discoloration composition b consisting of 50 parts of diester of pimeric acid and 2- (4-benzyloxyphenyl) ethanol as a component is encapsulated in a microcapsule and reversible thermal discoloration. Pigment B was prepared.
The average particle size of the microcapsules B is 2.0 μm, the complete decolorization temperature (t'4) is 78 ° C., the complete color development temperature (t'1) is -11 ° C., and the color changes from yellow to colorless due to temperature changes. Discolor.

Preparation of Multicolor Discoloring Ink Composition for Stamps 10.0 parts of the reversible thermochromic pigment A (previously cooled to -14 ° C or lower to develop a blue color), the reversible thermochromic pigment B (previously-). (Cooled to 11 ° C or lower to develop a yellow color) 10.0 parts, glycerin 50.0 parts, alkali-soluble acrylic emulsion [Rome & Haas Japan Co., Ltd., trade name: Primal DR73] 1. 5 parts, triethanolamine 0.9 parts, polyvinylpyrrolidone 50% aqueous solution 10.0 parts, silicon-based defoaming agent 0.2 parts, permeation leveling agent 0.5 parts, preservative 0.2 parts, water 16 parts .7 parts were mixed to obtain a multicolor discolorable ink composition for stamping.

Making stamps (see Fig. 4)
The ink composition was impregnated into the stamp material 2 having continuous pores, fixed to the stamp base material 3 so that the stamp surface of the stamp material was exposed, and the cap 5 was fitted to obtain a stamp.
A friction member 4 made of SEBS resin is provided at the rear end of the stamp base material.
When the stamp was repeatedly pressed against the target surface (paper), the ink composition smoothly flowed out from the stamp surface of the stamp material and moved to the target surface, and a stamp image could be formed.
The image shows a green color in which pigment A and pigment B are mixed at room temperature (25 ° C.), and when rubbed with a friction body provided on the stamp base material, pigment A is completely formed at 64 ° C. decoloration (t ₄₎ and impressions yellow by pigment B and is clearly visible, further friction to 78 ° C. to become the pigment B is colorless completely decolorized (t _'4) to.
Becomes a cooled to -11 ° C. In this state the pigment B is completely colored (t _'1) to yellow printed images are clearly visible, furthermore, at a -14 ° C. Pigment A completely colored (t ₁ ), And a green image in which the pigment A and the pigment B were mixed was visually recognized.
The state change in which the color changes reversibly to colorless between green and yellow can be clearly discriminated, and the visibility of the stepwise color change is excellent.
The stamp is used to form a green "toothpaste" image on the notebook, and after the toothpaste is finished, it is rubbed with a friction body to change the color to a yellow "toothpaste" image, and then rubbed. The image of "toothpaste" could be made colorless, and it was most suitable for the purpose of checking whether the toothpaste was finished, erasing it when it was not needed, and stamping it again.

Example 3
Preparation of reversible thermochromic pigment (a) Part 3,3-bis (4-diethylamino-2-ethoxyphenyl) -4-azaphthalide as a component (b), 1,1-bis (4'-hydroxyphenyl) as a component (b) ) A reversible thermochromic pigment A was prepared by encapsulating a reversible thermochromic composition a composed of 8 parts of n-decane, 25 parts of myristyl alcohol and 25 parts of butyl stearate as components (c) in a microcapsule.
The average particle size of the reversible thermochromic pigment A is 2.0 μm, the complete decolorization temperature (t4) is 15 ° C., the complete color development temperature (t1) is 7 ° C., and the color changes from blue-green to colorless due to a temperature change. To do.
(A) Part 2,6-bis (2,4-diethyloxyphenyl) -4- (4-diethylaminophenyl) -pyridine as a component, and 1,1-bis (4-hydroxyphenyl) hexa as the component (b) A reversible thermochromic pigment B was prepared by encapsulating a reversible thermochromic composition b consisting of 8 parts of fluoropropane and 50 parts of myristyl myristate as a component (c) in a microcapsule.
The average particle size of the reversible thermochromic pigment B is 2.0 μm, the complete decolorization temperature (t'4) is 40 ° C., and the complete color development temperature (t'1) is 30 ° C. It turns colorless.

Preparation of Multicolor Discoloring Ink Composition for Stamps 10.0 parts of the reversible thermochromic pigment A, 10.0 parts of the reversible thermochromic pigment B, 50.0 parts of glycerin, alkali-soluble acrylic emulsion [Rome &. Haas Japan Co., Ltd., trade name: Primal DR73] 1.5 parts, triethanolamine 0.9 parts, polyvinylpyrrolidone 50% aqueous solution 10.0 parts, silicon-based defoaming agent 0.2 parts, penetration leveling agent 0.5 part, 0.2 part of preservative and 16.7 parts of water were mixed to obtain a multicolor discolorable ink composition for stamping.

Preparation of Stamp The ink composition was impregnated into a stamp material 2 having continuous pores, fixed to a stamp base material so that the stamp surface of the stamp material was exposed, and a cap was fitted to obtain a stamp.
When the stamp was repeatedly pressed against the target surface (paper), the ink composition smoothly flowed out from the stamp surface of the stamp material and moved to the target surface, and a stamp image could be formed.
The impression has a yellow color due to the pigment B at room temperature (25 ° C.), heated rubbed with a finger from the state becomes 40 ° C. When the pigment B is completely decolored (t _'4) to It became colorless and the imprint was no longer visible.
If left at room temperature (25 ° C.) In this state, when the temperature becomes to 30 ° C. descending pigment B is completely colored (t _'1) to again clear yellow printed images were revealing.
Further, the image was left in the refrigerator (5 ° C.) for a while, and when the temperature reached 7 ° C., the pigment A was completely colored (t ₁ ), and the blue-green color of the pigment A and the yellow color of the pigment B were mixed. A yellow-green image was visually recognized.
The state change of reversibly changing to yellow, colorless, and yellowish green could be clearly discriminated, and the visibility of the stepwise color change was excellent.
A yellow floral stamp is formed using the stamp, and when heated by rubbing with a finger, the stamp disappears, and the yellow stamp appears again at room temperature (25 ° C.), and further stamped. The image could be cooled into a yellow-green image, which was ideal for magic applications.

Example 4
(A) 1 part of 3,3-bis (4-diethylamino-2-ethoxyphenyl) -4-azaphthalide as a component, (b) 8 parts of 1,1-bis (4'-hydroxyphenyl) n-decane as a component, A reversible thermochromic pigment A was prepared by encapsulating a reversible thermochromic composition a composed of 50 parts of myristyl myristate as a component (c) in microcapsules.
The average particle size of the reversible thermochromic pigment A is 2.0 μm, the complete decolorization temperature (t'4) is 40 ° C., the complete color development temperature (t'1) is 30 ° C. Discolors from to colorless.
(A) As a component, 2- (di-n-butylamino) -8- (di-n-amylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidin-5,1 ′ (3'H) -isobenzofuran] -3'-one 1 part, (b) component 1,1-bis (4-hydroxyphenyl) hexafluoropropane 8 parts, (c) component stearyl stearate 50 parts The reversible thermochromic composition b composed of the above was encapsulated in microcapsules to prepare a reversible thermochromic pigment B.
The average particle size of the reversible thermochromic pigment B is 2.0 μm, the complete decolorization temperature (t4) is 58 ° C., the complete color development temperature (t1) is 43 ° C., and the color changes from pink to colorless due to a temperature change. To do.

Preparation of Multicolor Discoloring Ink Composition for Stamps 10.0 parts of the reversible thermochromic pigment A, 10.0 parts of the reversible thermochromic pigment B, 50.0 parts of glycerin, alkali-soluble acrylic emulsion [Rome &. Haas Japan Co., Ltd., trade name: Primal DR73] 1.5 parts, triethanolamine 0.9 parts, polyvinylpyrrolidone 50% aqueous solution 10.0 parts, silicon-based defoaming agent 0.2 parts, penetration leveling agent 0.5 part, 0.2 part of preservative and 16.7 parts of water were mixed to obtain a multicolor discolorable ink composition for stamping.

Making stamps (see Fig. 4)
The ink composition was impregnated into the stamp material 2 having continuous pores, fixed to the stamp base material 3 so that the stamp surface of the stamp material was exposed, and the cap 5 was fitted to obtain a stamp.
A friction member 4 made of SEBS resin is provided at the rear end of the stamp base material.
When the stamp was repeatedly pressed against the target surface (paper), the ink composition smoothly flowed out from the stamp surface of the stamp material and moved to the target surface, and a stamp image could be formed.
The image is purple at room temperature (25 ° C.), and when heated by rubbing with a rubbing body from this state, the pigment A completely decolorizes (t ₄ ) at 40 ° C. and the pigment B by the pink impression is clearly visible, yet the temperature is to 58 ° C. increase pigment B is completely decolored (t _'4) to, impression will not be visible.
Thereafter, upon cooling, the temperature is then colored to 43 to become the pigment B is completely ° C. descent (t _'1) is visually recognized clearly are pink impressions, further comprising a 30 ° C. When the pigment A is completely colored At (t ₁ ), a purple image in which the bluish green of the pigment A and the pink of the pigment B were mixed was visually recognized.
The state change in which the color changes reversibly to colorless from purple and pink can be clearly discriminated, and the visibility of the stepwise color change is excellent.
The stamp can be used to form a purple image, which becomes pink when heated, becomes colorless when further heated, and can be changed from pink to yellow-green when left unattended, for magic purposes. It was optimal.

Example 5
Preparation of reversible thermochromic pigment (a) As a component, 3- (4-diethylamino-2-hexyloxyphenyl) -3- (1-ethyl-2-methylindole-3-yl) -4-azaphthalide, (2 parts, ( B) 8 parts of bis (3-methyl-4-hydroxyphenyl) sulfide, 5 parts of 1,1-bis (4'-hydroxyphenyl) hexafluoropropane as components, and 50 parts of 4-methylbenzyl palmitate as (c) components. A reversible thermochromic pigment A was prepared by encapsulating a reversible thermochromic composition comprising the same in microcapsules.
The average particle size of the reversible thermochromic pigment A is 2.0 μm, the complete decolorization temperature (t4) is 43 ° C., the complete color development temperature (t1) is -3 ° C., and the color changes from blue to colorless due to a temperature change. To do.
(A) Part 2,6-bis (2-ethyloxyphenyl) -4- (4-dimethylaminophenyl) -pyridine as a component, and 1,1-bis (4-hydroxyphenyl) hexafluoro as a component (b) A reversible thermochromic pigment B is prepared by encapsulating a reversible thermochromic composition consisting of 5 parts of propane and 50 parts of a diester of pimeric acid and 2- (4-benzyloxyphenyl) ethanol as a component (c) in a microcapsule. did.
The average particle size of the microcapsules B is 2.0 μm, the complete decolorization temperature (t4) is 78 ° C., the complete color development temperature (t1) is −11 ° C., and the color changes from yellow to colorless due to a temperature change.

Preparation of Multicolor Discoloring Ink Composition for Stamps 10.0 parts of the reversible thermochromic pigment A (previously cooled to -3 ° C or lower to develop a blue color), and the reversible thermochromic pigment B (previously- (Cooled to 11 ° C or lower to develop a yellow color) 10.0 parts, glycerin 50.0 parts, alkali-soluble acrylic emulsion [Rome & Haas Japan Co., Ltd., trade name: Primal DR73] 1. 5 parts, triethanolamine 0.9 parts, polyvinylpyrrolidone 50% aqueous solution 10.0 parts, silicon-based defoaming agent 0.2 parts, permeation leveling agent 0.5 parts, preservative 0.2 parts, water 16 parts .7 parts were mixed to obtain a multicolor discolorable ink composition for stamping.

Making stamps (see Fig. 4)
The ink composition was impregnated into the stamp material 2 having continuous pores, fixed to the stamp base material 3 so that the stamp surface of the stamp material was exposed, and the cap 5 was fitted to obtain a stamp.
A friction member 4 made of SEBS resin is provided at the rear end of the stamp base material.
When the stamp was repeatedly pressed against the target surface (paper), the ink composition smoothly flowed out from the stamp surface of the stamp material and moved to the target surface, and a stamp image could be formed.
The image formed from the stamp is green at room temperature (25 ° C.), and when rubbed with a friction body provided on the stamp base material, the pigment A is completely decolorized (t _{4) at} 43 ° C. ) that impressions yellow due pigment B is clearly visible, further friction and temperature is to 78 ° C. increases the pigment B is completely decolored (t _'4) to become colorless.
When cooled from this state to -3 ° C, the pigment A completely develops color (t ₁ ), a clear blue image is visually recognized, and when the temperature further decreases to -11 ° C, the pigment B is completely colored. color (t _'1) to become the original green impression.
The change of state in which the color changes reversibly to colorless, such as green, yellow, and blue, can be clearly discriminated, and the visibility of the stepwise color change is excellent.
The stamp can be used to form a green image on the notebook, and the important image can be rubbed with a friction body to change the color to a yellow image. In addition, if it was mistakenly turned yellow, the image could be made colorless by rubbing and stamped again, which was ideal for identifying important points.
Furthermore, an important image can be subdivided by changing the color of the image to blue using a cooling tool.

Example 6
Preparation of reversible thermochromic pigment (a) 2- (di-n-butylamino) -8- (di-n-amylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-) as a component g) Pyrimidine-5,1'(3'H) -isobenzofuran] -3'-one 1 part, (b) component 1,1-bis (4-hydroxyphenyl) hexafluoropropane 5 parts, (c) A reversible thermochromic pigment A was prepared by encapsulating a reversible thermochromic composition consisting of 50 parts of 4-methylbenzyl palmitate as a component in microcapsules.
The average particle size of the reversible thermochromic pigment A is 2.0 μm, the complete decolorization temperature (t4) is 43 ° C., the complete color development temperature (t1) is -3 ° C., and the color changes from pink to colorless due to temperature changes. Discolor.
(A) Part 1,6-bis (2,4-diethyloxyphenyl) -4- (4-bis (4-methylphenyl) aminophenyl) pyridine as a component, and 2,2-bis (b) as a component. A reversible thermochromic composition consisting of 8 parts of 4'-hydroxyphenyl) hexafluoropropane and 50 parts of a diester of pimelic acid and 2- (4-benzyloxyphenyl) ethanol as a component (c) is encapsulated in a microcapsule. A reversible thermochromic pigment B was prepared.
The average particle size of the microcapsules B is 2.0 μm, the complete decolorization temperature (t4) is 78 ° C., the complete color development temperature (t1) is −11 ° C., and the color changes from orange to colorless due to a temperature change.

Preparation of Multicolor Discoloring Ink Composition for Stamps 10.0 parts of the reversible thermochromic pigment A (previously cooled to -3 ° C or lower to develop a pink color), the reversible thermochromic pigment B (previously) (Cooled to -11 ° C or lower to develop an orange color) 10.0 parts, glycerin 50.0 parts, alkali-soluble acrylic emulsion [Rome & Haas Japan Co., Ltd., trade name: Primal DR73] 1 .5 parts, triethanolamine 0.9 parts, polyvinylpyrrolidone 50% aqueous solution 10.0 parts, silicon-based defoaming agent 0.2 parts, permeation leveling agent 0.5 parts, preservative 0.2 parts, water 16.7 parts were mixed to obtain a multicolor discolorable ink composition for stamping.

Making stamps (see Fig. 4)
The ink composition was impregnated into the stamp material 2 having continuous pores, fixed to the stamp base material 3 so that the stamp surface of the stamp material was exposed, and the cap 5 was fitted to obtain a stamp.
A friction member 4 made of SEBS resin is provided at the rear end of the stamp base material.
When the stamp was repeatedly pressed against the target surface (paper), the ink composition smoothly flowed out from the stamp surface of the stamp material and moved to the target surface, and a stamp image could be formed.
The image formed from the stamp is vermilion at room temperature (25 ° C.), and when rubbed with a friction body provided on the stamp base material, the pigment A is completely decolorized (t _{4) at} 43 ° C. ) that impressions orange due pigment B is clearly visible, further friction and temperature is to 78 ° C. increases the pigment B is completely decolored (t _'4) to become colorless.
When cooled from this state to -3 ° C, the pigment A completely develops color (t ₁ ), a clear pink image is visually recognized, and when the temperature further decreases to -11 ° C, the pigment B is completely colored. coloring (t _'1) were made to the original vermilion mark image to.
The change of state in which the color changes reversibly to be colorless, such as vermilion, orange, and pink, can be clearly discriminated, and the visibility of the stepwise color change is excellent.
It should be noted that the stamp can be used to form a vermilion image on the characters of a textbook, and the image can be rubbed with a friction body to change the color to an orange image, and then rubbed to make the image colorless. It was most suitable for the purpose of checking the part to be memorized (vermilion) and the part to be memorized (orange), erasing it when it is not needed, and stamping it again.
Further, by changing the color of the stamp image to pink using a cooling tool, it is possible to reliably distinguish the part to be memorized.

Example 7
Preparation of reversible thermochromic pigment (a) Part 3,3-bis (4-diethylamino-2-ethoxyphenyl) -4-azaphthalide as a component, and 1,1-bis (4'-hydroxyphenyl) as a component (b) ) A reversible thermochromic pigment A was prepared by encapsulating a reversible thermochromic composition consisting of 5 parts of n-decane and 50 parts of 4-methylbenzyl palmitate as a component (c) in microcapsules.
The average particle size of the reversible thermochromic pigment A is 2.0 μm, the complete decolorization temperature (t4) is 43 ° C., the complete color development temperature (t1) is -3 ° C., and the temperature changes from blue-green to colorless. Discolor.
(A) As a component, 2- (di-n-butylamino) -8- (di-n-amylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 ′ (3 ′ H) -isobenzofuran] -3 ′-one part, (b) component 1,1-bis (4-hydroxyphenyl) hexafluoropropane 5 part, (c) component pyrimidine and 2- A reversible thermochromic pigment B was prepared by encapsulating a reversible thermochromic composition consisting of 50 parts of a diester with (4-benzyloxyphenyl) ethanol in a microcapsule.
The average particle size of the microcapsules B is 2.0 μm, the complete decolorization temperature (t4) is 78 ° C., the complete color development temperature (t1) is −11 ° C., and the color changes from pink to colorless due to a temperature change.

Preparation of Multicolor Discoloring Ink Composition for Stamps 10.0 parts of the reversible thermochromic pigment A (previously cooled to -3 ° C or lower to develop a blue-green color), the reversible thermochromic pigment B (previously 10.0 parts of yellow dye (manufactured by Daiwa Kasei Co., Ltd., Kinolin Yellow WS300, C.I.), cooled to -11 ° C or lower to develop a pink color. I. 47005] 0.5 part, glycerin 50.0 part, alkali-soluble acrylic emulsion [Rome & Haas Japan Co., Ltd., trade name: Primal DR73] 1.5 part, triethanolamine 0.9 part, polyvinyl Multicolor discoloration for stamps by mixing 10.0 parts of 50% pyrrolidone aqueous solution, 0.2 parts of silicon defoamer, 0.5 part of permeation leveling agent, 0.2 parts of preservative, and 16.2 parts of water. A sex ink composition was obtained.

Making stamps (see Fig. 4)
The ink composition was impregnated into the stamp material 2 having continuous pores, fixed to the stamp base material 3 so that the stamp surface of the stamp material was exposed, and the cap 5 was fitted to obtain a stamp.
A friction member 4 made of SEBS resin is provided at the rear end of the stamp base material.
When the stamp was repeatedly pressed against the target surface (paper), the ink composition smoothly flowed out from the stamp surface of the stamp material and moved to the target surface, and a stamp image could be formed.
The image formed from the stamp is brown at room temperature (25 ° C.), and when rubbed with a friction body provided on the stamp substrate, the pigment A is completely decolorized (t _{4) at} 43 ° C. ) that is visually recognized clearly are vermilion impression by pigment B and the yellow dye, the yellow and further friction and temperature is to 78 ° C. increases the pigment B is completely decolored (t _'4) ..
When cooled from this state to -3 ° C, the pigment A completely develops color (t ₁ ), a clear yellow-green image is visually recognized, and when the temperature further decreases to -11 ° C, the pigment B is completely colored. and coloring (t _'1) to become impression of the original brown.
The state change that reversibly changes to purple, brown, vermilion, yellow, and yellow-green can be clearly discriminated, and the visibility of the stepwise color change is excellent.
The stamp can be used to form a purple picture (imprint), which can be rubbed with a friction body to turn it into an orange picture, and then rubbed to make the picture yellow, making it ideal for message cards. Met.
Furthermore, it was possible to change the color of the picture to yellowish green using a cooling tool, and it was possible to obtain a highly variable message card.

t ₁ complete color development temperature t ₂ color development start temperature t ₃ decolorization start temperature t ₄ complete decolorization temperature ΔH hysteresis width 1 stamp 2 stamp material 3 stamp base material 4 friction member 5 cap

Claims (6)

A reaction medium that reversibly causes an electron transfer reaction between (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) the above-mentioned (a) and (b) components in a specific temperature range. A reversible thermochromic pigment A containing a reversible thermochromic composition a, (a) an electron-donating color-developing organic compound, (b) an electron-accepting compound, and (c) the above (a). , (B) A reversible thermochromic pigment B containing a reversible thermochromic composition b composed of a reaction medium that reversibly causes an electron transfer reaction by a component in a specific temperature range, and a medium, the reversible heat. The discoloring pigments A and B are completely in the decolorized state when the temperature drops from the decolorized state and reach the complete decolorization temperature (t ₁ ), and are completely decolorized when the temperature rises from the decolorized state reaches the complete decolorization temperature (t ₄ ). to a pigment comprising a decolorized state, it has a complete decoloring temperature (t ₄₎ of the reversible thermochromic pigment B to the high temperature side than the complete decoloring temperature of the reversible thermochromic pigment a (t _4), or reversible complete coloring temperature (t ₁₎ than the stamp polychromatic color change ink composition having a complete coloring temperature (t ₁₎ of the reversible thermochromic pigment B in the low temperature side of the thermochromic pigment a. The multicolor discolorable ink composition for stamps according to claim 1, wherein the reversible thermochromic pigment B has a complete decolorization temperature of 10 ° C. or more higher than the complete decolorization temperature of the reversible thermochromic pigment A. The multicolor discolorable ink composition for stamps according to claim 2, wherein the reversible thermochromic pigment B has a complete decolorization temperature of 10 to 70 ° C. higher than the complete decolorization temperature of the reversible thermochromic pigment A. Claims 1 to 3 in which the complete decolorization temperature of the reversible thermochromic pigment A is 50 ° C. or higher, the complete color development temperature is 0 ° C. or lower, and the complete color development temperature of the reversible thermochromic pigment B is 0 ° C. or lower. The multicolor discolorable ink composition for stamps according to any one of the above. A stamp comprising a stamp material having continuous pores, and the stamp material is impregnated with the ink composition for a reversible thermochromic stamp according to any one of claims 1 to 4. The stamp according to claim 5, which comprises a friction body.

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