JP2021188049A - Aqueous ink composition for ball-point pen and ball-point pen therewith - Google Patents

Abstract

To provide an aqueous ink composition for ball-point pen which is aqueous ink using microcapsule pigment as colorant, is superior in dry up control under room temperature and can form clear handwriting on paper, and to provide a ball-point pen including the composition.SOLUTION: An aqueous ink composition for ball-point pen contains microcapsule pigment including a wall film consisting of polymers, polyurethane emulsion having the minimum film-forming temperature of higher than 20°C, shear decrease viscosity grant agent and water. The polymer has at least one of urea-binding or urethane-binding in a repeat unit. A glass transition temperature of the polyurethane is 10-90°C. A ball-point pen includes the aqueous ink composition for ball-point pen.SELECTED DRAWING: Figure 2

Description

The present invention relates to a water-based ink composition for a ballpoint pen containing a microcapsule pigment and a ballpoint pen containing the composition.

Conventionally, a water-based ink composition for a ballpoint pen using a microcapsule pigment (heat discolorable microcapsule pigment) containing a heat discolorable composition has been known. Since the microcapsule pigment is a pigment that easily precipitates or floats in the ink to cause ink separation, studies have been conducted to improve the dispersion stability of the microcapsule pigment in the ink. (See, for example, Patent Document 1)

Patent Document 1 describes a water-based ink for a ballpoint pen containing a heat-discolorable microcapsule pigment and a shear thinning substance (shear thinning agent).
This ink is said to have good dispersion stability of the microcapsule pigment when the ink is allowed to stand by a shear reducing viscosity imparting agent, and further, when a strong shearing force is applied from the ball to the ink during writing, the ink has a low viscosity. The ink is easily ejected from the pen tip and exhibits excellent writing feeling and writing ability. Therefore, the ink has both dispersion stability and writing performance of the microcapsule pigment.

However, when the ballpoint pen containing the ink of the prior art is stored at room temperature in a room with the pen tip exposed, water evaporates at the pen tip to impart agglomerates of microcapsule pigments and shear de-viscosity. Since a strong film is formed by the agent, rewriting tends to be difficult (the ballpoint pen dries up).
Further, in the ink of the prior art, the dispersion stability of the microcapsule pigment is restored together with the ink viscosity after being ejected onto the paper surface, but a part of the microcapsule pigment permeates the inside of the paper by the time the ink viscosity is restored. Since it did not stay on the surface of the paper, it was sometimes difficult to make the brush strokes clear.

Japanese Unexamined Patent Publication No. 09-124993

The present invention has been made in view of the above-mentioned drawbacks of the prior art. A water-based ink composition for a ballpoint pen capable of forming a handwriting, and a ballpoint pen containing the composition are provided.

The present invention
"1. An ink composition containing a microcapsule pigment having a wall film made of a polymer, a polyurethane emulsion having a minimum film forming temperature of more than 20 ° C., a shear reducing viscosity imparting agent, and water, wherein the polymer has a urea bond. Alternatively, a water-based ink composition for a ball pen, which has at least one of urethane bonds in a repeating unit and has a glass transition temperature of the polyurethane of 10 to 90 ° C.
2. 2. The microcapsule pigment comprises (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. The water-based ink composition according to Item 1, which is a thermochromic microcapsule pigment containing a sex composition.
3. The water-based ink composition according to item 1 or 2, wherein the minimum film forming temperature of the polyurethane emulsion is 90 ° C. or lower.
4. The water-based ink composition according to item 1 or 2, wherein the polyurethane has a glass transition temperature of 20 to 90 ° C.
5. A ballpoint pen containing the water-based ink composition according to any one of items 1 to 4. ".

According to the present invention, a water-based ink using a microcapsule pigment as a coloring material, an water-based ink composition for a ballpoint pen, which is excellent in suppressing dry-up at room temperature and can form a clear handwriting on a paper surface, and the like. A ballpoint pen containing the ink is provided.
Further, in the case of the thermochromic microcapsule pigment in which the microcapsule pigment contains a thermochromic composition, the handwriting formed on the paper surface is excellent in color change responsiveness.

It is explanatory drawing which shows the discoloration behavior of the microcapsule pigment (heat decolorization type) containing a reversible thermochromic composition. It is explanatory drawing which shows the discoloration behavior of the microcapsule pigment (heat decolorization type) containing another reversible thermochromic composition.

Hereinafter, embodiments of the present invention will be described in detail. In addition, in this specification, "part", "%", "ratio", etc. indicating a composition are based on mass unless otherwise specified.
Further, the indoor room temperature in the present invention means 20 ° C.

The water-based ink composition for a ballpoint pen according to the present invention (hereinafter, may be referred to as "water-based ink composition", "ink composition" or "composition") is a microcapsule pigment, a polyurethane emulsion and a shear reduction. It contains a viscosity-imparting agent and water. Hereinafter, each component constituting the ink composition according to the present invention will be described.

(Microcapsule pigment)
The microcapsule pigment has a wall film made of a polymer and can contain conventionally known dyes and pigments. As the dye, an acidic dye, a basic dye, a direct dye, a reactive dye, a bat dye, a sulfur dye, a gold-containing dye, a cationic dye, a disperse dye and the like can be used, and as a pigment, an inorganic pigment and an organic pigment can be used. can. More specifically, the pigments include carbon black, titanium oxide, zinc oxide, iron black, yellow iron oxide, petals, metal oxides such as composite oxide pigments, and ultramarine. Organic pigments include azo pigments, indigo pigments, phthalocyanine pigments, quinacridone pigments, thioindigo pigments, slen pigments, perinone pigments, perylene pigments, phthalone pigments, dioxane pigments, isoindolinone pigments, Examples thereof include metal complex pigments, methine / azomethine pigments, and diketopyrrolopyrrole pigments.
Further, metal powder pigments made of aluminum, brass and the like, resin-coated flaky metal pigments, pigments obtained by coating a transparent base material with a metal oxide, cholesteric liquid crystal type metallic gloss pigments and the like can also be applied. ..

Further, the microcapsule pigment may be a thermochromic microcapsule pigment containing a thermochromic composition. The thermochromic composition includes (a) an electron-donating color-developing organic compound, (b) an electron-accepting compound, and (c) a reversible thermochromic composition consisting of a reaction medium that determines the temperature at which the color reaction of both of them occurs. The thing is preferably used.

As the thermochromic microcapsule pigment, those described in Japanese Patent Publication No. 51-44706, Japanese Patent Publication No. 51-44707, Japanese Patent Publication No. 1-2398, and the like can be used. These microcapsule pigments change color before and after a predetermined temperature (discoloration point), and exhibit a decolorized state in a temperature range above the high temperature side discoloration point and a color development state in a temperature range below the low temperature side discoloration point. Is. Then, of the above two states, only one specific state exists in the normal temperature range, and the other state is maintained as long as the heat or cold required for the state to appear is applied. It has the characteristic that it returns to the state exhibited in the normal temperature range when the application of heat or cold heat is eliminated. Here, the composition contained in these microcapsule pigments is a heat decolorizing type (ΔH = 1 to 7 ° C.) having a characteristic (ΔH = 1 to 7 ° C.) in which the temperature range indicating the degree of hysteresis (hereinafter referred to as hysteresis width ΔH) is relatively small. It is a reversible thermochromic composition (see FIG. 1) that decolorizes by heating and develops color by cooling).

Further, the thermochromic microcapsule pigments described in JP-A-4-17154, JP-A-7-179777, JP-A-7-33997, JP-A-8-39936 and the like can also be used. .. These microcapsule pigments exhibit relatively large hysteresis characteristics (ΔH = 8 to 50 ° C.). That is, the shape of the curve plotting the change in coloring density due to the temperature change is significantly different between the case where the temperature is raised from the low temperature side of the discoloration temperature range and the case where the temperature is lowered from the high temperature side of the discoloration temperature range. The color changes along the route (see Fig. 2).

The hysteresis characteristics in the color concentration-temperature curve of the reversible thermochromic composition will be described in detail with reference to the figure as follows.

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 the temperature t 4} (hereinafter referred to as the complete decolorization temperature) at which the complete decolorization state is reached _{, and B is the temperature t 3} (hereinafter referred to as the decolorization start temperature) at which the decolorization starts. It is a point indicating the density at (referred to as), C is a point indicating the density at the temperature t ₂ (hereinafter referred to as the color development start temperature) at which color development is started, and D is the temperature t ₁ (hereinafter referred to as complete) at which the color development state is reached. It is a point indicating the density at the color development temperature).

The color change temperature range is _{a temperature range between t 1} and t ₄ , and can exhibit either a colored state or a decolorized state, and is a region between _{t 2} and t _{3 in which the difference in color density is large.} The temperature range is a substantially two-phase holding temperature range.

Further, the length of the line segment EF is a measure showing the contrast of discoloration, and the length of the line segment HG passing through the midpoint of the line segment EF is the hysteresis width ΔH. Of these, only one specific state can exist in the normal temperature range. Further, when the ΔH value is large, it becomes easy to maintain each state before and after discoloration.

Specifically, as a reversible thermochromic composition having color memory, a temperature at which a complete color development temperature t ₁ can be obtained only in a freezer, a cold region, or the like, that is, -50 to 0 ° C., preferably -40 to -5. ° C., more preferably -30 to-10 ° C., and complete decoloring temperature _{t 4} the frictional heat generated by friction body, the temperature obtained from the hair dryer familiar heating body, i.e. 45 to 95 ° C., preferably 50 to 90 By specifying the temperature in the range of ° C., more preferably 60 to 80 ° C., and specifying the ΔH value in the range of 40 to 100 ° C., it is possible to effectively function to maintain the color exhibited in the normal state (daily living temperature range).

The compounds are specifically exemplified below for each of the components (a), (b), and (c).

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 a phthalide compound, a fluorine compound, a stirinoquinoline compound, a diazarodamine lactone compound, a pyridine compound, a quinazoline compound, a bisquinazoline compound and the like, and among these, the phthalide compound and the fluorine compound are preferable. ..

Examples of the phthalide compound include diphenylmethanephthalide compound, phenylindrill phthalide compound, indolylphthalide compound, diphenylmethane azaphthalide compound, phenylindolyl azaphthalide compound, and derivatives thereof. , Phenylindrill azaphthalide compounds, as well as derivatives thereof.
In addition, examples of the fluorin compound include an aminofluorane compound, an alkoxyfluorane compound, and a derivative thereof.

The compounds that can be used for the component (a) are illustrated 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-dimethoxyfluoran,
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-dodecoxystylyl) 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) -8- -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]

As the fluorans, in addition to the compound having a substituent on the phenyl group forming the xanthene ring, the phenyl group having the substituent on the phenyl group forming the xanthene ring and the phenyl group forming the lactone ring also has a substituent (for example,). It may be a compound exhibiting a blue color or a black color having an alkyl group such as a methyl group and a halogen atom such as a chloro group).

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 has 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 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, 2-hydroxycarboxylic acid derivatives, N-substituted amino acid derivatives, acidic phosphate esters and their derivatives, azol compounds and their derivatives, 1,2,3-triazole and its derivatives, cyclic carbosulfoimides, carbon Examples thereof include halohydrins having a number of 2 to 5, sulfonic acids and derivatives thereof, and inorganic acids.

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, and the aromatic carboxylic acid anhydride. Aliper carboxylic acid anhydrides, anhydrous mixed acids of aromatic carboxylic acids and sulfonic acids, cycloolefin dicarboxylic acid anhydrides, urea and its derivatives, thiourea and its derivatives, guanidine and its derivatives, halogenated alcohols, etc. Can be mentioned.

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 compound having a phenolic hydroxyl group is widely included from a monophenol compound to a polyphenol compound, and further includes bis-type, tris-type phenol and the like, and a phenol-aldehyde condensed resin 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 carboxy group, and an ester or amide group thereof, a halogen group and the like.

Examples of the metal contained in the metal salt of 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.

As a compound having one phenolic hydroxyl group,
Phenol,
o-cresol,
m-cresol,
p-cresol,
4-Ethylphenol,
4-n-propylphenol,
4-n-butylphenol,
2-tert-butylphenol,
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,
4,4'-Dihydroxybenzophenone,
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, thymol,
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-benzoxathiol-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-benzylbenzotriazole,
1-Hydroxy-5-ethylbenzotriazole,
1-Hydroxy-5-n-octylbenzotriazole,
1-Hydroxy-5-n-butylbenzotriazole,
4-Hydroxybenzoate n-butyl,
4-Hydroxybenzoate n-octyl,
4-Hydroxybenzoate 2-heptadecafluorooctylethane,
Benzyl 4-hydroxybenzoate,
4-Hydroxybenzoate benzyl ester,
4-Hydroxybenzoate-o-methylbenzyl,
4-Hydroxybenzoate-m-methylbenzyl,
4-Hydroxybenzoate-p-methylbenzyl,
4-Hydroxybenzoate-p-ethylbenzyl,
4-Hydroxybenzoate-p-propylbenzyl,
4-Hydroxybenzoic acid-p-tert-butylbenzyl,
Phenylethyl 4-hydroxybenzoate,
4-Hydroxybenzoate-o-methylphenylethyl,
4-Hydroxybenzoate-m-methylphenylethyl,
4-Hydroxybenzoate-p-methylphenylethyl,
4-Hydroxybenzoate-p-ethylphenylethyl,
4-Hydroxybenzoate-p-propylphenylethyl,
Examples thereof include 4-hydroxybenzoic acid-p-tert-butylphenylethyl.

Examples of the compound having two phenolic hydroxyl groups include resorcin.
2-Methylresorcin,
4-n-hexyl resorcin,
4-n-octylresorcin,
4-tert-octylresorcin,
4-Benzoyl resorcin,
4-Nitroresorcin,
Methyl β-resorcinol,
Benzyl β-resorcinate,
2-Chloro-4-pentanoylresorcin,
6-Chloro-4-pentanoylresorcin,
2-Chloro-4-hexanoylresorcin,
6-Chloro-4-hexanoylresorcin,
2-Chloro-4-propanoylresorcin,
6-Chloro-4-propanoylresorcin,
2,6-Dichloro-4-propanoylresorcin,
6-Fluoro-4-propanoylresorcin,
2-Chloro-4-phenylacetylresorcin,
4-Phenylacetyl-6-chlororesorcin,
2-Chloro-4-β-Phenylpropanoid Resorcin,
6-Chloro-4-β-Phenylpropanoid Resorcin,
2-Chloro-4-phenoxyacetylresorcin,
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-Benzene diol ，
Hydroquinone,
Methyl hydroquinone,
Trimethylhydroquinone, catechol,
4-tert-Butylcatechol,
1,6-Dihydroxynaphthalene,
2,7-Dihydroxynaphthalene,
1,5-Dihydroxynaphthalene,
2,6-Dihydroxynaphthalene,
2,4-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-Pentyl Benzophenone,
2,4-Dihydroxy-4'-n-hexylbenzophenone,
2,4-Dihydroxy-4'-n-heptylbenzophenone,
2,4-Dihydroxy-4'-n-octylbenzophenone,
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-Dihydroxy-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'-trimethoxybenzophenone,
2,4-Dihydroxy-3', 4', 5'-trimethoxybenzophenone,
Examples thereof include 2,4-dihydroxy-3', 4', 5'-triethoxybenzophenone and the like.

Furthermore, as a 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-methylbutano,
1,1-bis (4-hydroxyphenyl) -3-methylpentane,
1,1-bis (4-hydroxyphenyl) -2,3-dimethylpentane,
1,1-bis (4-hydroxyphenyl) -2-ethylbutane,
1,1-bis (4-hydroxyphenyl) -2-ethylhexane,
1,1-bis (4-hydroxyphenyl) -3,7-dimethyloctane,
1,1-bis (4-hydroxyphenyl) cyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3,5-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) 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) methylpropionate,
2,2-Bis (4-hydroxyphenyl) butyl propionate,
2,2-Bis (4-hydroxy-3-methylphenyl) methylpropionate,
2,2-Bis (4-hydroxyphenyl) ethyl propionate,
2,2-Bis (4-hydroxyphenyl) -4-methylpentane,
2,2-Bis (4-hydroxyphenyl) -4-methylhexane,
2,2-Bis (4-hydroxyphenyl) hexafluoropropane,
2,2-bis (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) oxindole,
3,3-bis (4-hydroxy-3-methylphenyl) oxindole,
Bis (2-hydroxyphenyl) methane,
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-Ethylene oxydiphenol,
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'-hydroxydiphenyl sulfone,
4- (4-Methylbenzyloxy) -4'-hydroxydiphenylsulfone,
4- (4-Ethylbenzyloxy) -4'-hydroxydiphenyl sulfone,
4- (4-n-propylbenzyloxy) -4'-hydroxydiphenyl sulfone,
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'-hydroxydiphenyl sulfone,
4- (3-Isopropylbenzyloxy) -4'-dihydroxyphenylsulfone,
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-Ethylbenzyloxy) -4'-hydroxydiphenylsulfone,
4- (2-n-propylbenzyloxy) -4'-hydroxydiphenyl sulfone,
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'-Dihydroxydiphenyl sulfone,
3,4'-Dihydroxydiphenyl sulfone,
4-Hydroxydiphenyl sulfone,
4-Methyl-4'-hydrokidiciphenyl 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'-hydroxydiphenylsulfone,
4-Methoxy-4'-hydroxydiphenyl sulfone,
4-ethoxy-4'-hydroxydiphenyl sulfone,
4-n-propoxy-4'-hydroxydiphenyl sulfone,
4-isopropoxy-4'-hydroxydiphenyl sulfone,
4-n-Butyloxy-4'-hydroxydiphenyl sulfone,
4-isobutoxy-4'-hydroxydiphenyl sulfone,
4-sec-butoxy-4'-hydroxydiphenyl sulfone,
4-tert-Butyl-4'-hydroxydiphenyl sulfone,
4-n-Pentyloxy-4'-hydroxydiphenyl sulfone,
4-Isopentyloxy-4'-hydroxydiphenyl sulfone,
4- (1-propenyloxy) -4'-hydroxydiphenyl sulfone,
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-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-trihydroxydiphenyl sulfone,
4-isopropoxy-4'-hydroxydiphenyl sulfone,
4-n-propoxy-4'-hydroxydiphenyl sulfone,
4-allyloxy-4'-hydroxydiphenyl sulfone,
4-Benzyloxy-4'-hydroxydiphenyl sulfone,
4- (2-propenyloxy) -4'-hydroxydiphenyl sulfone,
3-Benzyl-4-benzyloxy-4'-hydroxydiphenyl sulfone,
3-Phenethyl-4-phenethyloxy-4'-hydroxydiphenyl sulfone,
3-Methylbenzyl-4-methylbenzyloxy-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-hydroxyphenyl sulfone) 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-hydroxyphenyl) 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-hydroxyphenyl) sulfide,
Bis (4-hydroxyphenylthioethoxy) methane,
1,5- (4-Hydroxyphenylthio) -3-oxypentane,
Examples thereof include 1,8-bis (4-hydroxyphenylthio) -3,6-dioxaoctane.

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

Furthermore, as a compound of Tris-type phenol,
4,4', 4 "-Methyllysine Trisphenol,
4,4', 4 "-Methyllysine Tris (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 "-Etlysine Trisphenol,
4,4', 4 "-Etlydintris (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} etylidene] bisphenol,
4,4'-[1- {4- [1- (4-Hydroxyphenyl) -1-methylethyl] phenyl} propyridene] bisphenol,
4,4'-[1- {4- [1- (4-Hydroxyphenyl) -1-methylethyl] phenyl} butylidene] bisphenol,
4,4'-[1- {4- [1- (4-Hydroxyphenyl) -1-methylethyl] phenyl} pentylden] 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} etylidene] bisphenol,
3,3'-[1- {4- [1- (3-Hydroxyphenyl) -1-methylethyl] phenyl} etylidene] 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} ethylidene] 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 ″ -Methyllysine 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-phenylpropyridene] 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,
4,4', 4 ", 4'"-(1,1,2,2-ethanetetrayl) Tetrakis (2-methylphenol),
4,4', 4 ", 4'"-(1,1,2,2-ethanetetrayl) Tetrakis (2,6-dimethylphenol),
4,4', 4 ", 4'"-(1,4-phenylene) bis (methidrine) tetrakis (2,6-dimethylphenol),
2,2'-Bis [4,4-bis (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) -p-xylene,
Bis [2-hydroxy-3- (4-hydroxy-2,3,5-trimethylbenzyl) -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) bicyclohexyl,
2,2'-bis [4,4-bis (4-hydroxyphenyl) cyclohexyl] propane,
4,4,4', 4'-Tetrakis (4-hydroxy-3-methylphenyl) bicyclohexyl,
Bis [3- (5-cyclohexyl-4-hydroxy-2-methylbenzyl) -4-hydroxy-5-methylphenyl] methane,
4,4,4', 4'-Tetrakis (3,5-dimethyl-4-hydroxyphenyl) 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} etylidene] 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} etylidene] 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,
2,2-bis [4,4', 4 ", 4'"-tetrakis (3,5-dihydroxymethyl-4-hydroxyphenyl) cyclohexyl] propane and the like can be mentioned.

As a carboxylic acid and its derivative,
3,5-di (α-methylbenzyl) salicylic acid,
4- (2-p-Methoxyphenyloxyethoxy) salicylic acid,
4-Hydroxyphenylbenzoic acid,
p-Chlorobenzoic acid,
4- [2- (p-Methoxyphenoxy) ethyloxy] salicylic acid,
4- [3- (p-tolylsulfonyl) propyloxy] salicylic acid,
5- [p- (2-p-methoxyphenoxyethoxy) cumyl] salicylic acid,
4-octyloxycarbonylaminosalicylic acid,
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-trilaminocarbonyl) -phenylalanine,
N- (m-tolylaminocarbonyl) -cysteine-S-benzyl,
N- (m-trilaminocarbonyl) -methionine,
N- (m-trilaminocarbonyl) -tyrosine,
N- (p-tolylaminocarbonyl) -phenylalanine,
N- (p-tolylaminocarbonyl) -cysteine-S-benzyl,
N- (p-tolylaminocarbonyl) -methionine,
N- (p-tolylaminocarbonyl) -methionine,
N- (Phenylaminocarbonyl) -Methionine,
N- (p-tolylaminocarbonyl) -tyrosine,
N- (m-trilaminocarbonyl) -methionine,
N- (p-tolylaminocarbonyl) -methionine,
N- (Phenylaminocarbonyl) -Methionine,
N- (m-tolylaminocarbonyl) -valine,
N- (m-trilaminocarbonyl) -phenylglycine,
N- (m-trilaminocarbonyl) -tyrosine,
2-O- (Phenylaminocarbonyl) -Mandelic acid,
2-O- (p-tolylaminocarbonyl) -mandelic acid,
2-O- (m-trilaminocarbonyl) -mandelic acid,
2-O- (o-trilaminocarbonyl) -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- (benzylaminocarbonyl) -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), which is a 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 esters, ketones, ethers, alcohols, and acid amides.

As the component (c), regarding the color density-temperature curve, a large hysteresis characteristic (a curve plotting the change in coloring density due to a temperature change changes the temperature from the low temperature side to the high temperature side, and from the high temperature side to the low temperature side). A carboxylic acid ester compound having a ΔT value (melting point-cloud point) of 5 ° C. or higher and lower than 50 ° C., which can form a reversible thermochromic composition showing color memory, which changes color depending on the change), for example. Carboxylic acid ester containing a substituted aromatic ring in the molecule, carboxylic acid containing an unsubstituted aromatic ring and an ester of an aliphatic alcohol having 10 or more carbon atoms, a carboxylic acid ester containing a cyclohexyl group in the molecule, 6 or more carbon atoms Esters of fatty acids and unsubstituted aromatic alcohols or phenols, esters of fatty acids having 8 or more carbon atoms and branched aliphatic alcohols, esters of dicarboxylic acids and aromatic alcohols or branched aliphatic alcohols, dibenzyl silicate, heptyl stearate, Didecyl adipate, dilauryl adipate, dimyristyl adipate, disetyl adipate, distearyl adipate, trilaurin, trimylistin, tristea, dimyristin, dystea and the like are used.

Further, an odd aliphatic monohydric alcohol having 9 or more carbon atoms and a fatty acid ester compound obtained from an aliphatic carboxylic acid having an even number of carbon atoms, n-pentyl alcohol or n-heptyl alcohol and an even fat having 10 to 16 carbon atoms. Aliphatic ester compounds having a total carbon number of 17 to 23 obtained from the group carboxylic 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 capricate, n-nonyl caprice, n-undecyl caprice, n-tridecyl caprice, n-pentadecyl caprice, n-pentyl laurate, lauric acid 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 eikosanoate, n-undecyl eikosanoate, n-tridecyl eikosanoate, n-pentadecyl eikosanoate, behenic acid Examples thereof include n-nonyl, n-undecyl behenate, n-tridecyl behenate, n-pentadecyl behenate and the like.

As the ketones, aliphatic ketones having a total carbon number of 10 or more are effective, and 2-decanone, 3-decanone, 4-decanone, 2-undecanone, 3-undecanone, 4-undecanone, 5-undecanone, 2 -Dodecanone, 3-Dodecanone, 4-Dodecanone, 5-Dodecanone, 2-Tridecanone, 3-Tridecanone, 2-Tetradecanone, 2-Pentadecanone, 8-Pentadecanone, 2-Hexadecanone, 3-Hexadecanone, 9-Heptadecanone, 2-Pentadecanone , 2-octadecanone, 2-nonadecanone, 10-nonadecanone, 2-eicosanone, 11-eicosanone, 2-heneicosanone, 2-docosanone, lauron, stearone and the like.

Also, arylalkyl ketones having a total carbon number of 12 to 24, for example, n-octadecanophenone, n-heptadecanophenone, n-hexadecanophenone, n-pentadecanophenone, n-tetradecano. Phenone, 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-acetonaphthone, 2-acetonafton, cyclopentylphenylketone And so on.

As 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, zidodecyl 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.

As alcohols, aliphatic monohydric saturated alcohols having 10 or more carbon atoms are effective, and decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, and heptadecyl are effective. Examples thereof include alcohol, octadecyl alcohol, eikosyl alcohol, docosyl alcohol and the like.

Examples of acid amides include hexanoic acid amides, heptanic acid amides, octanoic acid amides, nonanoic acid amides, decanoic acid amides, undecanoic acid amides, lauric acid amides, tridecanoic acid amides, myristic acid amides, palmitic acid amides, stearic acid amides, and the like. Docosanic acid amide and the like can be mentioned.

（ここで、Ｒ^１は水素原子又はメチル基を示し、ｑ１は０〜２の整数を示し、Ｘ^１のいずれか一方は−（ＣＨ_２）_ｋＯＣＯＲ’又は−（ＣＨ_２）_ｋＣＯＯＲ’、他方は水素原子を示し、ｋは０〜２の整数を示し、Ｒ’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はそれぞれ独立に炭素数１〜４のアルキル基、メトキシ基、又はハロゲンを示し、ｐ１はそれぞれ独立に０〜３の整数を示す。） Further, as the component (c), a compound represented by the following general formula (1) can also be used.

(Here, R ¹ indicates a hydrogen atom or a methyl group, q ¹ indicates an integer of 0 to 2, and one of X 1 is − (CH ₂ ) _k OCOR'or − (CH ₂ ) _k COOR',. The other indicates a hydrogen atom, k indicates an integer of 0 to 2, R'indicates an alkyl group or an alkenyl group having 4 or more carbon atoms, and Y ₁ independently indicates an alkyl group or a methoxy group having 1 to 4 carbon atoms, respectively. , Or halogen, and p1 independently indicates an integer of 0 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 The case where m is 0 is more preferable.

（ここでＲ^１ａは、炭素数８以上のアルキル基又はアルケニル基、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。） Of the compounds represented by the formula (1), the compound represented by the following general formula (1a) is more preferably used.

(Here, R ^1a is 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 compound includes -4-benzyloxyphenylethyl octanoic acid, -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 hexadecanoate, heptadecanoic acid Examples thereof include -4-benzyloxyphenylethyl and -4-benzyloxyphenylethyl octadecanoic acid.

（ここで、Ｒ^２は炭素数８以上のアルキル基又はアルケニル基を示し、ｐ２はそれぞれ独立に０〜３の整数を示し、Ｘ^２はそれぞれ独立に炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、又はハロゲンを示す。） Further, as the component (c), a compound represented by the following general formula (2) can also be used.

(Here, R ² indicates an alkyl group or an alkenyl group having 8 or more carbon atoms, p2 independently indicates an integer of 0 to 3, and X ² independently indicates an alkyl group having 1 to 4 carbon atoms and a carbon number of carbons. 1 to 4 alkoxy groups or 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, pentadecanoic acid 1,1-diphenylmethyl, hexadecanoic acid 1,1-diphenylmethyl, heptadecanoic acid 1,1-diphenylmethyl, octadecanoic acid 1,1-Diphenylmethyl can be exemplified.

（ここで、Ｘ^３はそれぞれ独立に炭素数１〜４のアルキル基、メトキシ基、又はハロゲン原子のいずれかを示し、ｐ３はそれぞれ独立に０〜３の整数を示し、ｑ３は１〜２０の整数を示す。） Further, as the component (c), a compound represented by the following general formula (3) can also be used.

(Wherein, ^{X 3} each independently represent an alkyl group having 1 to 4 carbon atoms, indicates one of a methoxy group, or a halogen atom, p3 is independently an integer of 0 to 3, q3 is 1 to 20 Indicates an integer.)

Examples of the compound include a diester of malonic acid and 2- [4- (4-chlorobenzyloxy) phenyl)] ethanol, a diester of succinic acid and 2- (4-benzyloxyphenyl) ethanol, and a diester of succinic acid and 2-. [4- (3-Methylbenzyloxy) phenyl)] Diester with ethanol, Diester with glutaric acid and 2- (4-benzyloxyphenyl) ethanol, Diester with glutaric acid 2- [4- (4-chlorobenzyloxy) Phenyl)] Diester with ethanol, diester with adipic acid and 2- (4-benzyloxyphenyl) ethanol, diester with pimelic acid and 2- (4-benzyloxyphenyl) ethanol, suberic acid and 2- (4-benzyloxyphenyl). Diester with benzyloxyphenyl) ethanol, diester with Sveric acid and 2- [4- (3-methylbenzyloxy) phenyl)] Diester with ethanol, Sveric 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.

（ここで、Ｒ^４はそれぞれ独立に炭素数１〜２１のアルキル基又はアルケニル基を示し、ｐ４はそれぞれ独立に１〜３の整数を示す。） Further, as the component (c), a compound represented by the following general formula (4) can also be used.

(Wherein, ^{R 4} each independently represents an alkyl or alkenyl group of 1 to 21 carbon atoms, p4 denotes each independently a 1-3 integer.)

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 1,3-bis (2-hydroxyethoxy) benzene and palmitic acid, Diester of 1,3-bis (2-hydroxyethoxy) benzene and cyclohexanoic acid carboxylic acid, diester of 1,3-bis (2-hydroxyethoxy) benzene and cyclohexanoic acid propionic acid, 1,4-bis (hydroxymethoxy) ) Diester of benzene and butyric acid, diester of 1,4-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, 1,4-bis (2-hydroxyethoxy) benzene and valeric acid diester, 1,4-bis (2-hydroxyethoxy) benzene and caproic acid diester , 1,4-Bis (2-hydroxyethoxy) benzene and capric acid diester, 1,4-bis (2-hydroxyethoxy) benzene and capric acid diester, 1,4-bis (2-hydroxyethoxy) Examples thereof include a diester of benzene and lauric acid, a diester of 1,4-bis (2-hydroxyethoxy) benzene and myristic acid, and a diester of 1,4-bis (2-hydroxyethoxy) benzene and cyclohexanepropionic acid.

（ここで、Ｘ^５はそれぞれ独立に炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、又はハロゲン原子のいずれかを示し、ｐ５はそれぞれ独立に０〜３の整数を示し、ｑ５は１〜２０の整数を示す。） Further, as the component (c), a compound represented by the following general formula (5) can also be used.

(Here, X ⁵ independently indicates any of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and p5 independently indicates an integer of 0 to 3, respectively. q5 indicates an integer of 1 to 20.)

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-decandycarboxylic acid and 2-phenoxyethanol. An example is an example of a diester of 1,18-octadecanedicarboxylic acid and 2-phenoxyethanol.

（ここで、Ｒ^６は炭素数４〜２２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４〜２２のアルケニル基のいずれかを示し、Ｘ^６は水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、ハロゲン原子のいずれかを示し、ｑ６は０又は１を示す。） Further, as the component (c), a compound represented by the following general formula (6) can also be used.

(Here, R ⁶ indicates any of an alkyl group having 4 to 22 carbon atoms, a cycloalkyl alkyl group, a cycloalkyl group, and an alkoxy group having 4 to 22 ^{carbon atoms, and X 6} is a hydrogen atom and 1 to 4 carbon atoms. Indicates any of an alkyl group, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom, and q6 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.

（ここで、Ｒ^７は炭素数３〜１８のアルキル基、または炭素数３〜１８の脂肪族アシル基のいずれかを示し、Ｘ^７は水素原子、炭素数１〜３のアルキル基、炭素数１または２のアルコキシ基、ハロゲン原子のいずれかを示し、Ｙ^７は水素原子、メチル基のいずれかを示し、Ｚ^７は水素原子、炭素数１〜４のアルキル基、炭素数１又または２のアルコキシ基、ハロゲン原子のいずれかを示す。） Further, as the component (c), a compound represented by the following general formula (7) can also be used.

(Here, R ⁷ indicates either an alkyl group having 3 to 18 carbon atoms or an aliphatic acyl group having 3 to 18 ^{carbon atoms, and X 7} is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and a carbon number of carbon atoms. 1 or 2 alkoxy group or halogen atom, Y ⁷ indicates either hydrogen atom or methyl group, Z ⁷ is hydrogen atom, alkyl group with 1 to 4 carbon atoms, 1 or 2 carbon atoms. Indicates either the alkoxy group or the halogen atom 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 vanillate. Dodecyl ether can be exemplified.

（ここで、Ｒ^８は炭素数４〜２２のアルキル基、炭素数４〜２２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^８は、それぞれ独立にアルキル基、アルコキシ基、ハロゲン原子のいずれかを示し、ｐ８は０または１を示し、ｑ８は０〜５を示し、ｒ８は０〜４を示す。） Further, as the component (c), a compound represented by the following general formula (8) can also be used.

(Wherein, R ⁸ is an alkyl group having 4 to 22 carbon atoms, an alkenyl group having 4 to 22 carbon atoms, a cycloalkyl group, indicates one of a cycloalkyl group, X ⁸ are each independently an alkyl group, an alkoxy It indicates either a group or a halogen atom, p8 indicates 0 or 1, q8 indicates 0 to 5, and r8 indicates 0 to 4).

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- of dodecyl p-hydroxybenzoate. Examples thereof include methoxybenzoic acid ester and benzoic acid ester of p-hydroxybenzoic acid cyclohexylmethyl.

（ここで、Ｒ^９は炭素数３〜１７のアルキル基、炭素数３〜８のシクロアルキル基、炭素数５〜８のシクロアルキルアルキル基を示し、Ｘ^９は水素原子、炭素数１〜５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、ｐ９は１〜３の整数を示す。） Further, as the component (c), a compound represented by the following general formula (9) can also be used.

(Here, R ⁹ 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 9} is a hydrogen atom and 1 to 5 carbon atoms. Alkyl group, methoxy group, ethoxy group and halogen atom are shown, and p9 is 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 An example is an example of a diester with an acid.

Further, a specific alkoxyphenol compound having a linear or side chain alkyl group having 3 to 18 carbon atoms may be used as the electron-accepting compound (Japanese Patent Laid-Open No. 11-129623, JP-A-11-5973), or a specific one. A hydroxybenzoic acid ester (Japanese Patent Laid-Open No. 2001-105732) or a gallic acid ester (Japanese Patent Laid-Open No. 51-444706, Japanese Patent Application Laid-Open No. 2003-253149) is used for heating and coloring (coloring by heating, It is also possible to apply a microcapsule pigment comprising a reversible thermochromic composition (which is decolorized by cooling).

The blending ratios of the components (a), (b), and (c) depend on the concentration, discoloration temperature, discoloration form, and type of each component, but in general, the component ratio at which the desired discoloration characteristics can be obtained is determined. (A) 1 part by mass of component (b) 0.1 to 50 parts by mass, preferably 0.5 to 20 parts by mass, (c) 1 to 800 parts by mass, preferably 5 to 200 parts by mass. Is the range of.

Here, it is also possible to blend a coloring material such as a non-heat-changing dye or pigment in the microcapsule pigment or the ink to exhibit a reciprocal color change from colored (1) to colored (2). can.

The method of encapsulating the dye, the pigment and the thermochromic composition in the microcapsules is not particularly limited, and for example, an interfacial polymerization method, an interfacial polycondensation method, an inSitu polymerization method, an in-liquid curing coating method, a phase separation method from an aqueous solution, etc. There are a phase separation method from an organic solvent, a melt dispersion cooling method, an air suspension coating method, a spray drying method, and the like, which are appropriately selected according to the intended use.

The wall film of the microcapsule pigment consists of a polymer having at least one of a urea bond or a urethane bond in the repeating unit. By having the above-mentioned bonds in the repeating unit, the polymer constituting the wall film exhibits excellent properties by interacting with polyurethane described later.

The polymer can be synthesized, for example, by binding an isocyanate prepolymer to a polyol or polyamine, and is used in the present invention by encapsulating the dye, pigment or thermochromic composition described above in microcapsules. Can produce microcapsule pigments.

Further, the surface of the microcapsules can be provided with a secondary resin film depending on the purpose to impart durability, or the surface characteristics can be modified for practical use.

As the microcapsule pigment, those having an average particle size preferably in the range of 0.1 to 5.0 μm, more preferably 0.1 to 4.0 μm, and further preferably 0.5 to 3.0 μm are used.

The mass ratio of the reversible thermochromic composition to the microcapsule wall film is such that the reversible thermochromic composition: wall film = 7: 1 to 1: 1 (mass ratio), preferably 6: 1 to 1: 1. It is preferable to meet the range.

If the average particle size of the microcapsule pigment exceeds 5.0 μm, it is difficult to obtain a smooth writing feeling when used in a writing instrument, and if the average value of the maximum outer diameter is less than 0.1 μm, it is difficult to exhibit high-concentration color development. ..

Microcapsule pigments having an average particle size in the above range, particularly in the range of 0.5 to 3.0 μm, exhibit high-concentration color development and easily obtain good ejection properties when used in a writing instrument.

When the ratio of the reversible thermochromic composition to the wall film becomes larger than the above range, the thickness of the wall film becomes too thin and the resistance to pressure and heat tends to decrease, and the ratio of the wall film to the reversible thermochromic composition. When is larger than the above range, the color density and sharpness at the time of color development are likely to decrease.

For the measurement of the 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 diameter) is calculated from the area of the particle area. It is a value calculated and measured as the average particle diameter of particles corresponding to equal volume spheres based on the value.

If the particle size of all or most of the particles exceeds 0.2 μm, it is equivalent to an equal volume sphere by the Coulter method using a particle size distribution measuring device (manufactured by Beckman Coulter Co., Ltd., product name: Multisizer 4e). It is also possible to measure as the average particle size of the particles of. In addition, 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 a standard sample or a measuring device by the Coulter method. It may be used to measure a volume-based particle size and an average particle size (median size).

The content of the microcapsule pigment is preferably 5 to 30% by mass, more preferably 10 to 25% by mass with respect to the total mass of the ink composition. When the content is within the above range, it becomes easy to sharpen the handwriting while suppressing the dry-up of the pen tip.

(Polyurethane emulsion)
The ink composition contains a polyurethane emulsion in which polyurethane is dispersed. Polyurethane is evenly dispersed in the ink composition.
As the polyurethane emulsion, one having a minimum film forming temperature (MFT) of more than 20 ° C. and a polyurethane glass transition temperature (Tg) of 10 to 90 ° C. is applied. By using such a polyurethane emulsion, it is possible to suppress dry-up even when the ballpoint pen containing the ink containing the microcapsule pigment is stored at room temperature in the room with the pen tip exposed.
Further, the polyurethane emulsion described above can also enhance the water resistance of handwriting.

Dry-up of a ballpoint pen is strong due to the evaporation of water from the ink remaining on the pen tip to form agglomerates of pigments in the ink flow path of the ballpoint pen tip, and the dense agglomeration of shear reducing viscosity imparting agents and the like. When the film is formed on the ink ejection portion at the tip of the ballpoint pen tip, the rotation of the ball is hindered and the ink ejection property is deteriorated.
In the ink composition of the present invention, polyurethane suppresses the aggregation of microcapsule pigments and the dense aggregation of shear thinning agents to form a strong film, thereby suppressing dry-up of the ballpoint pen. do. This is because polyurethane has a high affinity for urea bonds and urethane bonds in the polymer forming the microcapsule pigment wall film, so that when polyurethane particles are adsorbed on the surface of the microcapsule pigment and the moisture in the ink evaporates. Even when the microcapsule pigments are prevented from coming into contact with each other and the moisture in the ink evaporates to form a film, the film is formed by the polyurethane particles contained in the film during writing. It is presumed that this is because the film is inhomogeneous and fragile to the extent that it is easily destroyed by the rotation of the ball.

When the MFT of the polyurethane emulsion is 20 ° C or lower, when water evaporates from the ink remaining on the pen tip at room temperature in the room, a film of polyurethane is formed on the pen tip, the ink ejection property deteriorates, and dry-up occurs. Therefore, it is not suitable for ink compositions. Further, when the Tg of polyurethane is less than 10 ° C or higher than 90 ° C, the reason is not clear, but it is not suitable because the effect of suppressing dry-up at room temperature is insufficient. The MFT of the polyurethane emulsion is preferably 90 ° C. or lower, more preferably 80 ° C. or lower. The Tg of polyurethane is preferably 20 ° C. or higher, more preferably 30 ° C. or higher.
Specific examples of the polyurethane emulsion applicable to the ink composition include, for example, commercially available products, trade name: Superflex 210 (MFT: 23 ° C., polyurethane Tg: 41 ° C.), trade name: Superflex 820 (MFT: 40 ° C.). , Polyurethane Tg; 46 ° C.), trade name; Superflex 870 (MFT: 70 ° C., Tg: 78 ° C.) or higher, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.
The polyurethane emulsion applicable to the ink composition is not limited to these.
A plurality of types of polyurethane emulsions may be used in combination.
The MFT of the polyurethane emulsion in the present invention is measured using an MFT measuring machine manufactured by YOSHIMITUSEIKI. Specifically, a desired polyurethane emulsion is applied to a film (for example, 64 cm × 18 cm) with a blade so that the coating thickness is 300 μm, and then dried. At this time, the temperature and transparency at which a white powdery precipitate is formed are formed. It is obtained by measuring the boundary temperature [° C] with the temperature at which the film is formed.
As the Tg of polyurethane, the peak of the loss elastic modulus when the coating film is pulled and measured at a frequency of 10 Hz using a dynamic viscoelasticity measuring device Rheogel-E4000 manufactured by UBM Co., Ltd. is used as the glass transition temperature Tg. demand.

The polyurethane makes the handwriting formed on the paper surface clear when the ink composition is ejected onto the paper surface. It is presumed that this is because polyurethane adsorbs the microcapsule pigment on the paper fiber on the paper surface through itself to improve the fixability of the microcapsule pigment on the paper surface, thereby improving the color development of the brush stroke. To.
Further, in the case of the thermochromic microcapsule pigment in which the microcapsule pigment contains the thermochromic composition, the discoloration responsiveness of the handwriting becomes good. This is because the microcapsule pigment is fixed on the paper surface, so that when heat is applied to the handwriting due to rubbing or the like or when the handwriting is cooled, the microcapsule pigment is quickly absorbed and dissipated. Is considered to be.

The polyurethane emulsion applicable to the present invention is not particularly limited as long as the Tg of MFT or polyurethane is within the above range, and any of them can be applied to an ink composition.

The content of the polyurethane emulsion in the ink composition is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass, based on the total mass of the polyurethane. .. When the content is within the above range, it is easy to suppress dry-up, improve the sharpness of the handwriting, and improve the discoloration response of the handwriting. If the content is more than 5% by mass, the ink ejection property may be deteriorated, and if it is less than 0.1% by mass, the effect of suppressing dry-up, improving the sharpness of the handwriting and the discoloration response of the handwriting is poor.

(Shear thinning agent)
A water-soluble or dispersible substance is effective as a shear reducing viscosity-imparting agent, and is an organic acid-modified heteropolysaccharide whose constituent monosaccharides are glucose and galactose. Succinoglycan (average molecular weight of about 1 to 8 million), guar gum, locust bean gum and its derivatives, hydroxyethyl cellulose, argylic acid alkyl esters, and methacrylic acid alkyl esters with a molecular weight of 100,000 to 150,000. Carbohydrates with gelling ability extracted from seaweeds such as coalesced, glucomannan, agar and caragenin, polyN-vinyl-carboxylic acid amide cross-linked products, benzylidene sorbitol and benziliden xylitol or derivatives thereof, cross-linking acrylic acid polymers, Examples thereof include inorganic fine particles, nonionic surfactants having an HLB value of 8 to 12, metal salts and amine salts of dialkylsulfosuccinic acid. Further, N-alkyl-2-pyrrolidone and an anionic surfactant may be added in combination to the ink composition.
The shear thinning agent can be used in the range of 0.1 to 10% by mass, preferably 0.1 to 5% by mass in the ink composition.

(Phosphoric acid ester-based surfactant)
The ink composition preferably contains a phosphoric acid ester-based surfactant.
The phosphoric acid ester-based surfactant is also adsorbed on the surface of the ball and the surface of the ball receiving seat of the ball pen tip to form a lubricating layer made of the phosphoric acid ester-based surfactant on the ball surface and the surface of the ball receiving seat. The ball rotation during writing can be made smoother.

式中、Ｅ^１、Ｅ^２、Ｅ^３は、下記式（１１）、式（１２）に示す官能基および水酸基から選ばれるいずれかであり、Ｅ^１、Ｅ^２、Ｅ^３から選ばれる少なくとも１種は、式（１１）または（１２）に示す官能基である。

式中、Ｒ^１０は炭化水素基、Ｒ^１１はアルキレン基である。また、ｎは１以上の整数である。

式中、Ｒ^１２は炭化水素基、Ｒ^１３およびＲ^１４は互いに異なるアルキレン基である。また、ｏ、ｐは１以上の整数である。 The phosphoric acid ester-based surfactant used in the ink composition is a compound represented by the following formula (10).

In the formula, E ¹ , E ² , and E ³ are any of the functional groups and hydroxyl groups represented by the following formulas (11) and (12), and at least one selected from ^{E 1} , E ² , and E ^3. The species is a functional group represented by the formula (11) or (12).

In the formula, R ¹⁰ is a hydrocarbon group and R ¹¹ is an alkylene group. Further, n is an integer of 1 or more.

In the formula, R ¹² is a hydrocarbon group, and R ¹³ and R ¹⁴ are different alkylene groups. Further, o and p are integers of 1 or more.

A preferable phosphate ester-based surfactant for an ink composition is a phosphate ester-based surfactant in which R ¹⁰ and R ¹² are an alkyl group, an alkenyl group or an aryl group, and more preferably, the R ¹⁰ is an alkyl group. A phosphate ester-based surfactant having a group, an alkenyl group or an aryl group and the R ¹¹ being an ethylene group, and the R ¹² being an alkyl group, an alkenyl group or an aryl group and having the R ¹³ and R ¹⁴ One of the above is an ethylene group, and the other is a phosphate ester-based surfactant having a propylene group or a trimethylene group.

As the phosphoric acid ester-based surfactant, ^{any one selected from E 1 to} E ^{3 is a monoester type, E 1 to} E ³ which is a functional group represented by the formula (11) or the formula (12). any two selected from and (11) and (12) one at a diester functional group represented by formula, or ^E 1 to E ³ all, at (11) and (12) The triester type, which is one of the indicated functional groups, may be used alone, or two or more kinds selected from the monoester type, the diester type and the triester type may be used in combination.
Further, the phosphoric acid ester-based surfactant which is a monoester type or a diester type may be an alkali metal salt, an ammonium salt, an amine salt, an alkanolamine salt or the like.

Additives such as a pH adjuster, a preservative, and an antifungal agent can be added to the ink composition according to the present invention, if necessary.

Examples of the pH adjusting agent include inorganic salts such as ammonia, sodium carbonate, sodium phosphate, sodium hydroxide and sodium acetate, water-soluble amine compounds such as triethanolamine and diethanolamine, urea, dimethylurea, diethylurea and hydroxymethyl. Examples thereof include urea derivatives such as urea and hydroxyethylurea, organic basic compounds such as amide compounds such as acetamide and N-methylacetamide, and acidic compounds such as phosphoric acid, lactic acid and amino acids.

As preservatives or antifungal agents, 2-methyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 2-methyl- 4,5-Trimethylene-4-isothiazolin-3one, N- (n-butyl) -1,2-benzisothiazolin-3-one, 2-pyridinethiol-1-sodium oxide, 3-iodo-2-propynylbutyl Carbamate, benzotriazole and phenol, sodium benzoate, sodium dehydroacetate, potassium sorbate, propyl paraoxybenzoate, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine and the like can be mentioned.

Examples of the rust preventive include benzotriazole and its derivatives, tolyltriazole, dicyclohexylammonium nitrite, diisopropylammonium nitrite, sodium thiosulfate, saponin, and dialkylthiourea. Further, as the water-soluble resin, an acrylic resin, an alkyd resin, polyvinylpyrrolidone, polyvinyl alcohol and the like can be used. Further, as the resin emulsion, an emulsion containing an acrylic resin, a styrene-butadiene resin, a polyester resin, a vinyl acetate resin and the like can be added.

Further, a defoaming agent such as a fluorine-based surfactant, a silicone-based surfactant, a dextrin, a lubricant, a specific gravity adjusting agent, a bubble absorber, and dimethylpolysiloxane, which improve the permeability of the solvent, can be added.

The dextrin is preferably a sugar mixture containing a starch saccharified product having 8 or more sugars and / or a reduced product thereof. The sugar mixture preferably contains 30% by mass or more of starch saccharified product having 8 or more sugars, more preferably 50% or more, and particularly preferably 70% or more. Since such dextrin is excellent in film forming property, it is preferable because it has a great effect of suppressing the evaporation of water from the pen tip and suppressing the dry-up of the pen tip.

Examples of the lubricant include metal soap, 2,5-dimercapto-1,3,4-thiadiazole and salts and oligomers thereof, 3-amino-5-mercapto-1,2,4-triazole, thiocarbamate, and dimethyl. Dithiocarbamate, α-lipoic acid, condensate of N-acyl-L-glutamic acid and L-lysine and its salt, ethylene oxide addition type cationic activator, N-acylamino acid type surfactant, dicarboxylic acid type surface activity Examples thereof include agents, β-alanine type surfactants and the like. Further, as the specific gravity adjusting agent, sodium isotungstate, sodium metatungstate, sodium paratungstate and the like can be applied.

Examples of the bubble absorber include ascorbic acids, erythorbic acids, α-tocopherols, catechins, synthetic polyphenols, succinic acid, alkylhydroxylamines, oxime derivatives, α-glucosyllutin, α-lipoic acid, phosphonates and phosphinates. , Sulfate, sulfoxylate, subdithionate, thiosulfate, thiourea dioxide and the like can be exemplified.

The water-based ink composition according to the present invention can be produced by any conventionally known method. Specifically, each of the above components can be blended in a required amount and mixed with various stirrers such as a propeller stirrer, a homodisper, or a homomixer, or various dispersers such as a bead mill to produce the product.

A ballpoint pen for filling the ink composition will be described.
The ballpoint pen tip, which is the tip of the writing, is, for example, one in which a ball receiving seat and an ink lead-out part are formed by cutting metal, and a plurality of inward protrusions are formed on the inner surface near the tip of the metal pipe from the outer surface. It is possible to apply an ink outflow gap that is provided by pressing deformation and extends radially outward from the center between the inwardly protruding portions. In particular, the tip due to pressing deformation is with the rear end of the ball. The contact area is relatively small, and a smooth writing feeling can be given at a low writing pressure.
As an example, the metal pipe has a structure in which the tip portion is a straight cylindrical body (straight tubular cylindrical body) and the rear portion of the tip portion has an enlarged outer diameter and inner diameter. The shape of the pipe may be a structure composed of a straight cylindrical body as a whole.

The ball held by the ballpoint pen tip has an outer diameter of 0.1 to 2.0 mm, preferably 0.2 to 1.2 mm, more preferably 0.28, such as cemented carbide, stainless steel, ruby, and ceramic. A ball of ~ 0.7 mm is effective. 0. When using balls of 7 mm or less, it is necessary to increase the chip clearance for the purpose of increasing the amount of ink ejected and for the purpose of stably ejecting microcapsule pigments (especially 0.1 μm or more) having a larger particle size than ordinary coloring materials. Therefore, the ink remaining on the chip tends to evaporate water. Therefore, the ink of the present invention works more effectively.
The ballpoint pen tip is provided with an elastic member that repels the rear end of the ball forward in the tip, and the ball is pressed against the inner edge of the tip of the tip when not writing to bring the ball into a close contact state. It is also possible to retract the ball so that the ink can flow out, and it is possible to suppress ink leakage when not in use.
Examples of the elastic member include a spring made of a thin metal wire, a member having a straight portion (rod portion) at one end of the spring, a linear plastic processed body, and the like, and the elastic member can be pressed by an elastic force of 5 to 40 g. And apply.

As the shaft cylinder accommodating the ink composition, for example, a molded product made of a thermoplastic resin such as polyethylene, polypropylene, or polyethylene terephthalate is preferably used in terms of low ink evaporability and productivity.
In addition to directly connecting the chip to the shaft cylinder, the shaft cylinder and the chip may be connected via a connecting member.

Further, by using a transparent, colored transparent, or translucent molded body as the shaft cylinder, the ink color, the remaining amount of ink, and the like can be confirmed.
The shaft cylinder may be a form of a ballpoint pen refill that accommodates the refill in the outer shaft, or the shaft cylinder itself with a tip attached to the tip thereof is used as an ink container and directly in the shaft cylinder. Ink may be filled.

The ballpoint pen using the barrel can be applied to either a cap type or a haunting type. As a haunting type ballpoint pen, the writing tip provided in the ballpoint pen refill is housed in the outer shaft in a state of being exposed to the outside air, and the writing tip protrudes from the opening of the outer shaft by the operation of the hoisting mechanism. If there is, all can be used.
Examples of the operation method of the haunting mechanism include a knock type, a rotary type, and a slide type.
The knock type has a knock portion on the rear end portion of the outer shaft and the side surface of the outer shaft, and by pressing the knock portion, the writing tip portion of the ballpoint pen refill is made to appear and disappear from the front end opening of the outer shaft, or the outer shaft. By pressing the provided clip portion, a configuration in which the writing tip portion of the ballpoint pen refill is made to appear and disappear from the opening at the front end end of the outer shaft can be exemplified.
The rotary type has a rotating portion (rear shaft or the like) on the outer shaft, and by rotating the rotating portion, the writing tip portion of the ballpoint pen refill can be exemplified from the front end opening of the outer shaft.
The slide type has a slide portion on the side surface of the barrel, and the writing tip portion of the ballpoint pen refill can be retracted from the opening at the front end of the outer shaft by operating the slide, or the clip portion provided on the outer shaft can be slid. By doing so, it is possible to exemplify a configuration in which the writing tip portion of the ballpoint pen refill is made to appear and disappear from the opening at the front end end of the outer shaft.
The infestation type ballpoint pen may be a composite type infestation type ballpoint pen in which a plurality of ballpoint pen refills are accommodated in addition to the one in which one ballpoint pen refill is accommodated in the outer shaft. Further, the ink accommodating tube constituting the ballpoint pen refill may be made of resin or metal.

The rear end of the ink contained in the ballpoint pen refill can be filled with an ink backflow preventive body.
The ink backflow prevention body composition comprises a non-volatile liquid or a non-volatile liquid.
Specifically, vaseline, spindle oil, castor oil, olive oil, refined mineral oil, liquid paraffin, polybutene, α-olefin, α-olefin oligomer or co-oligomer, dimethyl silicone oil, methylphenyl silicone oil, amino-modified silicone oil, Examples thereof include polyether-modified silicone oil and fatty acid-modified silicone oil, and one or more of them can be used in combination.

It is preferable to add a gelling agent to the non-volatile liquid or the non-volatile liquid to increase the viscosity to a suitable viscosity, and the surface is treated with a hydrophobic treatment of silica, the surface is treated with a methylated fine particle silica, aluminum silicate, and swelling. Sexual mica, clay-based thickeners such as bentonite and montmorillonite treated with hydrophobicity, fatty acid metal soaps such as magnesium stearate, calcium stearate, aluminum stearate, zinc stearate, trivendilidene sorbitol, fatty acid amide, amide-modified polyethylene wax. , Hydrophobic acid oil, dextrin-based compounds such as fatty acid dextrin, and cellulose-based compounds can be exemplified.
Further, the liquid ink backflow prevention body composition and the solid ink backflow prevention body can be used in combination.

Further, together with the ballpoint pen, a friction member for discoloring or discoloring the handwriting by frictional heat can be used.
As the friction member, an elastic body such as an elastomer or a plastic foam which is rich in elastic feeling and can generate frictional heat by generating appropriate friction at the time of friction is suitable. Although it is possible to rub the handwriting using an eraser, the above-mentioned friction member is preferably used because an eraser residue is generated at the time of rubbing.
The materials of the friction member include styrene-based thermoplastic elastomers such as silicone resin, SEBS resin (styrene ethylene butadiene styrene block copolymer), SBS resin (styrene butylene styrene copolymer), polyester resin, polypropylene resin and styrene. A mixture of based thermoplastic elastomers, a mixture of polypropylene resin and polypropylene based thermoplastic elastomer, and the like are used.
As the friction member, a writing instrument set can be obtained by combining a ballpoint pen and a member (friction body) having an arbitrary shape, but by fixing the friction member to the exterior of the ballpoint pen, the form is excellent in portability.
In the case of a cap-type ballpoint pen, the place where the friction member is provided is not particularly limited, but for example, when the cap itself is formed of the friction member, the barrel itself is formed of the friction member, or when a clip is provided, the clip It can be formed by a friction member itself, or a friction member can be provided at the tip end portion (top) of the cap or the rear end portion of the barrel (the portion where the writing tip portion is not provided).
In the case of a haunting type ballpoint pen, the place where the friction member is provided is not particularly limited, but for example, the shaft cylinder itself may be formed of the friction member, or the clip itself may be formed of the friction member when the clip is provided. A friction member can be provided near the opening of the cylinder, at the rear end of the shaft cylinder (the portion where the writing tip is not provided), or at the knock portion.

Examples will be described below, but the present invention is not limited to these examples.
Table 1 shows the compositions of the water-based inks for ballpoint pens of Examples and Comparative Examples. The numerical values of the compositions in the table indicate parts by mass.
Further, in this embodiment, the average particle size is determined by the laser diffraction / scattering type particle size distribution measuring device (device name: LA-300, HORIBA, Ltd.) calibrated by the Coulter method (electrical detection band method). The average particle size (median size) and particle size based on the volume were measured using (manufactured by Mfg. Co., Ltd.).

The contents of the raw materials in the table will be explained according to the note numbers.
(1) Black microcapsule pigment (a) 4.5 parts of 2- (2-chloroanilino) -6-di-n-butylaminofluorane as a component, and 2,2-bis (4-hydroxyphenyl) as a component (b) ) Hexafluoropropane 5.0 parts, (c) 4-benzyloxyphenylethyl decanoate as a component 50. The reversible thermochromic composition consisting of 0 parts was uniformly heated and dissolved, and 40.0 parts of the aromatic polyvalent isocyanate prepolymer and the auxiliary solvent 50 were used as the wall film material. The solution mixed with 0 parts was emulsified and dispersed in a 10% polyvinyl alcohol aqueous solution so as to form fine droplets, and stirring was continued while heating, then 2.5 parts of water-soluble aliphatic modified polyamine was added, and further stirring was performed. Continued to obtain a microcapsule pigment suspension.
The suspension was filtered with a filter press to obtain a microcapsule pigment.
The average particle size of the microcapsule pigment is 2.3 μm, and the _{behavior has hysteresis characteristics of t 1} : -20 ° C, t ₂ : -9 ° C, t ₃ : 40 ° C, t ₄ : 57 ° C, and ΔH63 ° C. It was shown that the color changed reversibly from black to colorless and from colorless to black.
(2) Blue microcapsule pigment (a) As a component, 3- (4-diethylamino-2-hexyloxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide 2.0 parts , (B) Reversible thermal discoloration consisting of 8.0 parts of 2,2-bis (4-hydroxyphenyl) hexafluoropropane as a component and 50.0 parts by mass of -4-benzyloxyphenylethyl decanoate as a component (c). The composition was uniformly heated and dissolved, and 40.0 parts of an aromatic polyvalent isocyanate prepolymer as a wall film material, an auxiliary solvent 50. The solution mixed with 0 parts was emulsified and dispersed in a 10% polyvinyl alcohol aqueous solution so as to form fine droplets, and stirring was continued while heating, then 2.5 parts of water-soluble aliphatic modified polyamine was added, and further stirring was performed. Continued to obtain a microcapsule pigment suspension.
The suspension was filtered with a filter press to obtain a microcapsule pigment. The average particle size of the microcapsule pigment is 2.3 μm, and the _{behavior has a hysteresis characteristic of t 1} : -14 ° C, t ₂ : -6 ° C, t ₃ : 48 ° C, t ₄ : 60 ° C, and ΔH 64 ° C. It was shown that the color changed reversibly from blue to colorless and from colorless to blue.
(3) Dextrin (manufactured by Sanwa Cornstarch Co., Ltd., product name: Sandeck # 70)
(4) Polyoxyalkylene styrenated phenyl ether phosphate (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Plysurf AL, a mixture of monoester type and diester type)
(5) Benzoisothiazolin-3-one (Lonza Japan product name: Proxel XL-2)
(6) Fluorescent pigment dispersion (manufactured by Nippon Fluorescent Chemical Co., Ltd., trade name: Lumicol NKW-2306H, aqueous dispersion of styrene acrylic resin particles colored with fluorescent dye, active ingredient 45% by mass)
(7) Manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Superflex 210 (active ingredient 35% by mass, MFT: 23 ° C, polyurethane Tg: 41 ° C)
(8) Manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Superflex 820 (active ingredient 30% by mass, MFT: 40 ° C, polyurethane Tg: 46 ° C)
(9) Manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Superflex 870 (active ingredient 35% by mass, MFT: 70 ° C, polyurethane Tg: 78 ° C)
(10) Manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Superflex 420 (active ingredient 32% by mass, MFT: 20 ° C, polyurethane Tg: -10 ° C)
(11) Manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Superflex 126 (active ingredient 30% by mass, MFT: 5 ° C or lower, polyurethane Tg: 72 ° C)
(12) Acrylic resin emulsion (manufactured by Nissin Chemical Industry Co., Ltd., trade name: Vinibran 2585, active ingredient: 45% by mass, MFT: 30 ° C., Tg of acrylic resin: 25 ° C.)

Preparation of Inks Each component was prepared by adding each component to water, stirring at 2000 rpm for 1 hour with a disper, adding xanthan gum or succinoglycan, and stirring for another 1 hour.

Preparation of test ballpoint pen A test ballpoint pen was prepared using the inks prepared in the above Examples and Comparative Examples.
As the ballpoint pen for accommodating the ink, a trade name: friction ball 07 [manufactured by Pilot Corporation] was used.

The following test was performed using the ballpoint pen produced in the production of the ballpoint pen.
-Evaluation of handwriting sharpness A character was written on the old JIS P3201 writing paper A (written character: eternal), and the condition of the handwriting was confirmed.
〇… The outline of the characters is clear and the color is dark.
×… The outline of the character is unclear. Also, the color is light.
・ Evaluation of rewritability
The ballpoint pen confirmed to be writable was stored at 20 ° C. for 30 days with the pen tip exposed, and then 12 spiral circles were continuously written by hand and the handwriting was visually confirmed. The evaluation criteria were 〇 as a pass and △ and × as a failure.
〇… You can form a handwriting without blurring from the beginning of writing.
Δ: Although blurring occurred at the beginning of writing, the blurring disappeared while writing 12 spiral circles.
×… It is impossible to write. Or, the blurring is not eliminated while writing 12 spiral circles.

-Evaluation of handwriting erasability The handwriting formed by the evaluation of handwriting sharpness was rubbed with a friction ball 07 scraping material, and the decolorizing property of the handwriting was confirmed. The load on the handwriting at the time of rubbing was 200 g. As for the evaluation criteria, 〇 was accepted and Δ and × were rejected.
〇… The handwriting became invisible after one scratch.
Δ… The handwriting became invisible after a few scratches.
×… The handwriting can be visually recognized by rubbing three times.
The results of each of the above tests are shown in the table below.

t ₁ Complete color development temperature of the microcapsule pigment containing the _{reversible thermochromic composition t 2} Color development start temperature of the microcapsule pigment containing the _{reversible thermochromic composition t 3} Microcapsule pigment containing the reversible thermochromic composition Decolorization start temperature t ₄ Complete decolorization temperature of microcapsule pigment containing reversible thermochromic composition ΔH Hysteresis width

Claims (5)

An ink composition containing a microcapsule pigment having a wall film made of a polymer, a polyurethane emulsion having a minimum film forming temperature of more than 20 ° C., a shear reducing viscosity imparting agent, and water, wherein the polymer has a urea bond or a urethane bond. A water-based ink composition for a ball pen, which comprises at least one of the above in a repeating unit and has a glass transition temperature of the polyurethane of 10 to 90 ° C. The microcapsule pigment comprises (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. The water-based ink composition according to claim 1, which is a thermochromic microcapsule pigment containing a sex composition. The aqueous ink composition according to claim 1 or 2, wherein the minimum film forming temperature of the polyurethane emulsion is 90 ° C. or lower. The water-based ink composition according to claim 1 or 2, wherein the polyurethane has a glass transition temperature of 20 to 90 ° C. A ballpoint pen containing the water-based ink composition according to any one of claims 1 to 4.

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