JP2023159613A - Reversible thermochromic composition and reversible thermochromic microcapsule pigment including the same - Google Patents

Abstract

To provide a reversible thermochromic composition that employs a specific compound as an electron-accepting compound, exhibiting a reversible thermochromic function, and a reversible thermochromic microcapsule pigment including the same.SOLUTION: The present invention relates to: a reversible thermochromic composition (a) an electron-donating coloring organic compound, (b) a compound represented by formula (1) as an electron-accepting compound, and (c) a reaction medium that causes an electron exchange reaction to reversibly occur in a specific temperature range; and a reversible thermochromic microcapsule pigment including the same. (In the formula (1), X is a C1-12 alkyl group or the like, Y is a C1-12 alkyl group or the like, and n is an integer of 1-3, where X and Y are different).SELECTED DRAWING: None

Description

The present invention relates to a reversible thermochromic composition and a reversible thermochromic microcapsule pigment containing the composition. More specifically, the present invention relates to a reversible thermochromic composition that loses color when the temperature rises and develops color when the temperature falls, and a reversible thermochromic microcapsule pigment containing the composition.

Conventionally, reversible thermochromic compositions consisting of a compatible solution of an electron-donating color-forming organic compound, an electron-accepting compound, and a reaction medium that reversibly causes an electron transfer reaction in a specific temperature range, and reversible thermochromic compositions containing the same; Several proposals regarding color-changing microcapsule pigments have been disclosed (see, for example, Patent Documents 1 to 5).
The electron-accepting compounds contained in the reversible thermochromic composition include compounds having active protons, pseudo-acidic compounds (not acids, but electron-donating color-forming organic compounds that act as acids in the composition); A group of compounds that develop color], a group of compounds that have an electron hole, and the like.

Japanese Patent Application Publication No. 7-11242 Japanese Patent Application Publication No. 2002-53853 Japanese Patent Application Publication No. 2010-106052 Japanese Patent Application Publication No. 2012-229294 Japanese Patent Application Publication No. 2013-10810

The present invention aims to carry out an electron transfer reaction between (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) the components (a) and (b) above in a specific temperature range. As a result of examining (b) electron-accepting compounds that can be applied to reversible thermochromic compositions comprising a reversibly generated reaction medium, it was discovered that a reversible thermochromic function can be expressed by using a specific compound.

（式中、Ｘは、炭素数１～１２個のアルキル基、炭素数１～１２個のアルコキシ基、トリハロゲン化メチル基、ニトロ基、ハロゲン原子、あるいは水素原子を表す。Ｙは、炭素数１～１２個のアルキル基、炭素数１～１２個のアルコキシ基、水素原子、ハロゲン原子、或いは式（２）で示される置換基を表す。ｎは１～３の整数を表す。但し、ＸとＹは異なる。

式（２）中、Ｚは、Ｏ、Ｓ、炭素数１～１２の直鎖もしくは分岐のアルキレン基、ＮＨ、ＳＯ_２、Ｃ＝Ｏを表す。Ｒ_１およびＲ_２は、炭素数１～６のアルキル基、ニトロ基、ハロゲン原子または水素原子を表す。）
更には、式（１）において、Ｘは、炭素数１～６個のアルキル基、炭素数１～６個のアルコキシ基、ハロゲン原子を表し、Ｙは、水素原子、あるいはハロゲン原子を表すこと、前記可逆熱変色性組成物を内包してなる可逆熱変色性マイクロカプセル顔料、前記可逆熱変色性マイクロカプセル顔料と、ビヒクルとを含んでなる可逆熱変色性液状組成物、前記可逆熱変色性液状組成物が印刷用インキ、筆記具用インキ、塗布具用インキ、スタンプ用インキ、インクジェット用インキ、塗料、紫外線硬化型インキ、絵の具、化粧料、及び繊維用着色液からなる群から選ばれること、前記可逆熱変色性マイクロカプセル顔料と、賦形剤とを含んでなる可逆熱変色性塗布用固形成形体、前記可逆熱変色性塗布用固形成形体が固形筆記体又は固形化粧料であること、前記可逆熱変色性マイクロカプセル顔料と、成形用樹脂とを含んでなる可逆熱変色性成形用樹脂組成物、前記可逆熱変色性成形用樹脂組成物を成形してなる可逆熱変色性成形体、支持体と、前記可逆熱変色性マイクロカプセル顔料を含んでなる可逆熱変色層とを具備してなる可逆熱変色性積層体、前記筆記具用インキを収容してなる筆記具、前記筆記具がボールペンであること、前記筆記具がマーキングペンであること、前記筆記具による筆跡を摩擦熱で変色する摩擦部材を備えてなること等を要件とする。 The present invention comprises (a) an electron-donating color-forming organic compound, (b) a compound represented by formula (1) as an electron-accepting compound, and (c) electrons generated by the components (a) and (b). A reversible thermochromic composition comprising a reaction medium that reversibly causes a transfer reaction in a specific temperature range is required.

(In the formula, X represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a trihalogenated methyl group, a nitro group, a halogen atom, or a hydrogen atom. Y is a carbon number Represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a hydrogen atom, a halogen atom, or a substituent represented by formula (2). n represents an integer of 1 to 3. However, X and Y are different.

In formula (2), Z represents O, S, a linear or branched alkylene group having 1 to 12 carbon atoms, NH, SO ₂ or C=O. R ₁ and R ₂ represent an alkyl group having 1 to 6 carbon atoms, a nitro group, a halogen atom or a hydrogen atom. )
Further, in formula (1), X represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom, and Y represents a hydrogen atom or a halogen atom; A reversible thermochromic microcapsule pigment containing the reversible thermochromic composition, a reversible thermochromic liquid composition comprising the reversible thermochromic microcapsule pigment and a vehicle, and a reversible thermochromic liquid composition. The composition is selected from the group consisting of printing inks, writing instrument inks, applicator inks, stamp inks, inkjet inks, paints, ultraviolet curable inks, paints, cosmetics, and textile coloring liquids; A solid molded article for reversible thermochromic coating comprising a reversible thermochromic microcapsule pigment and an excipient, the solid molded article for reversible thermochromic coating being a solid writing body or a solid cosmetic; A reversible thermochromic molding resin composition comprising a reversible thermochromic microcapsule pigment and a molding resin, a reversible thermochromic molded article formed by molding the reversible thermochromic molding resin composition, and a support. a reversible thermochromic laminate comprising a body and a reversible thermochromic layer comprising the reversible thermochromic microcapsule pigment, a writing instrument containing the ink for a writing instrument, and the writing instrument being a ballpoint pen. , the writing instrument is a marking pen, and the writing instrument is provided with a friction member that discolors handwriting by the writing instrument due to frictional heat.

The present invention satisfies the electron transfer reaction with an electron-donating color-forming organic compound by using a specific compound as an electron-accepting compound; To obtain a reversible color-changing composition capable of sufficiently expressing a reversible thermochromic function by mixing it with a reaction medium that reversibly causes the reaction in a specific temperature range, and a reversible thermochromic microcapsule pigment containing the same. Can be done.

1 is a graph illustrating hysteresis characteristics in a color density-temperature curve of a heat-erasable reversible thermochromic composition. 1 is a graph illustrating hysteresis characteristics in a color density-temperature curve of a heat-erasable reversible thermochromic composition having color memory properties.

The reversible thermochromic composition of the present invention includes (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) occurrence of a coloring reaction between components (a) and (b). Examples include reversible thermochromic compositions of heat-erasing type (erasing colors by heating and developing colors by cooling), which contain at least three essential components of a reaction medium that determines temperature.
The reversible thermochromic composition has a temperature that changes at a predetermined temperature (color change point) as described in Japanese Patent Publication No. 51-44706, Japanese Patent Publication No. 51-44707, Japanese Patent Publication No. 1-29398, etc. It changes color before and after, exhibits a decolored state in a temperature range above the high temperature side discoloration point, and a colored state in a temperature range below the low temperature side discoloration point, and of the above two states, only one specific state exists in the normal temperature range, The other state is maintained as long as the heat or cold required to bring it about is applied, but once the heat or cold is no longer applied, it returns to the state it exhibits at room temperature, with a hysteresis width ( A reversible thermochromic composition having a relatively small ΔH) of 1 to 7° C. can be used (see FIG. 1).

In addition, Japanese Patent Publication No. 4-17154, Japanese Patent Application Publication No. 7-179777, Japanese Patent Application Publication No. 7-33997, Japanese Patent Application Publication No. 8-39936, Japanese Patent Application Publication No. 2005-1369, Japanese Patent Application Publication No. 2008-280523, etc. In other words, the shape of the curve plotting the change in coloring density due to temperature change shows that the hysteresis width (ΔH) described in The discoloration follows a very different path depending on whether the temperature is lowered from the high temperature side than the discoloration temperature range, and the color development state in the low temperature range below the complete color development temperature (t ₁ ) or the complete discoloration temperature. (t ₄ ) or higher, the heat decoloring type (heat decoloring type) which has color memory in a specific temperature range [temperature range between t ₂ and t ₃ (substantially two-phase retention temperature range)] A reversible thermochromic composition (which loses color when heated and develops color when cooled) can also be applied (see FIG. 2).
The hysteresis characteristic in the color density-temperature curve of the reversible thermochromic composition will be explained.
In FIG. 2, the vertical axis represents color density, and the horizontal axis represents temperature. Changes in color density due to temperature changes progress along the arrows. Here, A is a point indicating the density at a temperature t ₄ (hereinafter referred to as complete decolorization temperature) at which a completely decolorized state is reached, and B is a point indicating the density at a temperature t ₃ (hereinafter referred to as decolorization start temperature) at which decolorization starts. C is a point indicating the density at a temperature t ₂ (hereinafter referred to as the color development start temperature) at which color development starts, and D is a point indicating the density at the temperature t ₁ (hereinafter referred to as complete color development temperature) at which a complete color development state is reached. This point indicates the density at the color development temperature.
The discoloration temperature range is the temperature range between t ₁ and t ₄ , which can exhibit either a colored state or a discolored state, and is a region between t ₂ and t ₃ where there is a large difference in color density. The temperature range is the actual color change temperature range.
In addition, the length of the line segment EF is a measure of the contrast of discoloration, and the length of the line segment HG passing through the midpoint of the line segment EF is the temperature width (hereinafter referred to as hysteresis width ΔH) indicating the degree of hysteresis. If this ΔH value is small, only one of the two states before and after discoloration can exist in the normal temperature range. Further, when the ΔH value is large, each state before and after discoloration can be easily maintained.

Each component (a), component (b), and component (c) will be specifically explained below.
The component (a), that is, the electron-donating color-forming organic compound, is a component that determines color, and is a compound that donates electrons to the component (b), which is a color developer, to develop color.
Examples of the electron-donating color-forming organic compounds include phthalide compounds, fluoran compounds, styrinoquinoline compounds, diazalhodamine lactone compounds, pyridine compounds, quinazoline compounds, bisquinazoline compounds, etc. Among these, phthalide compounds and fluoran compounds preferable.
Examples of the phthalide compounds include diphenylmethane phthalide compounds, phenylindolylphthalide compounds, indolyl phthalide compounds, diphenylmethane azaphthalide compounds, phenylindolyl azaphthalide compounds, and derivatives thereof. Among these, phenylindolyl azaphthalide compounds and derivatives thereof are preferred.
Furthermore, examples of the fluoran compound include aminofluoran compounds, alkoxyfluoran compounds, and derivatives thereof.
Examples of these compounds are shown below.
3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide,
3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide,
3,3-bis(1-n-butyl-2-methylindol-3-yl)phthalide,
3,3-bis(2-ethoxy-4-diethylaminophenyl)-4-azaphthalide,
3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide,
3-(2-hexyloxy-4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide,
3-[2-ethoxy-4-(N-ethylanilino)phenyl]-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide,
3-(2-acetamido-4-diethylaminophenyl)-3-(1-propylindol-3-yl)-4-azaphthalide,
3,6-bis(diphenylamino)fluorane,
3,6-dimethoxyfluorane,
3,6-di-n-butoxyfluorane,
2-methyl-6-(N-ethyl-Np-tolylamino)fluoran,
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-Np-tolylamino)fluoran,
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-Np-tolylamino)fluoran,
1,2-benz-6-diethylaminofluorane,
1,2-benz-6-(N-ethyl-N-isobutylamino)fluoran,
1,2-benz-6-(N-ethyl-N-isoamylamino)fluoran,
2-(3-methoxy-4-dodecoxystyryl)quinoline,
Spiro[5H-(1)benzopyrano(2,3-d)pyrimidine-5,1'(3'H)isobenzofuran]-3'-one, 2-(diethylamino)-8-(diethylamino)-4-methyl ,
Spiro[5H-(1)benzopyrano(2,3-d)pyrimidine-5,1'(3'H)isobenzofuran]-3'-one, 2-(di-n-butylamino)-8-(di- -n-butylamino)-4-methyl,
spiro[5H-(1)benzopyrano(2,3-d)pyrimidine-5,1'(3'H)isobenzofuran]-3'-one, 2-(di-n-butylamino)-8-(diethylamino )-4-methyl,
spiro[5H-(1)benzopyrano(2,3-d)pyrimidine-5,1'(3'H)isobenzofuran]-3'-one, 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'-one, 2-(dibutylamino)-8-(dipentylamino)-4 - methyl,
4,5,6,7-tetrachloro-3-[4-(dimethylamino)-2-methoxyphenyl]-3-(1-butyl-2-methyl-1H-indol-3-yl)-1(3H )-isobenzofuranone,
4,5,6,7-tetrachloro-3-[4-(diethylamino)-2-ethoxyphenyl]-3-(1-ethyl-2-methyl-1H-indol-3-yl)-1(3H) -isobenzofuranone,
4,5,6,7-tetrachloro-3-[4-(diethylamino)-2-ethoxyphenyl]-3-(1-pentyl-2-methyl-1H-indol-3-yl)-1(3H) -isobenzofuranone,
4,5,6,7-tetrachloro-3-[4-(diethylamino)-2-methylphenyl]-3-(1-ethyl-2-methyl-1H-indol-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]
etc. can be mentioned.
In addition to the above-mentioned compounds having a substituent on the phenyl group forming the xanthene ring, examples of fluoranes include compounds having a substituent on the phenyl group forming the xanthene ring and also substituents on the phenyl group forming the lactone ring (e.g. , an alkyl group such as a methyl group, or a halogen atom such as a chloro group) that exhibits blue or black color.

（式（１）中、Ｘは、炭素数１～１２個のアルキル基、炭素数１～１２個のアルコキシ基、トリハロゲン化メチル基、ニトロ基、ハロゲン原子、あるいは水素原子を表す。Ｙは、炭素数１～１２個のアルキル基、炭素数１～１２個のアルコキシ基、水素原子、ハロゲン原子、或いは式（２）で示される置換基を表す。ｎは１～３の整数を表す。但し、ＸとＹは異なる。

式（２）中、Ｚは、Ｏ、Ｓ、炭素数１～１２の直鎖もしくは分岐のアルキレン基、ＮＨ、ＳＯ_２、Ｃ＝Ｏを表す。Ｒ_１およびＲ_２は、炭素数１～６のアルキル基、ニトロ基、ハロゲン原子または水素原子を表す。）
また、式（１）において、Ｘは、炭素数１～６個のアルキル基、炭素数１～６個のアルコキシ基、ハロゲン原子であることが好ましく、Ｙは、水素原子、あるいはハロゲン原子であることが好ましい。 The component (b), that is, the electron-accepting compound, is a compound that receives electrons from the component (a) and functions as a color developer for the component (a).
As the component (b), a 1,3-diphenylurea derivative of formula (1), which is a non-phenolic electron-accepting compound (color developer), is used.

(In formula (1), X represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a trihalogenated methyl group, a nitro group, a halogen atom, or a hydrogen atom. Y is , represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a hydrogen atom, a halogen atom, or a substituent represented by formula (2). n represents an integer of 1 to 3. However, X and Y are different.

In formula (2), Z represents O, S, a linear or branched alkylene group having 1 to 12 carbon atoms, NH, SO ₂ or C=O. R ₁ and R ₂ represent an alkyl group having 1 to 6 carbon atoms, a nitro group, a halogen atom or a hydrogen atom. )
Further, in formula (1), X is preferably an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom, and Y is a hydrogen atom or a halogen atom. It is preferable.

As the alkyl group having 1 to 12 carbon atoms in X of formula (1), methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group Examples of the alkoxy group having 1 to 12 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, etc. Examples of the trihalogenated methyl group include trifluorinated methyl base, and halogen atom Examples include fluorine, chlorine, and bromine.
Examples of the alkyl group having 1 to 12 carbon atoms in Y of formula (1) include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, etc. Examples of the alkoxy group having 1 to 12 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, hexyloxy group, octyloxy group, nonyloxy group, decyloxy group, etc., and halogen atoms include fluorine and chlorine. , bromine.
The straight chain or branched alkylene group having 1 to 12 carbon atoms in the substituent Z represented by formula (2) includes a methylene group, and the alkyl group having 1 to 6 carbon atoms in R ₁ and R ₂ includes a methyl group, Examples include ethyl group, and examples of halogen atoms include fluorine and chlorine.

Specific examples of the 1,3-diphenylurea derivative of formula (1) include the following compounds (1) to (156).

In addition to the above component (b), it may further contain a known electron-accepting compound.
The electron-accepting compounds include a group of compounds having active protons, a group of pseudoacidic compounds [a group of compounds that are not acids, but act as acids in the reversible thermochromic composition to color the component (a)], and Examples include compounds selected from the group of compounds having electron vacancies.
Groups of compounds with active protons include compounds with phenolic hydroxyl groups and their derivatives, carboxylic acids and their derivatives, acidic phosphoric acid esters and their derivatives, azole compounds and their derivatives, 1,2,3-triazole and Examples thereof include derivatives thereof, cyclic carbosulfimides, halohydrins having 2 to 5 carbon atoms, sulfonic acids and derivatives thereof, and inorganic acids. As the carboxylic acid and its derivatives, aromatic carboxylic acids and their derivatives, or aliphatic carboxylic acids having 2 to 5 carbon atoms and their derivatives are preferable.
The pseudoacidic compound group includes metal salts of compounds having a phenolic hydroxyl group, metal salts of carboxylic acids, metal salts of acidic phosphoric acid esters, metal salts of sulfonic acids, aromatic carboxylic acid anhydrides, aliphatic carboxylic acid anhydrides. , mixed anhydrides 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, and the like.
Examples of the group of compounds having electron holes include borates, borate esters, and inorganic salts.
Compounds having a phenolic hydroxyl group include a wide range from monophenol compounds to polyphenol compounds, and further include bisphenol compounds, trisphenol compounds, phenol-aldehyde condensation resins, and the like. The compound having a phenolic hydroxyl group preferably has at least two or more benzene rings. Further, the compound having a phenolic hydroxyl group may have a substituent such as an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, a carboxyl group and its ester or amide group, or a halogen atom.
Examples of metals contained in metal salts such as compounds having a phenolic hydroxyl group include sodium, potassium, calcium, zinc, zirconium, aluminum, magnesium, nickel, cobalt, tin, copper, iron, vanadium, titanium, lead, and molybdenum. etc. can be exemplified.

Examples of known electron-accepting compounds are shown below.
Examples of compounds having one phenolic hydroxyl group include:
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-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,
n-butyl 4-hydroxybenzoate,
n-octyl 4-hydroxybenzoate,
4-hydroxybenzoic acid 2-heptadecafluorooctylethane,
benzyl 4-hydroxybenzoate,
4-hydroxybenzoic acid benzyl ester,
o-methylbenzyl 4-hydroxybenzoate,
m-methylbenzyl 4-hydroxybenzoate,
p-methylbenzyl 4-hydroxybenzoate,
p-ethylbenzyl 4-hydroxybenzoate,
p-propylbenzyl 4-hydroxybenzoate,
p-tert-butylbenzyl 4-hydroxybenzoate,
phenylethyl 4-hydroxybenzoate,
o-methylphenylethyl 4-hydroxybenzoate,
m-methylphenylethyl 4-hydroxybenzoate,
p-methylphenylethyl 4-hydroxybenzoate,
p-ethylphenylethyl 4-hydroxybenzoate,
p-propylphenylethyl 4-hydroxybenzoate,
Examples include p-tert-butylphenylethyl 4-hydroxybenzoate.

Examples of compounds having two phenolic hydroxyl groups include:
resorcinol,
2-methylresorcin,
4-n-hexylresorcin,
4-n-octylresorcin,
4-tert-octylresorcin,
4-benzoylresorcin,
4-nitroresorcin,
Methyl β-resorucinate,
benzyl β-resorcate,
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-phenylacetyl resorcin,
6-chloro-4-phenylacetylresorcin,
2-chloro-4-β-phenylpropanoylresorcin,
6-chloro-4-β-phenylpropanoylresorcin,
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-benzenediol,
hydroquinone,
methylhydroquinone,
trimethylhydroquinone,
catechol,
4-tert-butylcatechol,
1,6-dihydroxynaphthalene,
2,7-dihydroxynaphthalene,
1,5-dihydroxynaphthalene,
2,6-dihydroxynaphthalene,
2,4-dihydroxybenzophenone,
4,4'-dihydroxybenzophenone,
2,4-dihydroxy-2'-methylbenzophenone,
2,4-dihydroxy-3'-methylbenzophenone,
2,4-dihydroxy-4'-methylbenzophenone,
2,4-dihydroxy-4'-ethylbenzophenone,
2,4-dihydroxy-4'-n-propylbenzophenone,
2,4-dihydroxy-4'-isopropylbenzophenone,
2,4-dihydroxy-4'-n-butylbenzophenone,
2,4-dihydroxy-4'-isobutylbenzophenone,
2,4-dihydroxy-4'-tert-butylbenzophenone,
2,4-dihydroxy-4'-n-pentylbenzophenone,
2,4-dihydroxy-4'-n-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 include 2,4-dihydroxy-3',4',5'-triethoxybenzophenone.

Furthermore, as bisphenol compounds, for example,
1,1-bis(4-hydroxyphenyl)ethane,
1,1-bis(4-hydroxyphenyl)propane,
1,1-bis(4-hydroxyphenyl)n-butane,
1,1-bis(4-hydroxyphenyl)n-pentane,
1,1-bis(4-hydroxyphenyl)n-hexane,
1,1-bis(4-hydroxyphenyl)n-heptane,
1,1-bis(4-hydroxyphenyl)n-octane,
1,1-bis(4-hydroxyphenyl)n-nonane,
1,1-bis(4-hydroxyphenyl)n-decane,
1,1-bis(4-hydroxy-3-methylphenyl)decane,
1,1-bis(4-hydroxyphenyl)n-dodecane,
1,1-bis(4-hydroxyphenyl)-2-methylpropane,
1,1-bis(4-hydroxyphenyl)-3-methylbutane,
1,1-bis(4-hydroxyphenyl)-3-methylpentane,
1,1-bis(4-hydroxyphenyl)-2,3-dimethylpentane,
1,1-bis(4-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)butylpropionate,
2,2-bis(4-hydroxy-3-methylphenyl)methylpropionate,
2,2-bis(4-hydroxyphenyl)ethylpropionate,
2,2-bis(4-hydroxyphenyl)-4-methylpentane,
2,2-bis(4-hydroxyphenyl)-4-methylhexane,
2,2-bis(4-hydroxyphenyl)hexafluoropropane,
2,2-bis(3,5-dihydroxymethyl-4-hydroxyphenyl)hexafluoropropane,
2,2-bis(4-hydroxy-3-methylphenyl)propane,
2,2-bis(4-hydroxy-3-methylphenyl)butane,
2,2-bis(4-hydroxy-3-isopropylphenyl)propane,
2,2-bis(3-sec-butylphenyl-4-hydroxy)propane,
2,2-bis(4-hydroxy-3-phenylphenyl)propane,
2,2-bis(3-tert-butyl-4-hydroxyphenyl)propane,
2,2-bis(3-fluoro-4-hydroxyphenyl)propane,
2,2-bis(3,5-dihydroxymethyl-4-hydroxyphenyl)propane,
9,9-bis(4-hydroxy-3-methylphenyl)fluorene,
1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene,
1,4-bis[2-(4-hydroxyphenyl)-2-propyl]benzene,
3,3-bis(4-hydroxyphenyl)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-ethyleneoxydiphenol,
1,4-bis(4-hydroxybenzoate)-3-methylbenzene,
4,4″-dihydroxy-3″-methyl-p-terphenyl,
4,4″-dihydroxy-3″-isopropyl-p-terphenyl,
2,2-dimethyl-1,3-bis(4-hydroxybenzoyloxy)propane,
2,2'-biphenol,
4,4′″-dihydroxy-p-quaterphenyl,
4,4-dihydroxydiphenyl ether,
Bis(4-hydroxyphenylthioethyl)ether bis(4-hydroxyphenyl)sulfone,
4-benzyloxy-4'-hydroxydiphenylsulfone,
4-(4-methylbenzyloxy)-4'-hydroxydiphenylsulfone,
4-(4-ethylbenzyloxy)-4'-hydroxydiphenylsulfone,
4-(4-n-propylbenzyloxy)-4'-hydroxydiphenylsulfone,
4-(4-isopropylbenzyloxy)-4'-hydroxydiphenylsulfone,
4-(4-n-butylbenzyloxy)-4'-hydroxydiphenylsulfone,
4-(4-isobutylbenzyloxy)-4'-hydroxydiphenylsulfone,
4-(4-sec-butylbenzyloxy)-4'-hydroxydiphenylsulfone,
4-(4-tert-butylbenzyloxy)-4'-hydroxydiphenylsulfone,
4-(3-methylbenzyloxy)-4'-hydroxydiphenylsulfone,
4-(3-ethylbenzyloxy)-4'-hydroxydiphenylsulfone,
4-(3-n-propylbenzyloxy)-4'-hydroxydiphenylsulfone,
4-(3-isopropylbenzyloxy)-4'-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'-hydroxydiphenylsulfone,
4-(2-isopropylbenzyloxy)-4'-hydroxydiphenylsulfone,
4-(2-n-butylbenzyloxy)-4'-hydroxydiphenylsulfone,
4-(2-isobutylbenzyloxy)-4'-hydroxydiphenylsulfone,
4-(2-sec-butylbenzyloxy)-4'-hydroxydiphenylsulfone,
4-(2-tert-butylbenzyloxy)-4'-hydroxydiphenylsulfone,
2,4'-dihydroxydiphenyl sulfone,
3,4'-dihydroxydiphenyl sulfone,
4-hydroxydiphenylsulfone,
4-methyl-4'-hydroxycyphenylsulfone,
4-ethyl-4'-hydroxydiphenylsulfone,
4-n-propyl-4'-hydroxydiphenylsulfone,
4-isopropyl-4'-hydroxydiphenylsulfone,
4-chloro-4'-hydroxydiphenylsulfone,
4-fluoro-4'-hydroxydiphenylsulfone,
4-chloro-2-methyl-4'-hydroxydiphenylsulfone,
4-methoxy-4'-hydroxydiphenylsulfone,
4-ethoxy-4'-hydroxydiphenylsulfone,
4-n-propoxy-4'-hydroxydiphenylsulfone,
4-isopropoxy-4'-hydroxydiphenylsulfone,
4-n-butoxy-4'-hydroxydiphenylsulfone,
4-isobutoxy-4'-hydroxydiphenylsulfone,
4-sec-butoxy-4'-hydroxydiphenylsulfone,
4-tert-butoxy-4'-hydroxydiphenylsulfone,
4-n-pentyloxy-4'-hydroxydiphenylsulfone,
4-isopentyloxy-4'-hydroxydiphenylsulfone,
4-(1-propenyloxy)-4'-hydroxydiphenylsulfone,
4-(2-propenyloxy)-4'-hydroxydiphenylsulfone,
4-benzyloxy-4'-hydroxydiphenylsulfone,
4-(β-phenoxyethoxy)-4'-hydroxydiphenylsulfone,
4-(β-phenoxypropoxyl)-4'-hydroxydiphenylsulfone,
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-methyldiphenylsulfone,
3,4,4'-trihydroxydiphenylsulfone,
bis(3,4-dihydroxyphenyl)sulfone,
2,3,4-trihydroxydiphenylsulfone,
4-isopropoxy-4'-hydroxydiphenylsulfone,
4-n-propoxy-4'-hydroxydiphenylsulfone,
4-allyloxy-4'-hydroxydiphenylsulfone,
4-benzyloxy-4'-hydroxydiphenylsulfone,
4-(2-propenyloxy)-4'-hydroxydiphenylsulfone,
3-benzyl-4-benzyloxy-4'-hydroxydiphenylsulfone,
3-phenethyl-4-phenethyloxy-4'-hydroxydiphenylsulfone,
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-hydroxyphenylsulfone)phenoxy}-p-xylene,
4,4'-{oxybis(ethylene oxide-p-phenylenesulfonyl)}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 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 trisphenol compounds, for example,
4,4′,4″-methylizinetrisphenol,
4,4′,4″-methylidine 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″-ethyridine trisphenol,
4,4′,4″-ethyridine tris(2-methylphenol),
4,4'-[(2-hydroxyphenyl)methylene]bis(2-cyclohexyl-5-methylphenol),
2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol,
2,4-bis[(2-hydroxy-5-methylphenyl)methyl]-6-cyclohexylphenol,
4,4'-[1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}methylidene]bisphenol,
4,4'-[1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bisphenol,
4,4'-[1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}propylidene]bisphenol,
4,4'-[1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}butylidene]bisphenol,
4,4'-[1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}pentylidene]bisphenol,
4,4'-[1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}hexylidene]bisphenol,
4,4'-[1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}heptylidene]bisphenol,
4,4'-[1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}isobutylidene]bisphenol,
4,4'-[1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}neopentylidene]bisphenol,
2,2′-[1-{4-[1-(2-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bisphenol,
3,3'-[1-{4-[1-(3-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bisphenol,
4,4'-[1-{4-[1-(3-fluoro-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis(2-fluorophenol),
4,4'-[1-{4-[1-(3-chloro-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis(2-chlorophenol),
4,4'-[1-{4-[1-(3-bromo-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis(2-bromophenol),
4,4'-[1-{4-[1-(4-hydroxy-3-methylphenyl)-1-methylethyl]phenyl}ethylidene]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}ethylidene]bis(2-tert-butylphenol),
4,4'-[1-{4-[1-(4-hydroxy-3-trifluoromethylphenyl)-1-methylethyl]phenyl}ethylidene]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-hydroxylphenyl)-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″-methylizinetrisphenol,
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}ethylidene]bis(2-tert-butylphenol),
4,4'-[1-{4-[1-(3,5-dimethyl-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]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}ethylidene]bis(2-cyclohexylphenol),
4,4'-[1-{4-[1-(3-fluoro-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bisphenol,
4,4'-[1-{4-[1-(3-fluoro-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis(2-methylphenol),
4,4'-[1-{4-[1-(3-fluoro-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]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″-methylidine tris(2,6-dimethylphenol),
α-(4-hydroxy-3-methylphenyl)-α,α′-bis(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene,
α'-(4-hydroxy-3-methylphenyl)-α,α-bis(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene,
α,α-bis(4-hydroxy-3-methylphenyl)-α′-(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene,
α,α′-bis(4-hydroxy-3-methylphenyl)-α-(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene,
1,1-bis(4-hydroxyphenyl)-4-[1-(4-hydroxyphenyl)-1-methylpropyl]cyclohexane,
2,6-bis[(3,5-dimethyl-4-hydroxyphenyl)methyl]-4-ethylphenol,
1,1'-bis(4-hydroxyphenyl)-4-[1-(4-hydroxyphenyl)propyl]cyclohexane,
1,1'-bis(4-hydroxy-3-methylphenyl)-4-[1-(4-hydroxyphenyl)propyl]cyclohexane,
1,1'-bis(3,5-dimethyl-4-hydroxyphenyl)-4-[1-(4-hydroxyphenyl)propyl]cyclohexane,
1-(4-hydroxyphenyl)-1-[4,4-bis(4-hydroxyphenyl)cyclohexyl]-4-isopropylcyclohexane,
4,4'-[3-(2,5-dimethyl-4-hydroxyphenyl)butylene]bis(2,5-dimethylphenol),
1,3,5-tri(4-hydroxy-3-phenylphenyl)adamantane,
1,3,5-tri(3-cyclohexyl-4-hydroxyphenyl)adamantane,
2,4-bis[(3,5-dimethyl-4-hydroxyphenyl)methyl]-6-cyclohexylphenol,
2,6-bis[(2,5-dimethyl-4-hydroxyphenyl)methyl]-4-cyclohexylphenol,
2,4-bis[(3-cyclohexyl-4-hydroxyphenyl)methyl]-6-methylphenol,
2,4-bis[(4-hydroxy-2,3,5-trimethylphenyl)methyl]-6-cyclohexylphenol,
2,6-bis[(5-fluoro-2-hydroxyphenyl)methyl]-4-fluorophenol,
2,6-bis[(3-fluoro-4-hydroxyphenyl)methyl]-4-fluorophenol,
2,4-bis[(3-fluoro-4-hydroxyphenyl)methyl]-6-methylphenol,
4,4'-[3-(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3-biphenylpropylidene]bis(5-cyclohexyl-2-methylphenol),
4,4'-[3-(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropylidene]bis(2,5-dimethylphenol),
2,4-bis[(2,5-dimethyl-4-hydroxyphenyl)methyl]-6-methylphenol, 1,1,2-tris(4-hydroxyphenyl)ethane,
1,1,3-tris(4-hydroxyphenyl)propane, 1,1,4-tris(4-hydroxyphenyl)butane,
1,2,2-tris(4-hydroxyphenyl)propane, 1,2,2-tris(4-hydroxyphenyl)butane,
1,2,2-tris(4-hydroxyphenyl)pentane, 1,2,2-tris(4-hydroxyphenyl)hexane,
1,2,2-tris(4-hydroxyphenyl)heptane, 1,2,2-tris(4-hydroxyphenyl)octane,
1,2,2-tris(4-hydroxyphenyl)-3-methylbutane 1,2,2-tris(4-hydroxyphenyl)-3,3-dimethylbutane,
1,2,2-tris(4-hydroxyphenyl)-4,4-dimethylpentane, 1,3,3-tris(4-hydroxyphenyl)butane,
1,3,3-tris(4-hydroxyphenyl)pentane, 1,3,3-tris(4-hydroxyphenyl)hexane,
1,3,3-tris(4-hydroxyphenyl)heptane, 1,3,3-tris(4-hydroxyphenyl)octane,
1,3,3-tris(4-hydroxyphenyl)nonane, 1,4,4-tris(4-hydroxyphenyl)pentane,
1,4,4-tris(4-hydroxyphenyl)hexane, 1,4,4-tris(4-hydroxyphenyl)heptane,
1,4,4-tris(4-hydroxyphenyl)octane, 1,4,4-tris(4-hydroxyphenyl)nonane,
1,4,4-tris(4-hydroxyphenyl)decane, 1,2,2-tris(2-hydroxyphenyl)propane,
1,1,2-tris(3-hydroxyphenyl)propane,
1-(4-hydroxyphenyl)-2,2-bis(2-hydroxyphenyl)propane,
1,2,2-tris(3-fluoro-4-hydroxyphenyl)propane,
1,2,2-tris(3-chloro-4-hydroxyphenyl)propane,
1,2,2-tris(3-bromo-4-hydroxyphenyl)propane,
2,2-bis(3-ethyl-4-hydroxyphenyl)-1-(4-hydroxyphenyl)propane,
2,2-bis(3-tert-butyl-4-hydroxyphenyl)-1-(4-hydroxyphenyl)propane,
2,2-bis(2-hydroxy-3-biphenylyl)-1-(4-hydroxyphenyl)propane,
2,2-bis(3-trifluoromethyl-4-hydroxyphenyl)-1-(4-hydroxyphenyl)propane,
2-(3-methyl-4-hydroxyphenyl)-1,2-bis(4-hydroxyphenyl)propane,
1-(3-methyl-4-hydroxyphenyl)-2,2-bis(4-hydroxyphenyl)propane,
3-(3-methyl-4-hydroxyphenyl)-1,3-bis(4-hydroxyphenyl)butane,
1-(3-methyl-4-hydroxyphenyl)-3,3-bis(4-hydroxyphenyl)butane,
4-(3-methyl-4-hydroxyphenyl)-1,4-bis(4-hydroxyphenyl)pentane,
1-(3-methyl-4-hydroxyphenyl)-4,4-bis(4-hydroxyphenyl)pentane,
1,2-bis(3-methyl-4-hydroxyphenyl)-2-(4-hydroxyphenyl)propane,
3,3-bis(3-methyl-4-hydroxyphenyl)-1-(4-hydroxyphenyl)butane,
1,3-bis(3-methyl-4-hydroxyphenyl)-3-(4-hydroxyphenyl)butane,
4,4-bis(3-methyl-4-hydroxyphenyl)-1-(4-hydroxyphenyl)pentane,
1,4-bis(3-methyl-4-hydroxyphenyl)-4-(4-hydroxyphenyl)pentane,
1,1,2-tris(3-methyl-4-hydroxyphenyl)ethane,
1,2,2-tris(3-methyl-4-hydroxyphenyl)propane,
1,1,3-tris(3-methyl-4-hydroxyphenyl)propane,
1,3,3-tris(3-methyl-4-hydroxyphenyl)butane,
1,1,4-tris(3-methyl-4-hydroxyphenyl)butane,
1,4,4-tris(3-methyl-4-hydroxyphenyl)pentane,
4,4'-[4-(4-hydroxyphenyl)-sec-butylidene]bis(2-methylphenol)
etc. can be exemplified.

Examples of compounds having four or more phenolic hydroxyl groups include:
bis[2-hydroxy-3-(2-hydroxy-5-methylbenzyl)-5-methylphenyl]methane,
4,6-bis[(4-hydroxyphenyl)methyl)-1,3-benzenediol,
4,4'-[(3,4-dihydroxyphenyl)methylene]bis(2,6-dimethylphenol),
4,4'-[(3,4-dihydroxyphenyl)methylene]bis(2-cyclohexyl-5-methylphenol),
4,4'-[(3,4-dihydroxyphenyl)methylene]bis(2-methylphenol),
4,4'-[(3,4-dihydroxyphenyl)methylene]bis(2,3,6-trimethylphenol),
1,1,2,2-tetrakis(4-hydroxyphenyl)ethane,
1,1,2,2-tetrakis(4-hydroxy-3-methylphenyl)ethane,
1,1,2,2-tetrakis(3,5-dimethyl-4-hydroxyphenyl)ethane,
α,α′,4α″,α′″-tetrakis(3,5-dimethyl-4-hydroxyphenyl)-1,4-dimethylbenzene,
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)-1,4-dimethylbenzene,
bis[3-(3,6-dimethyl-2-hydroxybenzyl)-2-hydroxy-5-methylphenyl]methane,
[3-(3,6-dimethyl-2-hydroxybenzyl)-2-hydroxy-5-methylphenyl],
[3-(2,5-dimethyl-4-hydroxybenzyl)-2-hydroxy-5-methylphenyl]methane,
bis[3-(2,5-dimethyl-4-hydroxybenzyl)-2-hydroxy-5-methylphenyl]methane,
bis[3-(3,5-dimethyl-4-hydroxybenzyl)-2-hydroxy-5-methylphenyl]methane,
bis[3-(2-hydroxy-3,4,6-trimethylbenzyl)-2-hydroxy-5-methylphenyl]methane,
bis[2-hydroxy-3-(4-hydroxy-2,3,5-trimethylbenzyl)-5-methylphenyl]methane,
4,4',4'',4'''-tetrakis(4-hydroxyphenyl)-1,1'-bicyclohexyl,
2,2'-bis[4,4-bis(4-hydroxyphenyl)cyclohexyl]propane,
4,4',4'',4'''-tetrakis(4-hydroxy-3-methylphenyl)-1,1'-bicyclohexyl,
bis[3-(5-cyclohexyl-4-hydroxy-2-methylbenzyl)-4-hydroxy-5-methylphenyl]methane,
4,4',4'',4'''-tetrakis(3,5-dimethyl-4-hydroxyphenyl)-1,1'-bicyclohexyl,
1,1-bis[3-(2-hydroxy-5-methylbenzyl)-5-cyclohexyl-4-hydroxyphenyl]cyclohexane,
1,1-bis[3-(3,5-dimethyl-4-hydroxybenzyl)-5-cyclohexyl-4-hydroxyphenyl]cyclohexane,
1,1-bis[3-(5-cyclohexyl-4-hydroxy-2-methylbenzyl)-5-cyclohexyl-4-hydroxyphenyl]cyclohexane,
4,6-bis[α-methyl-(4-hydroxyphenyl)benzyl-1,3-benzenediol,
2,2-bis[3-(4-hydroxy-3-methylbenzyl)-4-hydroxy-5-methylphenyl]propane,
2,6-bis[(3,5-dimethyl-4-hydroxyphenyl)benzyl]-4-[α-methyl-(3,5-dimethyl-4-hydroxyphenyl)benzyl]phenol,
4,4',4'',4'''-tetrakis(4-hydroxy-3-isopropylphenyl)-1,1'-bicyclohexyl,
4,4'-bis[(3,4-dihydroxyphenyl)methylene]bis(2-isopropylphenol),
2,4,6-tris(4-hydroxybenzyl)-1,3-benzenediol,
4,6-bis(3,5-dimethyl-4-hydroxybenzyl)pyrogallol,
3,3'-[(2-hydroxyphenyl)methylene]bis(5-methylcatechol),
2,6-bis(2,4-dihydroxybenzyl)-4-ethylphenol,
2,4-bis(2,4-dihydroxybenzyl)-6-cyclohexylphenol,
2,6-bis(5-tert-butyl-2,3-dihydroxybenzyl)-4-methylphenol,
2,4,6-tris(3,5-dimethyl-4-hydroxybenzyl)resorcin,
2,4,6-tris(3,5-dimethyl-2-hydroxybenzyl)resorcin,
2,6-bis(2,4-dihydroxybenzyl)-3,4-dimethylphenol,
2,6-bis[3-(2-hydroxy-5-methylbenzyl)-2,5-dimethyl-4-hydroxybenzyl]-3,4-dimethylphenol,
4,6-bis(α-methyl-4-hydroxybenzyl)pyrogallol,
4,4'-[1-{4-[1-(3,5-bis(4-hydroxybenzyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[2,6-bis( 4-hydroxybenzyl)phenol],
4,4'-[1-{4-[1-(3,5-bis(4-hydroxy-3-methylbenzyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]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}ethylidene]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}ethylidene] 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″-ethylidine tris {[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}ethylidene]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}ethylidene]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}ethylidene]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}ethylidene]bis[ 2,6-bis(3,5-dimethyl-2-hydroxyphenyl)phenol],
4,4'-[1-{4-[1-(3,5-bis(4-hydroxy-3-isopropylphenyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[2, 6-bis(4-hydroxy-3-isopropylphenyl)phenol],
bis[3-(α,α-bis(3,5-dimethyl-4-hydroxyphenyl)methyl-4-hydroxyphenyl]methane,
bis[3-(α,α-bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)methyl-4-hydroxyphenyl]methane,
4,4'-[4-hydroxy-3,5-bis(2-hydroxybenzyl)methylene]bis[2,6-bis(2-hydroxybenzyl)]phenol,
4,4'-[4-hydroxy-3,5-bis(4-hydroxybenzyl)methylene]bis[2,6-bis(4-hydroxybenzyl)]phenol,
4,4',4''-ethylidine tris [2,6-bis(2-hydroxybenzyl)phenol],
4,4′,4″-ethylidine tris [2,6-bis(4-hydroxybenzyl)phenol],
2,2-bis[3,5-bis(4-hydroxy-3-methylbenzyl)-4-hydroxyphenyl]propane,
1,8,15,22-tetraethyl-3,5,10,12,17,19,24,26-octahydroxy[1,1,1,1]-metacyclophane,
α,α′,α″,α′″-tetrakis(3,5-dimethyl-4-hydroxyphenyl)-1,4-dimethylbenzene,
4,4'-[1-{4-[1-(3,5-bis(2-hydroxy-5-isopropylphenyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[2, 6-bis(2-hydroxy-5-isopropylphenyl)phenol],
4,4'-[1-{4-[1-(3,5-bis(4-hydroxy-2,3,5-trimethylphenyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene] Bis[2,6-bis(4-hydroxy-2,3,5-trimethylphenyl)phenol],
4,4'-[1-{4-[1-(3,5-bis(3-sec-butyl-4-hydroxyphenyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]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}ethylidene]bis[ 2,6-bis(3-tert-butyl-4-hydroxyphenyl)phenol],
2,6-bis{[3-(2,4-dihydroxybenzyl)-2,5-dimethyl-4-hydroxy]benzyl}-4-methylphenol,
1,1-bis[5-(2,4-dihydroxybenzyl)-3-cyclohexyl-4-hydroxyphenyl]cyclohexane,
1,1-bis[5-(2,3,4-trihydroxybenzyl)-3-cyclohexyl-4-hydroxyphenyl]cyclohexane,
Examples include 2,2-bis[4,4',4'',4''-tetrakis(3,5-dihydroxymethyl-4-hydroxyphenyl)cyclohexyl]propane.

Examples of carboxylic acids and derivatives thereof include:
3,5-di(α-methylbenzyl)salicylic acid,
4-(2-p-methoxyphenyloxyethoxy) salicylic acid,
4-hydroxyphenylbenzoic acid,
4-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-distyrenated salicylic acid,
N-(p-toluenesulfonyl)-glycine,
N-(p-toluenesulfonyl)-alanine,
N-(p-toluenesulfonyl)-β-alanine,
N-phenylaminocarbonyl-glycine,
N-phenylaminocarbonyl-valine,
N-(m-tolylaminocarbonyl)-phenylalanine,
N-(m-tolylaminocarbonyl)-cysteine-S-benzyl,
N-(m-tolylaminocarbonyl)-methionine,
N-(m-tolylaminocarbonyl)-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,
2-O-(phenylaminocarbonyl)-mandelic acid,
2-O-(p-tolylaminocarbonyl)-mandelic acid,
2-O-(m-tolylaminocarbonyl)-mandelic acid,
2-O-(o-tolylaminocarbonyl)-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,
Examples include 2-O-(phenethylaminocarbonyl)-lactic acid.

Examples of acidic phosphoric acid ester compounds 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 acid phosphate. Examples include acid phosphate, monobutyl phosphate, dibutyl phosphate, monoisodecyl phosphate, and bis(2-ethylhexyl) phosphate.

The component (c) of the reaction medium that reversibly causes the electron transfer reaction between the component (a) and the component (b) in a specific temperature range will be explained.
Examples of the component (c) include alcohols, esters, ketones, ethers, and acid amides.
When the reversible thermochromic composition of the present invention is applied to secondary processing by encapsulating it in microcapsules, it is necessary to stably retain it within the capsule, since the low molecular weight composition evaporates outside the capsule when subjected to high heat treatment. Therefore, compounds having 10 or more carbon atoms are preferably used.

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

As the esters, esters having 10 or more carbon atoms are effective, and any combination of a monohydric carboxylic acid having an aliphatic and alicyclic ring or an aromatic ring and a monohydric alcohol having an aliphatic ring and an alicyclic ring or an aromatic ring is effective. Esters, aliphatic and alicyclic acids obtained from any combination of aliphatic and alicyclic or aromatic ring-containing polyhydric carboxylic acids and aliphatic and alicyclic or aromatic ring-containing monohydric alcohols. Alternatively, examples include esters obtained from any combination of a monovalent carboxylic acid having an aromatic ring and a polyhydric alcohol having an aliphatic and alicyclic ring or an aromatic ring, such as ethyl caprylate, octyl caprylate, and stearyl caprylate. , myristyl caprate, docosyl caprate, 2-ethylhexyl laurate, n-decyl laurate, 3-methylbutyl myristate, cetyl myristate, isopropyl palmitate, neopentyl palmitate, nonyl palmitate, cyclohexyl palmitate, n stearate -Butyl, 2-methylbutyl stearate, 3,5,5-trimethylhexyl stearate, n-undecyl stearate, pentadecyl stearate, stearyl stearate, cyclohexylmethyl stearate, isopropyl behenate, hexyl behenate, lauryl behenate , behenyl behenate, cetyl benzoate, stearyl 4-tert-butylbenzoate, dimyristyl phthalate, distearyl phthalate, dimyristyl oxalate, dicetyl oxalate, dicetyl malonate, dilauryl succinate, dilauryl glutarate, diundecyl adipate , dilauryl azelate, di-(n-nonyl) sebacate, dineopentyl 1,18-octadecylmethylenedicarboxylate, ethylene glycol dimyristate, propylene glycol dilaurate, propylene glycol distearate, hexylene glycol dipalmitate, 1, 5-pentanediol distearate, 1,2,6-hexanetriol trimyristate, 1,4-cyclohexanediol didecyl, 1,4-cyclohexanedimethanol dimyristate, xylene glycol dicaprinate, xylene glycol distear Rates etc. can be exemplified.

Also effective are esters of saturated fatty acids and branched aliphatic alcohols, and ester compounds of unsaturated fatty acids or saturated fatty acids with branches or substituents and aliphatic alcohols that are branched or have 16 or more carbon atoms. be.
Examples of the ester compounds include 2-ethylhexyl butyrate, 2-ethylhexyl behenate, 2-ethylhexyl myristate, 2-ethylhexyl caprate, 3,5,5-trimethylhexyl laurate, and 3,5,5-palmitate. Trimethylhexyl, 3,5,5-trimethylhexyl stearate, 2-methylbutyl caproate, 2-methylbutyl caprylate, 2-methylbutyl caprate, 1-ethylpropyl palmitate, 1-ethylpropyl stearate, 1-behenate Ethylpropyl, 1-ethylhexyl laurate, 1-ethylhexyl myristate, 1-ethylhexyl palmitate, 2-methylpentyl caproate, 2-methylpentyl caprylate, 2-methylpentyl caprate, 2-methylpentyl laurate, stearin 2-methylbutyl stearate, 2-methylbutyl stearate, 3-methylbutyl stearate, 1-methylheptyl stearate, 2-methylbutyl behenate, 3-methylbutyl behenate, 1-methylheptyl stearate, 1-methylheptyl behenate, 1-ethylpentyl caproate, 1-ethylpentyl palmitate, 1-methylpropyl stearate, 1-methyloctyl stearate, 1-methylhexyl stearate, 1,1-dimethylpropyl laurate, 1-methylpentyl caprate , 2-methylhexyl palmitate, 2-methylhexyl stearate, 2-methylhexyl behenate, 3,7-dimethyloctyl laurate, 3,7-dimethyloctyl myristate, 3,7-dimethyloctyl palmitate, stearin 3,7-dimethyloctyl acid, 3,7-dimethyloctyl behenate, stearyl oleate, behenyl oleate, stearyl linoleate, behenyl linoleate, 3,7-dimethyloctyl erucate, stearyl erucate, isostearyl erucate , cetyl isostearate, stearyl isostearate, 2-methylpentyl 12-hydroxystearate, 2-ethylhexyl 18-bromostearate, isostearyl 2-ketomyristate, 2-ethylhexyl 2-fluoromyristate, cetyl butyrate, stearyl butyrate , behenyl butyrate, and the like.

Furthermore, in order to show a large hysteresis characteristic with respect to the color density-temperature curve and change color, and to provide color memory depending on temperature changes, it is necessary to Carboxylic acid ester compounds exhibiting a ΔT value (melting point - clouding point), for example, carboxylic acid esters containing substituted aromatic rings in the molecule, carboxylic acids containing unsubstituted aromatic rings, and aliphatic alcohols having 10 or more carbon atoms. Esters, carboxylic acid esters containing a cyclohexyl group in the molecule, esters of fatty acids with 6 or more carbon atoms and unsubstituted aromatic alcohols or phenols, esters of fatty acids with 8 or more carbon atoms and branched aliphatic alcohols, dicarboxylic acids and aromatic esters with group alcohols or branched aliphatic alcohols, dibenzyl cinnamate, heptyl stearate, didecyl adipate, dilauryl adipate, dimyristyl adipate, dicetyl adipate, distearyl adipate, trilaurin, trimyristin, tristearin, di- Examples include myristicin and distearin.

In addition, a fatty acid ester compound obtained from an odd-numbered aliphatic monohydric alcohol having 9 or more carbon atoms and an even-numbered aliphatic carboxylic acid, n-pentyl alcohol or n-heptyl alcohol, and an even-numbered aliphatic monohydric alcohol having 10 to 16 carbon atoms. Fatty acid ester compounds having a total of 17 to 23 carbon atoms obtained from aliphatic carboxylic acids are also effective.
Examples of the fatty acid ester compounds include n-pentadecyl acetate, n-tridecyl butyrate, n-pentadecyl butyrate, n-undecyl caproate, n-tridecyl caproate, n-pentadecyl caproate, n-nonyl caprylate, and caprylic acid. n-undecyl, n-tridecyl caprylate, n-pentadecyl caprylate, n-heptyl caprate, n-nonyl caprate, n-undecyl caprate, n-tridecyl caprate, n-pentadecyl caprate, n- laurate Pentyl, n-heptyl laurate, n-nonyl laurate, n-undecyl laurate, n-tridecyl laurate, n-pentadecyl laurate, n-pentyl myristate, n-heptyl myristate, n-nonyl myristate, n-undecyl myristate, n-tridecyl myristate, n-pentadecyl myristate, n-pentyl palmitate, n-heptyl palmitate, n-nonyl palmitate, n-undecyl palmitate, n-tridecyl palmitate, palmitic acid n-pentadecyl, n-nonyl stearate, n-undecyl stearate, n-tridecyl stearate, n-pentadecyl stearate, n-nonyl eicosanoate, n-undersi eicosanoate, n-tridecyl eicosanoate, n- eicosanoate Examples include pentadecyl, n-nonyl behenate, n-undecyl behenate, n-tridecyl behenate, and n-pentadecyl behenate.

As the ketones, aliphatic ketones having a total carbon number of 10 or more are effective, such as 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, laurone, stearone and the like.
Furthermore, arylalkyl ketones having a total carbon number of 12 to 24, such as n-octadecanophenone, n-heptadecanophenone, n-hexadecanophenone, n-pentadecanophenone, n-tetradecanophenone, Nophenone, 4-n-dodecaacetophenone, n-tridecanophenone, 4-n-undecanoacetophenone, n-laurophenone, 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, cyclohexyl phenyl ketone, benzyl-n-butyl ketone, 4-n-butylacetophenone, n-hexanophenone, 4-isobutylacetophenone, 1-acetonaphthone, 2-acetonaphthone, cyclopentylphenyl Examples include ketones.

As the ethers, aliphatic ethers having a total carbon number of 10 or more are effective, such as dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, dinonyl ether, didecyl ether, diundecyl ether, and didodecyl ether. , ditridecyl 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 exemplified.

Examples of acid amides include acetamide, propionic acid amide, butyric acid amide, caproic acid amide, caprylic acid amide, capric acid amide, lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, and oleic acid amide. Acid amide, erucic acid amide, benzamide, caproic acid anilide, caprylic acid anilide, capric acid anilide, lauric acid anilide, myristic acid anilide, palmitic acid anilide, stearic acid anilide, behenic acid anilide, oleic acid anilide, erucic acid anilide, capron Acid N-methylamide, caprylic acid N-methylamide, capric acid N-methylamide, lauric acid N-methylamide, myristic acid N-methylamide, palmitic acid N-methylamide, stearic acid N-methylamide, behenic acid N-methylamide, oleic acid N-methylamide - Methylamide, erucic acid N-methylamide, lauric acid N-ethylamide, myristic acid N-ethylamide, palmitic acid N-ethylamide, stearic acid N-ethylamide, oleic acid N-ethylamide, lauric acid N-butylamide, myristic acid N-butylamide , palmitic acid N-butylamide, stearic acid N-butylamide, oleic acid N-butylamide, lauric acid N-octylamide, myristic acid N-octylamide, palmitic acid N-octylamide, stearic acid N-octylamide, oleic acid N-octylamide -Octylamide, lauric acid N-dodecylamide, myristic acid N-dodecylamide, palmitic acid N-dodecylamide, stearic acid N-dodecylamide, oleic acid N-dodecylamide, dilauric acid amide, dimiristic acid amide, dipalmitin Acid amide, distearamide, dioleic acid amide, trilauric acid amide, trimyristic acid amide, tripalmitic acid amide, tristearic acid amide, trioleic acid amide, succinic acid amide, adipic acid amide, glutaric acid amide, malonic acid amide , azelaic acid amide, maleic acid amide, succinic acid N-methylamide, adipic acid N-methylamide, glutaric acid N-methylamide, malonic acid N-methylamide, azelaic acid N-methylamide, succinic acid N-ethylamide, adipic acid N-ethylamide , glutaric acid N-ethylamide, malonic acid N-ethylamide, azelaic acid N-ethylamide, succinic acid N-butylamide, adipic acid N-butylamide, glutaric acid N-butylamide, malonic acid N-butylamide, adipic acid N-octylamide, Examples include adipic acid N-dodecylamide.

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

（式中、Ｒは炭素数８以上のアルキル基又はアルケニル基を示し、好ましくは炭素数１０～２４のアルキル基であり、より好ましくは炭素数１２～２２のアルキル基である。）
式（４）で示される化合物としては、例えば、オクタン酸４－ベンジルオキシフェニルエチル、ノナン酸４－ベンジルオキシフェニルエチル、デカン酸４－ベンジルオキシフェニルエチル、ウンデカン酸４－ベンジルオキシフェニルエチル、ドデカン酸４－ベンジルオキシフェニルエチル、トリデカン酸４－ベンジルオキシフェニルエチル、テトラデカン酸４－ベンジルオキシフェニルエチル、ペンタデカン酸４－ベンジルオキシフェニルエチル、ヘキサデカン酸４－ベンジルオキシフェニルエチル、ヘプタデカン酸４－ベンジルオキシフェニルエチル、オクタデカン酸４－ベンジルオキシフェニルエチル等を例示できる。 Furthermore, the component (iii) may be a compound represented by the following formula (3).

[In the formula, R ₁ represents a hydrogen atom or a methyl group, m represents an integer of 0 to 2, and either one of X ₁ and X ₂ is -(CH ₂ ) _n OCOR ₂ or -(CH ₂ ) _n COOR ₂ , the other represents a hydrogen atom, n represents an integer of 0 to 2, R ₂ represents an alkyl group or alkenyl group having 4 or more carbon atoms, Y ₁ and Y ₂ each independently represent a hydrogen atom, It represents an alkyl group having 1 to 4 carbon atoms, a methoxy group, or a halogen atom, and r and p each independently represent an integer of 1 to 3. ]
Among the compounds represented by formula (3), it is preferable that R ₁ is a hydrogen atom because a reversible thermochromic composition having a wider hysteresis width can be obtained, and furthermore, R ₁ is a hydrogen atom, and m is The case of 0 is more preferable.
Note that among the compounds represented by formula (3), a compound represented by formula (4) below is more preferred.

(In the formula, R represents an alkyl group or an alkenyl group having 8 or more carbon atoms, preferably an alkyl group having 10 to 24 carbon atoms, and more preferably an alkyl group having 12 to 22 carbon atoms.)
Examples of the compound represented by formula (4) include 4-benzyloxyphenylethyl octoate, 4-benzyloxyphenylethyl nonanoate, 4-benzyloxyphenylethyl decanoate, 4-benzyloxyphenylethyl undecanoate, and dodecane. 4-benzyloxyphenylethyl acid, 4-benzyloxyphenylethyl tridecanoate, 4-benzyloxyphenylethyl tetradecanoate, 4-benzyloxyphenylethyl pentadecanoate, 4-benzyloxyphenylethyl hexadecanoate, 4-benzyloxy heptadecanoate Examples include phenylethyl and 4-benzyloxyphenylethyl octadecanoate.

（式中、Ｒは炭素数８以上のアルキル基又はアルケニル基を示し、ｍ及びｎはそれぞれ独立して、１～３の整数を示し、Ｘ及びＹはそれぞれ独立して、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す。）
式（５）で示される化合物としては、例えば、オクタン酸１，１－ジフェニルメチル、ノナン酸１，１－ジフェニルメチル、デカン酸１，１－ジフェニルメチル、ウンデカン酸１，１－ジフェニルメチル、ドデカン酸１，１－ジフェニルメチル、トリデカン酸１，１－ジフェニルメチル、テトラデカン酸１，１－ジフェニルメチル、ペンタデカン酸１，１－ジフェニルメチル、ヘキサデカン酸１，１－ジフェニルメチル、ヘプタデカン酸１，１－ジフェニルメチル、オクタデカン酸１，１－ジフェニルメチル等を例示できる。 Furthermore, the component (iii) may be a compound represented by the following formula (5).

(In the formula, R represents an alkyl group or an alkenyl group having 8 or more carbon atoms, m and n each independently represent an integer of 1 to 3, and X and Y each independently represent a hydrogen atom, a carbon number Indicates either an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom.)
Examples of the compound represented by formula (5) include 1,1-diphenylmethyl octoate, 1,1-diphenylmethyl nonanoate, 1,1-diphenylmethyl decanoate, 1,1-diphenylmethyl undecanoate, and dodecane. 1,1-diphenylmethyl acid, 1,1-diphenylmethyl tridecanoate, 1,1-diphenylmethyl tetradecanoate, 1,1-diphenylmethyl pentadecanoate, 1,1-diphenylmethyl hexadecanoate, 1,1-heptadecanoate Examples include diphenylmethyl and 1,1-diphenylmethyl octadecanoate.

（式中、Ｘは水素原子、炭素数１～４のアルキル基、メトキシ基、ハロゲン原子のいずれかを示し、ｍは１～３の整数を示し、ｎは１～２０の整数を示す。）
式（６）で示される化合物としては、例えば、マロン酸と２－〔４－(４－クロロベンジルオキシ）フェニル〕エタノールとのジエステル、こはく酸と２－（４－ベンジルオキシフェニル）エタノールとのジエステル、こはく酸と２－〔４－(３－メチルベンジルオキシ）フェニル〕エタノールとのジエステル、グルタル酸と２－（４－ベンジルオキシフェニル）エタノールとのジエステル、グルタル酸と２－〔４－(４－クロロベンジルオキシ）フェニル〕エタノールとのジエステル、アジピン酸と２－（４－ベンジルオキシフェニル）エタノールとのジエステル、ピメリン酸と２－（４－ベンジルオキシフェニル）エタノールとのジエステル、スベリン酸と２－（４－ベンジルオキシフェニル）エタノールとのジエステル、スベリン酸と２－〔４－(３－メチルベンジルオキシ）フェニル〕エタノールとのジエステル、スベリン酸と２－〔４－(４－クロロベンジルオキシ）フェニル〕エタノールとのジエステル、スベリン酸と２－〔４－(２，４－ジクロロベンジルオキシ）フェニル〕エタノールとのジエステル、アゼライン酸と２－（４－ベンジルオキシフェニル）エタノールとのジエステル、セバシン酸と２－（４－ベンジルオキシフェニル）エタノールとのジエステル、１，１０－デカンジカルボン酸と２－（４－ベンジルオキシフェニル）エタノールとのジエステル、１，１８-オクタデカンジカルボン酸と２－（４－ベンジルオキシフェニル）エタノールとのジエステル、１，１８－オクタデカンジカルボン酸と２－〔４－(２－メチルベンジルオキシ）フェニル〕エタノールとのジエステル等を例示できる。 Furthermore, the component (iii) may be a compound represented by the following formula (6).

(In the formula, X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, or a halogen atom, m represents an integer of 1 to 3, and n represents an integer of 1 to 20.)
Examples of the compound represented by formula (6) include diesters of malonic acid and 2-[4-(4-chlorobenzyloxy)phenyl]ethanol, and diesters of succinic acid and 2-(4-benzyloxyphenyl)ethanol. Diester, diester of succinic acid and 2-[4-(3-methylbenzyloxy)phenyl]ethanol, diester of glutaric acid and 2-(4-benzyloxyphenyl)ethanol, glutaric acid and 2-[4-( Diester with 4-chlorobenzyloxy)phenyl]ethanol, diester with adipic acid and 2-(4-benzyloxyphenyl)ethanol, diester with pimelic acid and 2-(4-benzyloxyphenyl)ethanol, and diester with suberic acid. Diester with 2-(4-benzyloxyphenyl)ethanol, diester with suberic acid and 2-[4-(3-methylbenzyloxy)phenyl]ethanol, diester with suberic acid and 2-[4-(4-chlorobenzyloxy) ) phenyl]ethanol, diester of suberic acid and 2-[4-(2,4-dichlorobenzyloxy)phenyl]ethanol, azelaic acid and 2-(4-benzyloxyphenyl)ethanol, diester of sebacin Diester of acid and 2-(4-benzyloxyphenyl)ethanol, diester of 1,10-decanedicarboxylic acid and 2-(4-benzyloxyphenyl)ethanol, diester of 1,18-octadecanedicarboxylic acid and 2-(4-benzyloxyphenyl)ethanol -benzyloxyphenyl)ethanol, diesters of 1,18-octadecanedicarboxylic acid and 2-[4-(2-methylbenzyloxy)phenyl]ethanol, and the like.

（式中、Ｒは炭素数１～２１のアルキル基又はアルケニル基を示し、ｎは１～３の整数を示す。）
式（７）で示される化合物としては、例えば、１，３－ビス（２－ヒドロキシエトキシ）ベンゼンとカプリン酸とのジエステル、１，３－ビス（２－ヒドロキシエトキシ）ベンゼンとウンデカン酸とのジエステル、１，３－ビス（２－ヒドロキシエトキシ）ベンゼンとラウリン酸とのジエステル、１，３－ビス（２－ヒドロキシエトキシ）ベンゼンとミリスチン酸とのジエステル、１，４－ビス（ヒドロキシメトキシ）ベンゼンと酪酸とのジエステル、１，４－ビス（ヒドロキシメトキシ）ベンゼンとイソ吉草酸とのジエステル、１，４－ビス（２－ヒドロキシエトキシ）ベンゼンと酢酸とのジエステル、１，４－ビス（２－ヒドロキシエトキシ）ベンゼンとプロピオン酸とのジエステル、１，４－ビス（２－ヒドロキシエトキシ）ベンゼンと吉草酸とのジエステル、１，４－ビス（２－ヒドロキシエトキシ）ベンゼンとカプロン酸とのジエステル、１，４－ビス（２－ヒドロキシエトキシ）ベンゼンとカプリル酸とのジエステル、１，４－ビス（２－ヒドロキシエトキシ）ベンゼンとカプリン酸とのジエステル、１，４－ビス（２－ヒドロキシエトキシ）ベンゼンとラウリン酸とのジエステル、１，４－ビス（２－ヒドロキシエトキシ）ベンゼンとミリスチン酸とのジエステル等を例示できる。 Furthermore, the component (iii) may be a compound represented by the following formula (7).

(In the formula, R represents an alkyl group or alkenyl group having 1 to 21 carbon atoms, and n represents an integer of 1 to 3.)
Examples of the compound represented by formula (7) include a diester of 1,3-bis(2-hydroxyethoxy)benzene and capric acid, and a diester of 1,3-bis(2-hydroxyethoxy)benzene and undecanoic acid. , diester of 1,3-bis(2-hydroxyethoxy)benzene and lauric acid, diester of 1,3-bis(2-hydroxyethoxy)benzene and myristic acid, 1,4-bis(hydroxymethoxy)benzene and Diester of 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-hydroxy) diester of 1,4-bis(2-hydroxyethoxy)benzene and propionic acid, diester of 1,4-bis(2-hydroxyethoxy)benzene and valeric acid, diester of 1,4-bis(2-hydroxyethoxy)benzene and caproic acid, 1, Diester of 4-bis(2-hydroxyethoxy)benzene and caprylic acid, diester of 1,4-bis(2-hydroxyethoxy)benzene and capric acid, 1,4-bis(2-hydroxyethoxy)benzene and laurin Examples include diesters with acids, diesters with 1,4-bis(2-hydroxyethoxy)benzene and myristic acid, and the like.

（式中、Ｘ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、ｍは１～３の整数を示し、ｎは１～２０の整数を示す。）
式（８）で示される化合物としては、例えば、こはく酸と２－フェノキシエタノールとのジエステル、スベリン酸と２－フェノキシエタノールとのジエステル、セバシン酸と２－フェノキシエタノールとのジエステル、１，１０－デカンジカルボン酸と２－フェノキシエタノールとのジエステル、１，１８－オクタデカンジカルボン酸と２－フェノキシエタノールとのジエステル等を例示できる。 Furthermore, the component (iii) may be a compound represented by the following formula (8).

(In the formula, X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom; )
Examples of the compound represented by formula (8) include diester of succinic acid and 2-phenoxyethanol, diester of suberic acid and 2-phenoxyethanol, diester of sebacic acid and 2-phenoxyethanol, and 1,10-decanedicarboxylic acid. and 2-phenoxyethanol, and 1,18-octadecanedicarboxylic acid and 2-phenoxyethanol.

（式中、Ｒ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、ｎは０又は１を示す。）
式（９）で示される化合物としては、例えば、４－フェニル安息香酸デシル、４－フェニル安息香酸ラウリル、４－フェニル安息香酸ミリスチル、４－フェニル安息香酸シクロヘキシルエチル、４－ビフェニル酢酸オクチル、４－ビフェニル酢酸ノニル、４－ビフェニル酢酸デシル、４－ビフェニル酢酸ラウリル、４－ビフェニル酢酸ミリスチル、４－ビフェニル酢酸トリデシル、４－ビフェニル酢酸ペンタデシル、４－ビフェニル酢酸セチル、４－ビフェニル酢酸シクロペンチル、４－ビフェニル酢酸シクロヘキシルメチル、４－ビフェニル酢酸ヘキシル、４－ビフェニル酢酸シクロヘキシルメチル等を例示できる。 Furthermore, the component (iii) may be a compound represented by the following formula (9).

(In the formula, R represents an alkyl group having 4 to 22 carbon atoms, a cycloalkylalkyl group, a cycloalkyl group, or an alkenyl group having 4 to 22 carbon atoms, and X is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and n represents 0 or 1.)
Examples of the compound represented by formula (9) include decyl 4-phenylbenzoate, lauryl 4-phenylbenzoate, myristyl 4-phenylbenzoate, cyclohexylethyl 4-phenylbenzoate, octyl 4-biphenylacetate, and 4-phenylbenzoate. Nonyl biphenylacetate, decyl 4-biphenylacetate, lauryl 4-biphenylacetate, myristyl 4-biphenylacetate, tridecyl 4-biphenylacetate, pentadecyl 4-biphenylacetate, cetyl 4-biphenylacetate, cyclopentyl 4-biphenylacetate, 4-biphenylacetate Examples include cyclohexylmethyl, hexyl 4-biphenylacetate, and cyclohexylmethyl 4-biphenylacetate.

（式中、Ｒは炭素数３～１８のアルキル基又は炭素数３～１８の脂肪族アシル基を示し、Ｘは水素原子、炭素数１～３のアルキル基、炭素数１又は２のアルコキシ基、ハロゲン原子のいずれかを示し、Ｙは水素原子又はメチル基を示し、Ｚは水素原子、炭素数１～４のアルキル基、炭素数１又は２のアルコキシ基、ハロゲン原子のいずれかを示す。）
式（１０）で示される化合物としては、例えば、４－ブトキシ安息香酸フェノキシエチル、４－ペンチルオキシ安息香酸フェノキシエチル、４－テトラデシルオキシ安息香酸フェノキシエチル、４－ヒドロキシ安息香酸フェノキシエチルとドデカン酸とのエステル、バニリン酸フェノキシエチルのドデシルエーテル等を例示できる。 Furthermore, the component (iii) may be a compound represented by the following formula (10).

(In the formula, R represents an alkyl group having 3 to 18 carbon atoms or an aliphatic acyl group having 3 to 18 carbon atoms, and X is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 or 2 carbon atoms. , a halogen atom, Y represents a hydrogen atom or a methyl group, and Z represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 or 2 carbon atoms, or a halogen atom. )
Examples of the compound represented by formula (10) include phenoxyethyl 4-butoxybenzoate, phenoxyethyl 4-pentyloxybenzoate, phenoxyethyl 4-tetradecyloxybenzoate, phenoxyethyl 4-hydroxybenzoate and dodecanoic acid. and dodecyl ether of phenoxyethyl vanillate.

（式中、Ｒ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は水素原子、アルキル基、アルコキシ基、ハロゲン原子のいずれかを示し、Ｙは水素原子、アルキル基、アルコキシ基、ハロゲン原子のいずれかを示し、ｎは０又は１を示す。）
式（１１）で示される化合物としては、例えば、４－ヒドロキシ安息香酸オクチルの安息香酸エステル、４－ヒドロキシ安息香酸デシルの安息香酸エステル、４－ヒドロキシ安息香酸ヘプチルの４－メトキシ安息香酸エステル、４－ヒドロキシ安息香酸ドデシルの２－メトキシ安息香酸エステル、４－ヒドロキシ安息香酸シクロヘキシルメチルの安息香酸エステル等を例示できる。 Furthermore, the component (iii) may be a compound represented by the following formula (11).

(In the formula, R represents an alkyl group having 4 to 22 carbon atoms, an alkenyl group having 4 to 22 carbon atoms, a cycloalkylalkyl group, or a cycloalkyl group, and X represents a hydrogen atom, an alkyl group, an alkoxy group, or a halogen (Y represents either a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom, and n represents 0 or 1.)
Examples of the compound represented by formula (11) include benzoate ester of octyl 4-hydroxybenzoate, benzoate ester of decyl 4-hydroxybenzoate, 4-methoxybenzoate ester of heptyl 4-hydroxybenzoate, Examples include 2-methoxybenzoate ester of dodecyl -hydroxybenzoate and benzoate ester of cyclohexylmethyl 4-hydroxybenzoate.

（式中、Ｒは炭素数３～１８のアルキル基、炭素数６～１１のシクロアルキルアルキル基、炭素数５～７のシクロアルキル基、炭素数３～１８のアルケニル基のいずれかを示し、Ｘは水素原子、炭素数１～４のアルキル基、炭素数１～３のアルコキシ基、ハロゲン原子のいずれかを示し、Ｙは水素原子、炭素数１～４のアルキル基、メトキシ基、エトキシ基、ハロゲン原子のいずれかを示す。）
式（１２）で示される化合物としては、例えば、４－ヒドロキシ安息香酸ノニルのフェノキシエチルエーテル、４－ヒドロキシ安息香酸デシルのフェノキシエチルエーテル、４－ヒドロキシ安息香酸ウンデシルのフェノキシエチルエーテル、バニリン酸ドデシルのフェノキシエチルエーテル等を例示できる。 Furthermore, the component (iii) may be a compound represented by the following formula (12).

(In the formula, R represents any one of an alkyl group having 3 to 18 carbon atoms, a cycloalkylalkyl group having 6 to 11 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, an alkenyl group having 3 to 18 carbon atoms, X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a halogen atom, and Y represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, or an ethoxy group. , indicates one of the halogen atoms.)
Examples of the compound represented by formula (12) include phenoxyethyl ether of nonyl 4-hydroxybenzoate, phenoxyethyl ether of decyl 4-hydroxybenzoate, phenoxyethyl ether of undecyl 4-hydroxybenzoate, and dodecyl vanillate. Examples include phenoxyethyl ether.

（式中、Ｒは炭素数３～８のシクロアルキル基又は炭素数４～９のシクロアルキルアルキル基を示し、ｎは１～３の整数を示す。）
式（１３）で示される化合物としては、例えば、１，３－ビス（２－ヒドロキシエトキシ）ベンゼンとシクロヘキサンカルボン酸とのジエステル、１，４－ビス（２－ヒドロキシエトキシ）ベンゼンとシクロヘキサンプロピオン酸とのジエステル、１，３－ビス（２－ヒドロキシエトキシ）ベンゼンとシクロヘキサンプロピオン酸とのジエステル等を例示できる。 Furthermore, the component (iii) may be a compound represented by the following formula (13).

(In the formula, R represents a cycloalkyl group having 3 to 8 carbon atoms or a cycloalkylalkyl group having 4 to 9 carbon atoms, and n represents an integer of 1 to 3.)
Examples of the compound represented by formula (13) include a diester of 1,3-bis(2-hydroxyethoxy)benzene and cyclohexanecarboxylic acid, and a diester of 1,4-bis(2-hydroxyethoxy)benzene and cyclohexanepropionic acid. Examples include diesters of 1,3-bis(2-hydroxyethoxy)benzene and cyclohexanepropionic acid.

（式中、Ｒ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のいずれかを示し、Ｘ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、ハロゲン原子のいずれかを示し、ｎは１～３の整数を示す。）
式（１４）で示される化合物としては、例えば、４－フェニルフェノールエチレングリコールエーテルとシクロヘキサンカルボン酸とのジエステル、４－フェニルフェノールジエチレングリコールエーテルとラウリン酸とのジエステル、４－フェニルフェノールトリエチレングリコールエーテルとシクロヘキサンカルボン酸とのジエステル、４－フェニルフェノールエチレングリコールエーテルとオクタン酸とのジエステル、４－フェニルフェノールエチレングリコールエーテルとノナン酸とのジエステル、４－フェニルフェノールエチレングリコールエーテルとデカン酸とのジエステル、４－フェニルフェノールエチレングリコールエーテルとミリスチン酸とのジエステル等を例示できる。 Furthermore, the component (iii) may be a compound represented by the following formula (14).

(In the formula, R represents an alkyl group having 3 to 17 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a cycloalkylalkyl group having 5 to 8 carbon atoms; X is a hydrogen atom; 5 represents an alkyl group, methoxy group, ethoxy group, or halogen atom, and n represents an integer of 1 to 3.)
Examples of the compound represented by formula (14) include diester of 4-phenylphenol ethylene glycol ether and cyclohexane carboxylic acid, diester of 4-phenylphenol diethylene glycol ether and lauric acid, and 4-phenylphenol triethylene glycol ether. Diester of cyclohexanecarboxylic acid, diester of 4-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 Examples include diester of phenylphenol ethylene glycol ether and myristic acid.

The reversible thermochromic composition of the present invention has the above-mentioned (a) component, (b) component, and (c) component as essential components, and the proportion of each component is determined by the concentration, color change temperature, color change form, and type of each component. Generally speaking, the component ratio at which desired characteristics can be obtained is 0.1 to 100, preferably 0.1 to 50, more preferably 0. .5 to 20, component (c) 5 to 200, preferably 5 to 100, more preferably 10 to 100 (all the above ratios are parts by mass).

Furthermore, various light stabilizers may be added to the reversible thermochromic composition if necessary.
The light stabilizer is contained in order to prevent photodeterioration of the reversible thermochromic composition consisting of component (a), component (b), and component (c), and is 0% by mass of component (a). It is blended in a proportion of .3 to 24% by weight, preferably 0.3 to 16% by weight. Further, among the light stabilizers, the ultraviolet absorber effectively cuts ultraviolet rays contained in sunlight and the like, and prevents photodeterioration caused by the excited state caused by the photoreaction of the component (a). Furthermore, antioxidants, singlet oxygen quenchers, superoxide anion quenchers, ozone quenchers, and the like suppress oxidation reactions caused by light.
The light stabilizers may be used alone or in combination of two or more.

Among the light stabilizers, examples of ultraviolet absorption absorbers include:
2,4-hydroxybenzophenone,
2-hydroxy-4-methoxybenzophenone,
2,2'-dihydroxy-4,4'-dimethoxybenzophenone,
2,2',4,4'-tetrahydroxybenzophenone,
2-hydroxy-4-methoxybenzophenone-5-sulfonic acid,
2-hydroxy-4-octyloxybenzophenone,
bis-(5-benzoyl-4-hydroxy-2-methoxyphenyl)-methane,
2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzophenone,
4-dodecyloxy-2-hydroxybenzophenone,
2-hydroxy-4-octadecyloxybenzophenone,
2,2'-dihydroxy-4-methoxybenzophenone,
4-benzyloxy-2-hydroxybenzophenone,
Benzophenone ultraviolet absorbers such as 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzophenone,
phenyl salicylate,
4-tert-butylphenyl salicylate,
4-octylphenyl salicylate,
2,4-di-tert-butylphenyl-4-hydroxybenzoate,
1-hydroxybenzoate,
3-tert-butyl-1-hydroxybenzoate,
1-hydroxy-3-tert-octylbenzoate,
Salicylic acid-based UV absorbers such as resorcinol monobenzoate,
2-ethyl-2-cyano-3,3'-diphenyl acrylate,
2-ethylhexyl-2-cyano-3,3'-diphenylacrylate,
Cyanoacrylate ultraviolet absorbers such as 2-ethylhexyl-2-cyano-3-phenyl cinnate,
2-(5-tert-butyl-2-hydroxyphenyl)benzotriazole,
2-(2-hydroxy-5-methylphenyl)benzotriazole,
2-[3,5-bis(a,a-dimethylbenzyl)-2-hydroxyphenyl]-2H-benzotriazole,
2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole,
2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole,
2-(3,5-di-tert-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole,
2-(3,5-di-tert-amyl-2-hydroxyphenyl)benzotriazole,
β-[3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propionic acid-polyethylene glycol 300 ester,
2-(3-dodecyl-2-hydroxy-5-methylphenyl)benzotriazole,
bis{β-[3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]}propionic acid-polyethylene glycol 300 ester,
2-(3-tert-butyl-2-hydroxyphenyl-5-propyloctylate)-5-chlorobenzotriazole,
2-[2-hydroxyphenyl-3,5-di-(1,1′-dimethylbenzyl)phenyl]-2H-benzotriazole,
2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole,
2-(3-tert-butyl-5-octyloxycarbonylethyl-2-hydroxyphenyl)benzotriazole,
2-(2-hydroxy-5-tetraoctylphenyl)benzotriazole,
2-(2-hydroxy-4-octoxyphenyl)benzotriazole,
2-[2'-hydroxy-3'-(3'',4'',5'',6''-tetrahydrophthalimidomethyl)-5'-methylphenyl]benzotriazole,
Benzotriazole ultraviolet absorbers such as 2-(5-tert-butyl-2-hydroxyphenyl)benzotriazole,
ethanediamide-N-(2-ethoxyphenyl)-N'-(4-isododecylphenyl),
2,2,4,4-tetramethyl-20-(β-lauryl-oxycarbonyl)-ethyl-7-oxa-3,20-diazodispiro(5,1,11,2)heneicoic acid-21-one, etc. Oxalic acid anilide ultraviolet absorber,
2,4-diphenyl-6-(2-hydroxy-4-methoxyphenyl)-1,3,5-triazine,
2,4-diphenyl-6-(2-hydroxy-4-ethoxyphenyl)-1,3,5-triazine,
2,4-diphenyl-6-(2-hydroxy-4-propoxyphenyl)-1,3,5-triazine,
2,4-diphenyl-6-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine,
2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazine,
2,4-diphenyl-6-(2-hydroxy-4-pentoxyphenyl)-1,3,5-triazine,
2,4-diphenyl-6-(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,
2,4-diphenyl-6-(2-hydroxy-4-dodecyloxyphenyl)-1,3,5-triazine,
2,4-diphenyl-6-(2-hydroxy-4-benzyloxyphenyl)-1,3,5-triazine,
2,4-diphenyl-6-[2-hydroxy-4-(2-butoxyethoxy)phenyl]-1,3,5-triazine,
2,4-di-p-trail-6-(2-hydroxy-4-methoxyphenyl)-1,3,5-triazine,
2,4-di-p-trail-6-(2-hydroxy-4-propoxyphenyl)-1,3,5-triazine,
2,4-di-p-trail-6-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine,
2,4-di-p-trail-6-(2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazine,
2,4-di-p-trail-6-(2-hydroxy-4-pentoxyphenyl)-1,3,5-triazine,
2,4-di-p-trail-6-(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,
2,4-di-p-trail-6-(2-hydroxy-4-benzyloxyphenyl)-1,3,5-triazine,
2,4-di-p-trail-6-[2-hydroxy-4-(2-hexyloxyethoxy)phenyl]-1,3,5-triazine,
2-{4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,
2-{4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,
2-[4-{[2-hydroxy-3-(2'-ethyl)hexyl]oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5- triazine,
2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-[2,4-bis(butyloxyphenyl)]-1,3,5-triazine,
Triazine-based UV absorbers such as 2-{2-hydroxy-4-[(1-octyloxycarbonylethoxy)phenyl]}-4,6-bis(4-phenylphenyl)-1,3,5-triazine, etc. I can give an example.

Examples of antioxidants (antiaging agents) include:
dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate,
Poly{[6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazin-2-4-diyl][(2,2,6,6-tetramethyl-4-piperidyl ) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl)imino]} hexamethylene,
2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonate bis(1,2,2,6,6-pentapetyl-4-piperidyl),
N,N'-bis(3-aminopropyl)ethylenediamine-2,4-bis[N-butyl-N-(1,2,2,6,6-pentapetyl-4-piperidyl)amino]-6-chloro- 1,3,5-triazine condensate,
bis(1,2,2,6,6-pentamethyl-4-piperidylsebacic acid),
4-benzoyloxy-2,2,6,6-tetramethylpiperidine,
bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate,
Hindered amine antioxidants such as 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4,5]decane-2,4-dione,
2,6-di-tert-butyl-4-methylphenol,
2-tert-butyl-4-methoxyphenol,
2,6-di-tert-butyl-4-ethylphenol,
octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate,
2,2-methylenebis(4-methyl-6-tert-butylphenol),
4,4-thiobis(2-methyl-6-tert-butylphenol),
2,2-thiobis(4-methyl-6-tert-butylphenol),
4,4-butylidenebis(3-methyl-6-tert-butylphenol),
3,9-bis{1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl},
2,4,8,10-tetraoxaspiro[5,5]undecane,
1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,
1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,
Tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane,
2,2-ethylenebis(4,6-di-tert-butylphenol),
bis[3,3-bis-(4'-hydroxy-3'-tert-butylphenyl)butyric acid]-glycol ester,
1,3,5-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)-S-triazine-2,4,6-[1H,3H,5H]-trione,
tocopherol,
1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,
Pentaerythritol tetrakis (3-laurylthiopropionate),
triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate],
1,6-hexadiol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],
2,2-thioethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],
N,N'-hexamethylenebis(3,5-tert-butyl-4-hydroxy-hydrocinnamamide),
tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,
2,2,4-trimethyl-1,2-hydroquinone,
styrate phenol,
2,5-di-tert-butylhydroquinone,
Phenolic antioxidants such as bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate,
dilauryl-3,3'-thiodipropionate,
dimyristyl-3,3'-thiodipropionate,
distearyl-3,3'-thiodipropionate,
Sulfur-based antioxidants such as stearylthiopropylamide,
tris(2,4-di-tert-butylphenyl) phosphite,
bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,
3,5-di-tert-butyl-4-hydroxy-benzylphosphanate diethyl ester,
triphenyl phosphite,
diphenylisodecyl phosphite,
phenylisodecyl phosphite,
4,4'-butylidene-bis(3-methyl-6-tert-butylphenylditridecyl) phosphite,
octadecyl phosphite,
Tris (nonylphenyl) phosphite,
diisodecyl pentaerythritol diphosphite,
9,10-dihydroxy-9-oxa-10-phosphaphenanthrene,
10-(3,5-di-tert-butyl-4-hydroxybenzyl)-9,10-dihydroxy-9-oxa-10-phosphaphenanthrene-10-oxide,
10-decyloxy-9,10-dihydroxy-9-oxa-10-phosphaphenanthrene,
cyclic neopentanetetrayl bis(2,4-di-tert-butylphenyl) phosphite,
cyclic neopentane tetrayl bis(2,6-di-tert-butyl-4-methylphenyl) phosphite,
2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite,
2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine,
Examples include phosphoric acid antioxidants such as octylated diphenylamine.

Examples of singlet oxygen quenchers include carotenes, pigments, amines, phenols, nickel complexes, sulfides, etc., such as 1,4-diazabicyclo[2,2,2]octane (DABCO), β-carotene, 1,3-cyclohexadiene, 2-diethylaminomethylfuran, 2-phenylaminomethylfuran, 9-diethylaminomethylanthracene, 5-diethylaminomethyl-6-phenyl-3,4-dihydroxypyran, nickel dimethyldithiocarbamate , nickel 3,5-di-tert-butyl-4-hydroxybenzyl-O-ethylphosphonate, nickel 3,5-di-tert-butyl-4-hydroxybenzyl-O-butylphosphonate, nickel [2,2 '-thiobis(4-tert-octylphenolate)]n-butylamine, nickel[2,2'-thiobis(4-tert-octylphenolate)]2-ethylhexylamine, nickel bis[2,2'-thiobis( 4-tert-octylphenolate)], nickel bis[2,2'-sulfonebis(4-octylphenolate)], nickel bis(2-hydroxy-5-methoxyphenyl-Nn-butyraldimine), nickel Examples include bis(dithiobenzyl) and nickel bis(dithiobiacetyl).

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

Examples of ozone quenchers include 4,4'-thiobis(6-tert-butyl-m-cresol), 2,4,6-tri-tert-butylphenol, 1,4-diazabicyclo[2,2,2] Octane, N-phenyl-β-naphthylamine, α-tocopherol, 4,4'-methylene-bis(2,6-di-tert-butylphenol), P,P'-diaminodiphenylmethane, 2,2'-methylene-bis Examples include (6-tert-butyl-p-cresol), N,N'-diphenyl-p-phenylenediamine, N,N'-diphenylethylenediamine, and N-isopropyl-N'-phenyl-p-phenylenediamine.

The reversible thermochromic composition of the present invention is effective when applied as is, but it can be encapsulated in microcapsules to form reversible thermochromic microcapsule pigments (hereinafter sometimes referred to as "microcapsule pigments" or "pigments"). ) or dispersed in a thermoplastic resin or thermosetting resin to form reversible thermochromic resin particles (hereinafter sometimes referred to as "resin particles").
The reversible thermochromic composition is preferably encapsulated in microcapsules to form a reversible thermochromic microcapsule pigment. By encapsulating it in microcapsules, it is possible to construct a chemically and physically stable pigment, and furthermore, under various usage conditions, the reversible thermochromic composition maintains the same composition and remains the same. This is because it can produce effects.
Note that microencapsulation can be carried out by conventionally known isocyanate-based interfacial polymerization methods, melamine-formalin-based in-situ polymerization methods, in-liquid curing coating methods, phase separation methods from aqueous solutions, phase separation methods from organic solvents, and melting. There are dispersion cooling methods, air suspension coating methods, spray drying methods, etc., which are appropriately selected depending on the application. Furthermore, depending on the purpose, a secondary resin film can be further provided on the surface of the microcapsule to impart durability or to modify the surface characteristics for practical use.
In the reversible thermochromic microcapsule pigment, the mass ratio of the inclusions to the wall film is preferably 7:1 to 1:1, and by having the mass ratio of the inclusions to the wall film within the above range, it is possible to A decrease in color density and sharpness is prevented. More preferably, the mass ratio of inclusions to wall membrane is 6:1 to 1:1.

The average particle diameter of the reversibly thermochromic microcapsule pigment or resin particles is preferably in the range of 0.01 to 50 μm, more preferably 0.1 to 30 μm, and still more preferably 0.5 to 20 μm. If the average particle diameter of the microcapsule pigment or resin particles exceeds 50 μm, dispersion stability and processing suitability will be lacking when blended into inks, paints, or resins. On the other hand, if the average particle diameter of the microcapsule pigment or resin particles is less than 0.01 μm, it becomes difficult to exhibit high-density color development.
To measure the average particle diameter, the area of the particles is determined using image analysis particle size distribution measurement software [manufactured by Mountech Co., Ltd., product name: Macview], and the projected area circle equivalent diameter ( Heywood diameter) is calculated, and the value is measured as the average particle diameter of particles equivalent to an equal volume sphere based on the calculated value.
In addition, if the particle diameter of all or most of the particles exceeds 0.2 μm, use a particle size distribution analyzer [manufactured by Beckman Coulter, Inc., product name: Multisizer 4e] to measure equal volume spheres using the Coulter method. It is also possible to measure it as the average particle size of the corresponding particles.
Furthermore, a laser diffraction/scattering particle size distribution measuring device [manufactured by Horiba, Ltd., product name: LA-960V2] was calibrated based on the values measured using the software or the Coulter method measuring device. ] The volume-based particle diameter and average particle diameter may be measured.

A reversible thermochromic coloring agent such as a reversible thermochromic composition, a reversible thermochromic microcapsule pigment, or a resin particle is dispersed in a vehicle containing water and/or an organic solvent and optionally various additives to form an ink composition. (hereinafter sometimes referred to as "ink") is a printing ink used for screen printing, offset printing, process printing, gravure printing, coater, tampo printing, etc. / brush painting, spray painting, electrostatic painting , paints used for electrodeposition coating, flow coating, roller coating, dipping coating, etc. / inkjet ink / ultraviolet curing ink / ink for writing instruments such as marking pens, ballpoint pens, fountain pens, brush pens, etc. / for applicators It can be used as a reversible thermochromic liquid composition such as ink/stamp ink/paint/cosmetic/textile coloring liquid.

Various additives can be added to the reversible thermochromic liquid composition.
Additives include resins, crosslinking agents, curing agents, desiccants, plasticizers, viscosity modifiers, dispersants, ultraviolet absorbers, antioxidants, light stabilizers, anti-settling agents, smoothing agents, gelling agents, and quenching agents. Examples include foaming agents, matting agents, penetrating agents, pH adjusting agents, foaming agents, coupling agents, humectants, antifungal agents, preservatives, and rust preventives.

Examples of the writing instrument vehicle used in the writing instrument ink include an oil-based vehicle containing an organic solvent, or an aqueous vehicle containing water and, if necessary, an organic solvent.
Examples of organic solvents include ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, ethylene glycol monomethyl ether, and ethylene. Examples include glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, etc. can.

Examples of inks for writing instruments include shear-thinning inks that contain shear-thinning agents in the vehicle, and cohesive inks that contain polymer flocculants in the vehicle and suspend microcapsule pigments in a mildly agglomerated state. It will be done.

An ink containing a shear-thinning agent in the vehicle (shear-thinning ink) can suppress aggregation and sedimentation of microcapsule pigments, and can also suppress blurring of handwriting, so that good handwriting can be formed.
Furthermore, when shear-thinning ink is stored in a ballpoint pen-type writing instrument, it is possible to prevent ink from leaking from the gap between the ball and the tip when the writing instrument is not in use, or to prevent the writing tip from being left facing upward (upright). This can prevent backflow of ink.

Examples of shear thinning agents include xanthan gum, welan gum, succinoglycan (average molecular weight of about 1 million to 8 million), which is an organic acid-modified heteropolysaccharide whose constituent monosaccharides are glucose and galactose, alkali gum, guar gum, and locust bean. Gum and its derivatives, hydroxyethylcellulose, alginate alkyl esters, polymers with a molecular weight of 100,000 to 150,000 whose main components are methacrylic acid alkyl esters, glucomannan, gelling ability extracted from seaweed such as agar and carrageenan. thickening polysaccharides, benzylidene sorbitol and benzylidene xylitol or their derivatives, crosslinkable acrylic acid polymers, inorganic fine particles, polyglycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyethylene glycol fatty acid esters, polyoxyethylene castor oil, Nonionic surfactants with HLB values of 8 to 12 such as oxyethylene lanolin, lanonine alcohol, beeswax derivatives, polyoxyethylene alkyl ethers, polyoxypropylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, fatty acid amides, dialkyl or di- Examples include salts of alkenylsulfosuccinic acid, mixtures of N-alkyl-2-pyrrolidone and anionic surfactants, and mixtures of polyvinyl alcohol and acrylic resins.

Ink containing a polymer flocculant in the vehicle (flocculating ink) is a type of ink in which the microcapsule pigments form loose aggregates via the polymer flocculant, and the microcapsule pigments are prevented from coming into contact with each other and agglomerating. Therefore, the dispersibility of the pigment can be improved.

Examples of polymer flocculants include polyvinylpyrrolidone, polyethylene oxide, water-soluble polysaccharides, and the like.
Examples of water-soluble polysaccharides include gum tragacanth, guar gum, pullulan, cyclodextrin, and water-soluble cellulose derivatives.
Furthermore, examples of water-soluble cellulose derivatives include methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxyethylmethylcellulose, and hydroxypropylmethylcellulose.
Among the polymer flocculants, hydroxyethyl cellulose is preferred because it has excellent dispersibility.

Specifically, the polymer flocculants include Sumitomo Seika Co., Ltd., product names: HEC A grade, HEC S grade, HEC CF grade, Daicel Fichem Co., Ltd., product names: HEC Daicel SP type, Examples include SE type, EE type, manufactured by Dow Chemical Japan Co., Ltd., product name: CELLOSIZE WP type, QP type, EP type, manufactured by Sansho Co., Ltd., product name: SANHEC.
The polymer flocculant is preferably blended in an amount of 0.1 to 1% by mass, more preferably 0.3 to 0.5% by mass, based on the total amount of the ink. By being within the above range, the microcapsule pigment can form a loose aggregate, and the effect of improving the dispersibility of the pigment can be sufficiently exhibited.

Furthermore, the dispersibility of the microcapsule pigment can be improved by incorporating a dispersant into the ink.
In addition, a polymer flocculant and a dispersant can be used together, and when both are used together, the dispersibility of the microcapsule pigment can be improved, and the microcapsule pigment formed via the polymer flocculant can be The dispersibility of loose aggregates can be further improved.

Examples of dispersants include synthetic resins such as polyvinylpyrrolidone, polyvinyl butyral, polyvinyl ether, styrene-maleic acid copolymers, ketone resins, hydroxyethyl cellulose and its derivatives, styrene-acrylic acid copolymers, acrylic polymers, Examples include PO/EO adducts and amine oligomers of polyester.
Among the dispersants, acrylic polymer dispersants are preferred because they have excellent dispersibility for microcapsule pigments, and acrylic polymer dispersants having a carboxyl group are more preferred. More preferred are acrylic polymer dispersants.
Particularly preferred as the dispersant is an acrylic polymer dispersant with a comb-shaped structure having a plurality of carboxyl groups in the side chain, and a specific example is Solsperse 43000, manufactured by Nippon Lubrizol Co., Ltd.
The dispersant is preferably blended in an amount of 0.01 to 2% by mass, more preferably 0.1 to 1.5% by mass, based on the total amount of the ink. When the blending ratio of the dispersant exceeds 2% by mass, the microcapsule pigment tends to settle or float when external vibrations or the like are applied. On the other hand, if the blending ratio of the dispersant is less than 0.01% by mass, the effect of improving dispersibility will be difficult to exhibit.

In addition, by using an acrylic polymer dispersant with a comb-shaped structure having a carboxyl group in the side chain and an organic nitrogen sulfur compound together with a polymer flocculant, microcapsule pigments formed via the polymer flocculant can be The dispersibility of loose aggregates can be improved.
Organic nitrogen sulfur compounds are used to disperse loose aggregates of microcapsule pigments using a comb-shaped acrylic polymer dispersant having a carboxyl group in the side chain. When put into practical use, sedimentation of the microcapsule pigment due to vibration can be further suppressed.

Examples of organic nitrogen sulfur compounds include compounds selected from thiazole compounds, isothiazole compounds, benzothiazole compounds, and benzisothiazole compounds, such as 2-(4-thiazoyl)-benzimidazole (TBZ), One or more selected from 2-(thiocyanatemethylthio)-1,3-benzothiazole (TCMTB), 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, etc. Two or more types of compounds can be exemplified.
Among the organic nitrogen sulfur compounds, 2-(4-thiazoyl)-benzimidazole (TBZ), 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, One or more selected compounds are preferred.
Specifically, the organic nitrogen sulfur compounds are manufactured by Permakem Asia Co., Ltd., product names: Topside 88, 133, 170, 220, 288, 300, 400, 500, 600, Examples include 700Z, 800, 950, manufactured by Hokuko Sangyo Co., Ltd., product names: Hokster HP, E50A, Hokuside P200, 6500, 7400, MC, 369, and R-150.
The mass ratio of the comb-shaped acrylic polymer dispersant having a carboxyl group in the side chain to the organic nitrogen sulfur compound is preferably 1:1 to 1:10, more preferably 1:1 to 1:5. be. By being within the above range, it is possible to sufficiently exhibit the gentle dispersibility of the microcapsule pigment aggregates and the effect of suppressing the sedimentation of the microcapsule pigment due to vibration.

Furthermore, by blending a water-soluble resin into the ink, it is possible to provide adhesion and viscosity to the handwriting on the paper surface, and the ink contains an acrylic polymer dispersant with a comb-shaped structure having a carboxyl group in the side chain and organic nitrogen sulfur. The function of increasing the dispersibility of the microcapsule pigment in the ink containing the compound can be further improved.

Examples of water-soluble resins include alkyd resins, acrylic resins, styrene-maleic acid copolymers, cellulose derivatives, polyvinylpyrrolidone, polyvinyl alcohol, and dextrin.
Among the water-soluble resins, polyvinyl alcohol is preferred, and partially saponified polyvinyl alcohol having a saponification degree of 70 to 89 mol% is more preferred since the ink is highly soluble even in an acidic region.
The water-soluble resin is preferably blended in an amount of 0.3 to 3.0% by mass, more preferably 0.5 to 1.5% by mass, based on the total amount of the ink.

Furthermore, if the viscosity of the vehicle is low by incorporating a specific gravity adjusting agent into the ink, microcapsule pigments may settle or float in the ink when the ink is subjected to external stimuli such as vibrations, causing local It is possible to prevent this from becoming a reality.

The specific gravity of the microcapsule pigment depends on the particle size of the microcapsule pigment, the components and contents contained in the microcapsules, the components and film thickness of the capsule wall film, the coloring state of the microcapsule pigment, and the temperature. The specific gravity is preferably 1.05 to 1.20, more preferably 1.10 to 1.20, and more preferably 1.05 to 1.20, more preferably 1.10 to 1.20, when the microcapsule pigment is completely colored and water is used as a reference substance in an environment of 20°C. It is preferably in the range of 1.12 to 1.15. In addition, microcapsule pigments with a large hysteresis width (ΔH) often use a component (c) having two or more aromatic rings in the molecule, and have a high specific gravity as described above. Even if the viscosity of the vehicle is low in an ink containing a specific gravity adjuster, the microcapsule pigment is prevented from settling or floating in the ink when it is affected by external vibrations during transportation, etc. Ru.
Note that the specific gravity of the microcapsule pigment can be measured by the following method.

(Method for measuring specific gravity of microcapsule pigment)
1. 30 ml of an aqueous glycerin solution and 1 g of a fully colored microcapsule pigment are placed in a screw tube bottle and mixed to obtain a microcapsule pigment dispersion.
2. The temperature of 30 ml of the microcapsule pigment dispersion is adjusted to 20° C., and the mixture is centrifuged at a rotation speed of 1000 rpm for 30 seconds. In addition, as a centrifuge, a refrigerated tabletop centrifuge [manufactured by Kokusan Co., Ltd., product name: H103N] can be used.
3. Observe the microcapsule pigment dispersion.
If most of the microcapsule pigment has precipitated at the bottom of the beaker, perform steps 1 and 2 again using an aqueous solution with a higher glycerin concentration than the aqueous glycerin solution used at this time, and observe the state of the dispersion.
If it is confirmed that most of the microcapsule pigment is floating on the liquid surface, repeat steps 1 and 2 using an aqueous solution with a lower glycerin concentration than the one used at this time, and observe the state of the dispersion. .
The above series of operations is performed so that most of the microcapsule pigment is not floating on the liquid surface or precipitated, and the parts other than the liquid surface of the glycerin aqueous solution and the bottom of the screw tube bottle are uniformly colored. Repeat until the condition is visually confirmed. When this state is observed, the specific gravity of the glycerin aqueous solution is measured and taken as the specific gravity of the microcapsule pigment. The specific gravity of the glycerin aqueous solution can be measured by the float method described in JIS K0061 Section 7.1 using an aqueous solution whose temperature is controlled to 20°C.

The sedimentation and flotation stability of the pigment is maximized when the difference in specific gravity between the vehicle and the pigment is minimal, and the specific gravity adjuster brings the specific gravity of the vehicle close to that of the microcapsule pigment. The specific gravity of the vehicle depends on the specific gravity of the water-soluble substance dissolved in the vehicle and the amount added, so adding and dissolving a larger amount of a specific gravity adjuster with a higher specific gravity in the vehicle will increase the specific gravity of the vehicle. Can be made larger.

Examples of the specific gravity adjusting agent include those that can be dissolved in the vehicle and adjusted so that the specific gravity of the vehicle approaches the specific gravity of the microcapsule pigment. An example is salt.

The oxyacids and salts thereof are selected from the group consisting of oxyacids of transition metal elements and salts thereof, and the oxyacid ion is a tetrahedral or tetrahedral structure in which oxygen atoms are usually 4 or 6 coordinated to a metal atom, etc. It is said to form an octahedron.
The tetrahedral or octahedral unit may be a single unit, or may be a polyacid or a polyacid salt thereof having a structure in which these units are bonded through edges and vertices. A polyacid is a multiple acid produced by the condensation of oxygen acids of metal elements, but a polyacid that is composed of only one type of metal and in which all the condensed anions are of the same type is called isopolyacid; A polyacid condensed with is called a heteropolyacid. The respective salts are called isopolya salts and heteropolya salts. The above-mentioned polyacids include isopolyacids, heteropolyacids, etc., and the above-mentioned polyacids include isopolyacids, heteropolyacids, etc.

Specific gravity adjusters include single oxygen acids and their salts, isopoly acids and their salts, heteropolyacids and their salts, and the like.
Examples of single oxygen acids include molybdic acid and tungstic acid, and examples of single salts of oxygen acids include sodium molybdate, potassium molybdate, ammonium molybdate, sodium tungstate, potassium tungstate, and tungsten. Examples include ammonium acid, lithium tungstate, and magnesium tungstate.
Isopolyacids include, for example, metamolybdic acid, paramolybdic acid, metatungstic acid, paratungstic acid, isotungstic acid, etc., and isopolyacid salts include sodium metamolybdate, potassium metamolybdate, and metamolybdate. Ammonium molybdate, sodium paramolybdate, potassium paramolybdate, ammonium paramolybdate, sodium metatungstate, potassium metatungstate, ammonium metatungstate, barium metatungstate, sodium paratungstate, sodium isotungstate, etc. I can give an example.
Examples of heteropolyacids include molybdophosphoric acid, molybdosilicic acid, tungstophosphoric acid, and tungstosilicic acid.Furthermore, examples of heteropolyacids include sodium molybdophosphate, sodium molybdosilicate, sodium tungstophosphate, and sodium tungstosilicate. I can give an example.
The oxygen acids and salts thereof may be used alone or in combination of two or more.

Among the specific gravity adjusting agents, metatungstic acid, paratungstic acid, sodium metatungstate, potassium metatungstate, ammonium metatungstate, barium metatungstate, sodium paratungstate, sodium isotungstate, tungstophosphoric acid, tungstosilica The acid, sodium tungstophosphate, and sodium tungstosilicate are preferred, and sodium isotungstate, sodium metatungstate, and sodium paratungstate are more preferred.
The above-mentioned sodium isotungstate, sodium metatungstate, and sodium paratungstate are not only highly safe but also have high specific gravity themselves, so it is easy to adjust a high specific gravity liquid according to the amount added, suitable.

The specific gravity adjuster is preferably blended in an amount of 2 to 20% by mass, more preferably 5 to 15% by mass, based on the total amount of the ink. When the proportion of the specific gravity adjuster exceeds 20% by mass, the microcapsule pigment tends to aggregate. On the other hand, if the blending ratio of the specific gravity adjuster is less than 2% by mass, the specific gravity adjusting effect of the vehicle will be poor.
The mass ratio of microcapsule pigment to specific gravity adjuster is preferably 1:0.05 to 4.0, more preferably 1:0.075 to 2.0, and even more preferably 1:0.1 to 1. It is 5.

When the vehicle for writing instruments is an aqueous vehicle, the vehicle contains at least water, and the water is preferably blended in an amount of 30 to 80% by mass, more preferably 40 to 70% by mass, based on the total amount of the ink. be done.

Furthermore, by incorporating a water-soluble organic solvent into the ink, water evaporation of the ink is suppressed, and fluctuations in the specific gravity of the vehicle are prevented to maintain good dispersion stability of the microcapsule pigment. Alternatively, the structure of loose aggregates formed by the polymer flocculant and the dispersant can be stabilized.
Examples of water-soluble organic solvents include ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thioethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, and ethylene glycol monomethyl. Ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone etc. can be exemplified.
When the hysteresis width (ΔH) of the microcapsule pigment blended into the ink is large, the specific gravity of the microcapsule pigment is greater than 1, and when adjusting the specific gravity of the vehicle, if a water-soluble organic solvent whose specific gravity is larger than water is used, the specific gravity will be lowered. Glycerin or the like having a specific gravity of more than 1.1 is preferred as the water-soluble organic solvent because it can be easily adjusted.

The water-soluble organic solvent is preferably blended in an amount of 1 to 40% by weight, more preferably 5 to 30% by weight, and still more preferably 10 to 25% by weight, based on the total amount of the ink. When the blending ratio of the water-soluble organic solvent exceeds 40% by mass, the dissolution stability of the specific gravity adjuster tends to decrease. On the other hand, if the blending ratio of the water-soluble organic solvent is less than 1% by mass, the effect of suppressing water evaporation will be poor.

In addition, when the ink for writing instruments is used for ballpoint pens, the ink contains higher fatty acids such as oleic acid, nonionic surfactants having long-chain alkyl groups, polyether-modified silicone oil, and thiophosphite tri(alkoxycarbonyl methyl ester). and thiophosphite triesters such as thiophosphite tri(alkoxycarbonyl ethyl ester), phosphoric acid monoesters of polyoxyethylene alkyl ether or polyoxyethylene alkylaryl ether, polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether. It is preferable to add a lubricant such as phosphoric acid diester, or a metal salt, ammonium salt, amine salt, or alkanolamine salt thereof to prevent wear of the ball seat.

In addition, various additives such as a pH adjuster, a rust preventive, a preservative, or a fungicide may be added as necessary.
Examples of the pH adjuster include inorganic salts such as sodium carbonate, sodium phosphate, and sodium acetate, and organic basic compounds such as water-soluble amine compounds.
Examples of the rust preventive include benzotriazole, tolyltriazole, dicyclohexylammonium nitrite, diisopropylammonium nitrite, and saponin.
Examples of preservatives or antifungal agents include carbolic acid, sodium salt of 1,2-benzthiazolin-3-one, sodium benzoate, sodium dehydroacetate, potassium sorbate, propyl paraoxybenzoate, 2,3,5, Examples include 6-tetrachloro-4-(methylsulfonyl)pyridine.
Other additives include urea, nonionic surfactants, reduced or non-reduced starch hydrolysates, oligosaccharides such as trehalose, sucrose, cyclodextrin, glucose, dextrin, sorbitol, mannitol, sodium pyrophosphate, etc. Examples include wetting agents, antifoaming agents, dispersants, fluorosurfactants that improve ink permeability, nonionic surfactants, and the like.

The ink contains a reversible thermochromic microcapsule pigment in an amount of preferably 5 to 40% by weight, more preferably 10 to 40% by weight, and still more preferably 10 to 30% by weight based on the total amount of the ink. Ru. When the blending ratio of the microcapsule pigment is within the above range, a desired color density can be obtained and a decrease in ink flowability can be prevented.

The ink composition according to the present invention can be produced by any conventionally known method. Specifically, the above-mentioned components can be blended in required amounts and mixed using various stirrers such as propeller stirring, homodisper, or homomixer, and various dispersion machines such as bead mills.

When the ink for a writing instrument according to the present invention is used in a ballpoint pen, its viscosity is measured at a rotation speed of 3.84 sec ^-1 in an environment of 20 ° C., since it can suppress sedimentation or aggregation of the microcapsule pigment. It is preferably in the range of 1 to 2000 mPa·s, more preferably 3 to 1500 mPa·s, and still more preferably 500 to 1000 mPa·s. In addition, when measured at a rotation speed of 384 sec ^-1 in an environment of 20°C, the viscosity is preferably 1 to 200 mPa・s, since the ink ejection performance from the tip of a ballpoint pen can be made good. It is more preferably in the range of 10 to 100 mPa·s, and even more preferably in the range of 20 to 50 mPa·s.
When the viscosity is within the above range, the dispersion stability of the microcapsule pigment and the free flow of the ink within the mechanism of the ballpoint pen can be maintained at a high level.
The viscosity was measured using a digital viscometer [manufactured by Brookfield, product name: DV-II, cone rotor (CPE-42)] at a shear rate of 3.84 sec when the ink was placed in an environment of 20°C ^{. 1} (1 rpm) or a shear rate of 384 sec ^-1 (100 rpm).

When the ink for writing instruments according to the present invention is used in a ballpoint pen, its surface tension is preferably in the range of 20 to 50 mN/m, more preferably 25 to 45 mN/m in an environment of 20°C. When the surface tension is within the above range, it is easy to suppress bleeding of written lines and strike-through onto the paper surface, and it is also possible to improve the wettability of the ink to the paper surface.
The surface tension was measured using a surface tension measuring device [manufactured by Kyowa Kaimen Kagaku Co., Ltd., product name: DY-300] by placing the ink in an environment of 20°C and using a platinum plate using the vertical plate method. can do.

When the ink for writing instruments according to the present invention is used in a ballpoint pen, its pH is preferably in the range of 3 to 10, more preferably 4 to 9. When the pH is within the above range, it is possible to suppress aggregation or sedimentation of the microcapsule pigment contained in the ink in a low temperature range.
Note that the pH can be measured by placing the ink in an environment at 20° C. using a pH meter (manufactured by DKK Toa Co., Ltd., product name: IM-40S type).

When the ink for writing instruments according to the present invention is used in a marking pen, its viscosity is preferably 3 to 25 mPa·s, more preferably 4 to 20 mPa·s, when measured at a rotation speed of 6 rpm in an environment of 20°C. s, more preferably in the range of 5 to 15 mPa·s. Furthermore, when measured under the condition of a rotation speed of 12 rpm, it is preferably in the range of 2 to 20 mPa·s, more preferably 3 to 15 mPa·s, and still more preferably 4 to 15 mPa·s. When measured at a rotation speed of 30 rpm, it is preferably in the range of 1 to 20 mPa·s, more preferably 2 to 15 mPa·s, and still more preferably 3 to 10 mPa·s. When the viscosity is within the above range, the fluidity of the ink and the dispersion stability of the microcapsule pigment can be improved.
The viscosity should be measured using a BL type rotational viscometer [manufactured by Toki Sangyo Co., Ltd., product name: TVB-M type viscometer, B type rotor] by placing the ink in an environment of 20°C. Can be done.

When the ink for writing instruments according to the present invention is used in a marking pen, its surface tension is preferably 25 to 50 mN/m, more preferably 25 to 45 mN, even more preferably 35 to 45 mN/m in an environment of 20°C. range. When the surface tension is within the above range, it is easy to suppress bleeding of written lines and strike-through onto the paper surface, and it is also possible to improve the wettability of the ink to the paper surface.
The surface tension is measured using a surface tension measuring device [manufactured by Kyowa Kaimen Kagaku Co., Ltd., product name: DY-300] by placing the ink in an environment of 20°C and using a glass plate using the vertical plate method. be able to.

When the ink for writing instruments according to the present invention is used in a marking pen, its pH is preferably in the range of 3 to 8, more preferably 4 to 7, even more preferably 5 to 6. When the pH is within the above range, it is possible to suppress aggregation or sedimentation of the microcapsule pigment contained in the ink in a low temperature range.
Note that the pH can be measured by placing the ink in an environment at 20° C. using a pH meter (manufactured by DKK Toa Co., Ltd., product name: IM-40S type).

A writing instrument containing the ink for a writing instrument according to the present invention contains a reversible thermochromic microcapsule pigment in the range of 5 to 40% by mass in the total amount of the ink for a writing instrument, and complies with the old JIS P3201 at 20°C. The ink consumption of the writing instrument when writing for 50 meters on writing paper A is 60 to 280 mg, and the value C obtained by dividing the density value of the handwriting in the colored state by the density value of the handwriting in the decolored state is 20 or more. It is preferable.

If the blending ratio of the microcapsule pigment exceeds 40% by mass, the ink flowability tends to decrease, and the amount of the microcapsule pigment deposited on the paper surface becomes excessive, and more powder is added to erase or discolor the handwriting in the colored state. Since heat is required, handwriting tends to be burdensome when rubbed to erase or change color. On the other hand, if the blending ratio of the microcapsule pigment is less than 5% by mass, it becomes difficult to obtain the desired color density.

Writing instruments such as ballpoint pens and marking pens that contain the above-mentioned writing instrument ink will be explained.
When filling a ballpoint pen, the structure and shape of the ballpoint pen itself are not particularly limited. For example, the ink storage tube may include an ink storage tube filled with shear-thinning ink in the barrel, and the ink storage tube may hold the ball at the tip. An example of a ballpoint pen is a ballpoint pen that communicates with a ballpoint pen tip attached to the ink and further has a liquid stopper for preventing backflow in close contact with the end surface of the ink.
Ballpoint pen tips include, for example, a tip made by holding a ball in a ball holding part made by pressing the tip of a metal pipe inward from its outer surface, and a ball formed by cutting a metal material with a drill or the like. A chip in which a ball is held in a holding part, a chip in which a resin ball receiving seat is provided inside a metal or plastic chip, or a ball held in the above-mentioned chip is urged forward by a spring body. Can give examples of things, etc.
Note that the material of the ballpoint pen tip and ball is not particularly limited, and examples thereof include cemented carbide (carbide), stainless steel, ruby, ceramic, resin, and rubber.
The diameter of the ball is preferably about 0.3 to 2.0 mm, more preferably about 0.3 to 1.5 mm, and still more preferably about 0.3 to 1.0 mm.
In general, ballpoint pens with small-diameter balls consume less ink and tend to have lower handwriting density, while ballpoint pens containing writing instrument ink containing reversible thermochromic microcapsule pigments can produce higher handwriting density. It tends to be difficult to Furthermore, since the amount of ink on the ball surface is small, the ball surface dries up (dry-up) and is likely to cause poor handwriting such as smudges. When increasing the solid content in the ink, the dry-up resistance tends to deteriorate. However, when the ink for writing instruments according to the present invention is used in a ballpoint pen equipped with a ball having a diameter of 0.3 to 0.5 mm, it is possible to increase the density of handwriting without increasing the solid content of the pigment. It is possible to improve the density of handwriting without impairing dry-up resistance, and to obtain a writing instrument with excellent contrast between the colored state and the decolored state.
In addition, ballpoint pens with large diameter balls generally consume a large amount of ink, and ballpoint pens containing writing instrument ink containing reversible thermochromic microcapsule pigments can achieve high handwriting density; There is a tendency for residual color to be easily recognized when the color is erased. However, when the ink for writing instruments according to the present invention is used in a ballpoint pen equipped with a ball having a diameter of 0.5 to 1.0 mm, it is possible to make the residual color of the handwriting in the decolored state difficult to be seen, and the color development A writing instrument with excellent contrast between the state and the decolored state can be obtained.

As the ink storage tube, for example, a molded body made of a thermoplastic resin such as polyethylene, polypropylene, polyethylene terephthalate, or nylon, or a metal tubular body is used.
In addition to directly connecting the chip to the ink storage tube, the ink storage tube and the chip may be connected via a connecting member.
The ink storage tube may be in the form of a refill, and the refill may be stored in a cylinder made of resin or metal, or the cylinder itself with a tip attached to the tip may be used as an ink storage body. The ink may be directly filled into the ink.

In addition, when storing ink in a retractable ballpoint pen, the structure and shape of the retractable ballpoint pen are not particularly limited. Any structure can be used as long as it is housed and the writing tip protrudes from the barrel opening when the protruding/retracting mechanism is activated.
For example, (1) an operating section (clip) that can be moved in the front-rear direction from the rear side wall of the barrel is protruded radially outward, and by sliding the operating section forward, the front end of the barrel can be moved. (2) A rear end knock that makes the writing tip come out and go out from the opening at the front end of the barrel by pushing forward the operating section provided at the rear end of the barrel. (3) A side-knock-type ejection mechanism that causes the writing tip to protrude and retract from the front end opening of the barrel by pressing an operating part protruding from the outer surface of the side wall of the barrel in the radial direction; (4) a shaft; An example is a rotary ejection mechanism that causes the writing tip to protrude and retract from the front end opening of the barrel by rotating an operating section at the rear of the barrel.
The retractable ballpoint pen is a compound type retractable ballpoint pen that has a plurality of ballpoint pen refills housed in a barrel, and the writing tip of one of the ballpoint pen refills is retracted from the front end opening of the barrel by the operation of a retractable mechanism. Good too.

An ink backflow preventer is filled at the rear end of the ink filled in the ink storage tube.
The ink backflow preventer composition consists of a non-volatile liquid or a hardly volatile liquid, such as vaseline, spindle oil, castor oil, olive oil, refined mineral oil, liquid paraffin, polybutene, α-olefin, oligomer or cooligomer of α-olefin. , dimethyl silicone oil, methylphenyl silicone oil, amino-modified silicone oil, polyether-modified silicone oil, fatty acid-modified silicone oil, and the like.
The ink backflow preventer composition may be used alone or in combination of two or more types.

It is preferable to add a thickener to the non-volatile liquid and/or the slightly volatile liquid to thicken it to a suitable viscosity.
Examples of thickeners include silica with a hydrophobically treated surface, fine particle silica with a methylated surface, aluminum silicate, swelling mica, clay thickeners such as hydrophobically treated bentonite and montmorillonite, and magnesium stearate. Examples include fatty acid metal soaps such as calcium stearate, aluminum stearate, and zinc stearate, dextrin-based compounds such as tribenzylidene sorbitol, fatty acid amide, amide-modified polyethylene wax, hydrogenated castor oil, fatty acid dextrin, and cellulose-based compounds.
Furthermore, the liquid ink backflow preventer composition and the solid ink backflow preventer composition may be used in combination.

When filling a marking pen, the structure and shape of the marking pen itself are not particularly limited. A marking pen, in which the ink absorber is impregnated with cohesive ink, and the tip is a marking pen in which the ink absorber and the tip are connected, and the ink absorber is impregnated with cohesive ink. An example is a marking pen in which a tip and an ink storage tube are disposed via a valve body that opens when pressed, and ink is directly stored in the ink storage tube.

As a marking pen tip, for example, a porous material with continuous pores selected from a conventional general-purpose material with a porosity in the range of 30 to 70%, such as a resin-processed fiber, a fusion-processed heat-fusible fiber, a felt material, etc. For example, the member can be put into practical use by processing one end into a shape according to the purpose, such as a bullet shape, a rectangular shape, a chisel shape, or the like.

The ink storage body is made up of crimped fibers bundled in the longitudinal direction, and is constructed by incorporating it into a covering such as a plastic cylinder or film, and adjusting the porosity to a range of approximately 40 to 90%. Ru.

Further, although a conventionally general-purpose pumping type valve body can be used, it is preferable that the valve body is set to a spring pressure that can be pressed and released by pen pressure.

Furthermore, the forms of the ballpoint pens and marking pens are not limited to those mentioned above, and may include composite writing instruments (double-headed type, pen nib type, It may be a steering type, etc.).

Handwriting obtained by writing on a surface to be written using a writing instrument containing the writing instrument ink can be discolored by rubbing with a finger or by using a heating tool or a cooling tool.
Examples of heating tools include electrical heating discoloration tools equipped with a resistance heating element such as a PTC element, heating discoloration tools filled with a medium such as hot water, heat discoloration tools using steam or laser light, hair dryers, etc. . Preferably, a friction member is used because the color can be changed by a simple method.
Examples of the cooling device include an energized cold/heat discoloration device using a Peltier element, a cold/heat discoloration device filled with a refrigerant such as cold water or ice chips, a cold storage agent, and applications for refrigerators and freezers.

As the friction member, an elastic body such as an elastomer or a plastic foam that has a rich elastic feel and can generate appropriate friction and generate frictional heat during rubbing is suitable.
Note that handwriting may be rubbed using a general eraser for erasing pencil handwriting, but since eraser scum is generated during rubbing, it is preferable to use the friction member that hardly generates eraser scum. It will be done.
Examples of the material of the friction member include silicone resin, SEBS resin (styrene-ethylene-butadiene-styrene block copolymer), polyester resin, and the like.

Furthermore, a writing instrument set can be obtained by combining a writing instrument and a friction member (friction body) of an arbitrary shape that is separate from the writing instrument, but by providing the friction member on the writing instrument, the writing instrument is superior in portability. be able to.
In the case of a writing instrument equipped with a cap, the location where the friction member is provided is not particularly limited. For example, the cap itself may be formed from the friction member, the barrel itself may be formed from the friction member, or when a clip is provided, the friction member may be formed from the friction member. The writing device itself can be made of a friction member, or a friction member can be provided at the tip (top) of the cap or the rear end of the barrel (the portion where the writing tip is not provided).
In the case of a retractable writing instrument, the location where the friction member is provided is not particularly limited. For example, the barrel itself may be made of a friction member, or if a clip is provided, the clip itself may be made of a friction member, or the shaft may be made of a friction member. A friction member can be provided near the tube opening, at the rear end of the barrel (the portion where the writing tip is not provided), or at the knock portion.

Further, the ink can also be used as a stamp ink.
Water is used as a medium for the stamp ink, but a water-soluble organic solvent can also be used if necessary.
Examples of water-soluble organic solvents include glycols such as glycerin, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,3-butylene glycol, and ethylene glycol monomethyl ether, and their lower alkyl ethers, 2-pyrrolidone, N - Examples include vinylpyrrolidone and urea.
When a reversible thermochromic microcapsule pigment is used in stamp ink, glycerin and propylene glycol are preferred among the water-soluble organic solvents.

The water-soluble organic solvent is preferably blended in an amount of 30 to 60% by mass, more preferably 30 to 55% by mass, and even more preferably 40 to 50% by mass, based on the total amount of the ink. When the proportion of the water-soluble organic solvent is within the above range, the ink does not dry out or absorb moisture, making it easier to obtain clear printed images.
When the blending ratio of the water-soluble organic solvent exceeds 60% by mass, hygroscopicity tends to increase, and the printed image becomes blurred or uneven, making it difficult to obtain a clear printed image. On the other hand, if the blending ratio of the water-soluble organic solvent is less than 30% by mass, the stamp surface becomes dry and the printed image becomes blurred, making it difficult to obtain a clear printed image.

In addition to the water-soluble organic solvent, an organic solvent can also be used as the medium.
Examples of organic solvents include castor oil fatty acid alkyl esters, cellosolve solvents such as methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, and ethyl cellosolve acetate, ethylene glycol acetate, ethylene glycol diethyl ether, ethylene glycol monobutyl ether, and diethylene glycol monoethyl. Ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl Alkylene glycol solvents such as ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether, ethyl formate, amyl Formate, ethyl acetate, ethyl acetoacetate, propyl acetate, butyl acetate, 3-methyl-3-methoxybutyl acetate, amyl acetate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3 -Ethoxypropionate, propyl-3-methoxypropionate, butyl-3-methoxypropionate, methyl lactate, ethyl lactate, ethyl-2-hydroxybutyrate, butyl butyrate, butyl stearate, ethyl caprate, Carbonization of ester solvents such as diethyl oxalate, ethyl pyruvate, ethyl benzoate, etc., n-pentane, n-hexane, n-octane, n-dodecane, diisobutylene, dipentene, hexene, methylcyclohexene, bicyclohexyl, mineral spirits, etc. Hydrogen solvents, halogenated hydrocarbon solvents such as amyl chloride and butyl chloride, alcohol solvents such as 3-methoxy-3-methylbutanol and 3-methoxy-3-methylpentanol, diethyl ether, dipropyl ether, ethyl Ether solvents such as isobutyl ether, dibutyl ether, diisopropyl ether, diamyl ether, dihexyl ether, acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, ethyl amyl ketone, methyl hexyl ketone, methyl Ketone solvents such as nonyl ketone, diisopropyl ketone, diisobutyl ketone, methoxymethylpentanone, and cyclohexanone, propionic acid solvents such as 3-methoxypropionic acid and 3-ethoxypropionic acid, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N- Examples include highly polar solvents such as methylpyrrolidone and benzonitrile, and mixed solvents thereof.

Furthermore, a thickener can also be added to the ink.
Examples of thickeners include xanthan gum, welan gum, succinoglycan (average molecular weight of about 1 million to 8 million), which is an organic acid-modified heteropolysaccharide whose constituent monosaccharides are glucose and galactose, guar gum, locust bean gum, and derivatives thereof. , hydroxyethyl cellulose, alginate alkyl esters, polymers with a molecular weight of 100,000 to 150,000 whose main components are alkyl esters of methacrylic acid, glycomannan, thickeners with gelling ability extracted from seaweed such as agar and carrageenan. Saccharides, benzylidene sorbitol and benzylidene xylitol or derivatives thereof, crosslinkable acrylic acid polymer, inorganic fine particles, polyglycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene lanolin. Nonionic surfactants with an HLB value of 8 to 12 such as lanolin alcohol/beeswax derivatives, polyoxyethylene alkyl ether/polyoxypropylene alkyl ether, polyoxyethylene alkyl phenyl ether, fatty acid amide, salts of dialkyl or dialkenyl sulfosuccinic acids etc. can be exemplified.
Among the thickeners, alkali-soluble acrylic emulsions are preferred.
When an alkali-soluble acrylic emulsion is used as a thickener, the pH of the ink is preferably adjusted to 6 to 11, more preferably 7 to 11, and even more preferably 7 to 10.

Furthermore, by adding a binder resin to the ink, it is possible to improve the adhesion of the printed image and adjust the viscosity of the ink.
Examples of the binder resin include resin emulsions, alkali-soluble resins, water-soluble resins, and the like.
Examples of the resin emulsion include polyacrylic acid ester, styrene-acrylic acid copolymer, polyvinyl acetate, ethylene-vinyl acetate copolymer, ethylene-vinyl chloride copolymer, methacrylic acid-maleic acid copolymer, and ethylene. Examples include aqueous dispersions of -methacrylic acid copolymers, α-olefin-maleic acid copolymers, polyesters, and polyurethanes.
Examples of the alkali-soluble resin include styrene-maleic acid copolymer, ethylene-maleic acid copolymer, styrene-acrylic acid copolymer, and the like.
Examples of the water-soluble resin include polyvinyl alcohol and polyvinyl butyral.
The resin emulsion may be used alone or in combination of two or more.

In addition, various additives such as a pH adjuster, a preservative, or an antifungal agent may be added as necessary.
Examples of the pH adjuster include inorganic salts such as ammonia, sodium carbonate, sodium phosphate, sodium hydroxide, and sodium acetate, and organic basic compounds such as water-soluble amine compounds such as triethanolamine and diethanolamine. .
Examples of preservatives or antifungal agents include carbolic acid, sodium salt of 1,2-benzisothiazolin-3-one, sodium benzoate, sodium dehydroacetate, potassium sorbate, propyl paraoxybenzoate, 2,3,5, Examples include 6-tetrachloro-4-(methylsulfonyl)pyridine.
Other additives include fluorine surfactants, nonionic surfactants, anionic surfactants, cationic surfactants, dimethylpolysiloxane, etc. that improve the permeability of solvents.

Further, if necessary, resins such as acrylic resin, styrene-maleic acid copolymer, cellulose derivative, polyvinylpyrrolidone, polyvinyl alcohol, and dextrin may be added to impart adhesion to the paper surface and viscosity.

In addition, rust inhibitors such as benzotriazole, tolyltriazole, dicyclohexylammonium nitrite, diisopropylammonium nitrite, saponin, urea, nonionic surfactants, reduced or non-reduced starch hydrolysates, oligosaccharides such as trehalose, and sucrose. , cyclodextrin, glucose, dextrin, sorbitol, mannitol, wetting agents such as sodium pyrophosphate, antifoaming agents, dispersants, fluorine surfactants that improve ink permeability, nonionic surfactants, etc. You can also do that.

The reversible thermochromic microcapsule pigment is preferably blended in the ink in an amount of 10 to 40% by mass, more preferably 10 to 35% by mass, and even more preferably 10 to 30% by mass based on the total amount of the ink. Ru. When the blending ratio of the microcapsule pigment exceeds 40% by mass, the dispersion stability of the microcapsule pigment in the ink tends to decrease. On the other hand, if the blending ratio of the microcapsule pigment is less than 10% by mass, the color density tends to decrease.

The stamp ink can be used as a stamp pad ink or a stamp ink provided with a stamp material having continuous pores.
For example, a stamp pad can be obtained by impregnating the stamp pad with ink to supply the ink to the stamp surface of the stamp that is brought into contact with the stamp pad. Further, a stamp can also be obtained by impregnating a stamp material having continuous pores with ink.

A stamp with a stamp material having continuous pores is made of a rubber-like elastic material having continuous pores impregnated with ink. When the stamp material is pressed against a surface to be stamped, ink is applied to the surface to be stamped from the openings of the continuous pores. The surface shape of the stamp is transferred. Areas where transfer is not desired are made into recesses or their openings are closed to prevent ink from adhering to the stamped surface.
Examples of the surface shape of the stamp include a date, a symbol, and characters such as "Top Secret", "CONFIDENTIAL", "Complete", and "Received".

The stamp material having continuous pores is housed in a stamp base material so that its stamp surface is exposed, and the exposed surface is preferably provided with a cap to prevent the ink from drying out when not in use or from being contaminated by accidental contact.
Note that an ink storage section for supplying ink to the stamp material may be provided at the rear of the stamp material having continuous pores to increase the number of impressions.

Further, in addition to impregnating the stamp material with ink in advance and attaching it to the stamp, it is also possible to impregnate the stamp material of the stamp to which the stamp material is attached with ink.
When impregnating the stamp material of the stamp with the stamp material attached, the ink may be impregnated from the front surface of the stamp material, or the ink may be impregnated from the rear surface of the stamp material.
Similarly, for a stamp having an ink reservoir, the ink reservoir may be filled with ink in advance and attached to the stamp, or the ink reservoir of a stamp provided with a stamp material and an ink reservoir may be filled with ink. good.

The stamp is capable of forming an impression on various surfaces to be stamped. Furthermore, the printed image formed with the stamp ink can be discolored by rubbing with a finger or by applying the above-mentioned heating or cooling tool. As the heating tool, the above-mentioned friction member is preferable because the color can be changed by a simple method.

It is also possible to obtain a stamp set by combining a stamp and a friction member (friction body) of an arbitrary shape that is separate from the stamp, but by providing the aforementioned friction member on the stamp, it is possible to obtain a stamp set with excellent portability. can do.

When applying or printing a reversible thermochromic liquid composition, the material of the support is not particularly limited, and all materials are effective, such as paper, synthetic paper, fiber, fabric, synthetic leather, leather, plastic, and glass. , ceramic materials, metals, wood, stone, etc.
The shape of the support is not limited to a planar shape, and may be an uneven shape.
By providing a reversible thermochromic layer containing a reversible thermochromic coloring agent such as a reversible thermochromic composition, a reversible thermochromic microcapsule pigment, or a resin particle on a support, a reversible thermochromic laminate (reversible thermochromic laminate) color-changing prints) can be obtained.
If a non-thermochromic colored layer (non-thermochromic image) is previously formed on the support, the colored layer or image can be hidden by the reversible thermochromic layer by changing the temperature, The aspects of this can be further diversified.

Furthermore, a reversible thermochromic composition, a reversible thermochromic colorant such as a reversible thermochromic microcapsule pigment, or a reversible thermochromic coloring agent such as resin particles is melt-blended with an excipient and molded into a reversible thermochromic solid molded product for application. It can be used as a solid cursive or as a solid cosmetic.
Examples of solid writing materials include crayons, pencil leads, mechanical pencil leads, and solid gel markers.
Examples of solid cosmetics include foundation, eyeliner, eyebrow, eyeshadow, and lipstick.

Excipients used in solid writing include wax, gelling agents, clay, and the like.
The wax is not particularly limited as long as it is conventionally known, and examples thereof include carnauba wax, wood wax, beeswax, microcrystalline wax, montan wax, candelilla wax, sucrose fatty acid ester, dextrin fatty acid ester, Examples include polyolefin wax, styrene-modified polyolefin wax, and paraffin wax.
The gelling agent is not particularly limited as long as it is conventionally known, and examples include 12-hydroxystearic acid, dibenzylidene sorbitol, tribenzylidene sorbitol, amino acid oil, and alkali metal salts of higher fatty acids. I can give an example.
Examples of clay minerals include kaolin, bentonite, and montmorillonite.

Among the excipients, it is preferable to contain at least one of polyolefin wax, sucrose fatty acid ester, or dextrin fatty acid ester, since this facilitates improving handwriting density.
Examples of the polyolefin wax include waxes such as polyethylene, polypropylene, polybutylene, α-olefin polymers, ethylene-propylene copolymers, and ethylene-butene copolymers.

Further, among the above-mentioned polyolefin waxes, those having a softening point in the range of 100 to 130°C and a penetration rate of 10 or less are preferred because they are easy to write on.
If the penetration level exceeds 10, the solid cursive becomes too soft and difficult to write on, and when erasing the handwriting, the handwriting stretches on the paper surface (the wax becomes a thin layer), resulting in blank spaces on the writing surface. This may contaminate the paper, or cause color transfer or staining to other papers.
Note that the softening point and penetration of the polyolefin wax can be measured according to the measurement method specified in JIS K2207, and the penetration value is expressed as 0.1 mm as penetration 1. In other words, the smaller the penetration value of the solid writing material, the harder it is, and the larger the penetration value, the softer it is.

Specifically, the polyolefin waxes include Yasuhara Chemical Co., Ltd. product name: Neowax series, Sanyo Chemical Industries Co., Ltd. product name: Sunwax series, Mitsui Chemicals Co., Ltd. product name: Hiwax series, Examples include Honeywell, product name: AC polyethylene.

As the sucrose fatty acid ester, esters having fatty acids having 12 to 22 carbon atoms as constituent fatty acids are preferred, and palmitic acid and stearic acid are more preferred.
Specific examples of the sucrose fatty acid ester include Mitsubishi Chemical Foods Co., Ltd., product name: Ryoto Sugar Ester Series, Daiichi Kogyo Seiyaku Co., Ltd., product name: Sugar Wax Series, and the like.

As the dextrin fatty acid ester, esters whose constituent fatty acids are fatty acids having 14 to 18 carbon atoms are preferable, and palmitic acid, myristic acid, and stearic acid are more preferable. : Examples include the Leopard series.

Further, as the excipient material used in the solid writing material, side chain crystalline polyolefin is preferable. Here, the side chain crystalline polyolefin has a structure in which relatively long side chains are bonded to a linear main chain. Normal linear polyolefins tend to melt over a wide temperature range because the linear main chain folds and crystallizes, whereas side-chain crystalline polyolefins crystallize mainly in the polyolefin main chain. As a result, it has a low melting point (Mp) and melting occurs in a narrow temperature range.
Among such side chain crystalline polyolefins, those having a long chain alkyl group having 12 to 28 carbon atoms in the side chain are particularly preferred. Further, the long-chain alkyl group on the side chain is not particularly limited and may be either a straight-chain type or a branched type, but a straight-chain long-chain alkyl group is preferable because it has excellent crystallinity.
Note that the alkyl group in the side chain may have a substituent, but the substituent tends to lower the crystallinity, so in order to adjust the crystallinity, the side chain of the side chain crystalline polyolefin may be replaced with, for example, styrene. It can also be denatured. Further, it is preferable that the long-chain alkyl group has a functional group that forms a hydrogen bond, since the long-chain alkyl groups are bonded to each other and aggregated by the hydrogen bond, thereby improving crystallinity.

Further, side chain crystalline polyolefins include polyolefins having a highly branched structure (hereinafter referred to as "highly branched polyolefins"), which can also be used as excipients. Highly branched polyolefins have a low melting point because their main chains are difficult to fold during crystallization, and melting occurs within a narrow temperature range.

In addition, the excipient material preferably has a weight average molecular weight (Mw) of 2,000 to 50,000, and 10 ,000 to 30,000 is more preferable. Further, those having a number average molecular weight (Mn) of 1,000 to 10,000 are preferable.
Note that the weight average molecular weight and number average molecular weight are values measured by gel permeation chromatography (GPC) using polystyrene as a standard.

Specifically, the side chain crystalline polyolefins include HS Crysta 4100 (Mw: 16,000, Mp: 44.4°C), manufactured by Toyokuni Oil Co., Ltd., and HS 6100 (Mw: 28,000, melting point: 60.6°C), manufactured by Idemitsu Kosan Co., Ltd., product names: Elcrysta 4100 (Mw: 16,000), Elcrysta 6100 (Mw: 28,000), etc.
Specifically, the highly branched polyolefins are manufactured by Baker Hughes, product name: VYBAR103 (Mw: 17,348, Mn: 4,400, Mp: 67.7°C), VYBAR260 (Mw: 20,278, Mn: 2 , 600, Mp: 54.7°C), VYBAR343 (Mw: 10,164, Mp: 36.0°C), and VYBAR825 (Mn: 2,800).

The excipient is preferably blended in an amount of 0.2 to 70% by mass, more preferably 0.5 to 40% by mass, based on the total amount of solid writing material. When the blending ratio of the excipient is within the above range, it is easy to obtain the shape of a solid writing body, and the handwriting density of the solid writing body is likely to be high.
When the proportion of excipients exceeds 70% by mass, it becomes difficult to obtain sufficient writing density. On the other hand, if the blending ratio of the excipient is less than 0.2% by mass, it becomes difficult to obtain a shape as a writable core material.

In addition, by adding a filler to the solid writing material, it is possible to improve the strength of the solid writing material and adjust the writing feel.
Examples of fillers include talc, clay, silica, calcium carbonate, barium sulfate, alumina, mica, boron nitride, potassium titanate, and glass flakes.
Among the fillers, talc or calcium carbonate is preferred because they have excellent moldability and do not impair thermochromic properties when microcapsule pigments are used.

The filler is preferably blended in an amount of 10 to 65% by mass based on the total amount of the solid writing material. If the blending ratio of filler exceeds 65% by mass, color development and writing quality tend to deteriorate. On the other hand, if the blending ratio of the filler is less than 10% by mass, the strength of the solid writing material tends to decrease.

Furthermore, the strength of the solid writing material can be improved by blending a binder resin into the solid writing material.
Examples of the binder resin include natural resins, synthetic resins, etc., such as olefin resins, cellulose resins, vinyl alcohol resins, pyrrolidone resins, acrylic resins, styrene resins, amide resins, and basic group-containing resins. Examples include resin.
Among the binder resins, ethylene-vinyl acetate copolymer resins, ethylene-vinyl alcohol copolymer resins, and polyvinyl alcohol resins are preferred, and molding stability can be improved by using these resins and polyester polyol resins in combination. can.
The binder resin is preferably blended in an amount of 0.5 to 5% by mass based on the total amount of the solid writing body.

Furthermore, by blending a hindered amine compound into the solid writing material, it is possible to make it difficult to visually recognize the afterimage of the area where the handwriting on the writing surface has been erased. Therefore, the appearance of the surface to be written on is not spoiled, and rewriteability can be satisfied, and the marketability can be improved.

The hindered amine compound preferably has a molecular weight of 1000 or less because it is highly compatible with other components, does not easily bleed out, and can form clear handwriting even after a period of time.
Moreover, it is preferable that the melting point is 120°C or less. Due to the low melting point, the solid writing material can be manufactured without applying excessive heat during production, and the reversible thermochromic composition, reversible thermochromic microcapsule pigment or resin particles contained in the solid writing material. It is possible to prevent deterioration of reversible thermochromic colorants such as.

In addition, various additives may be added as necessary.
Examples of additives include viscosity modifiers, antifungal agents or preservatives, antibacterial agents, ultraviolet inhibitors, antioxidants, lubricants, fragrances, and the like.

The solid writing body may be used alone as a writing body, or may have a core-sheath structure (double core) in which an outer shell is used as an inner core and covers the outer peripheral surface of the solid writing body.
The outer shell prevents the solid writing body (inner core) inside from being damaged by physical contact, and contributes to improving the mechanical strength of the solid writing body as a whole. The outer shell may or may not contain a reversible thermochromic coloring agent such as a reversible thermochromic composition, a reversible thermochromic microcapsule pigment, or a resin particle that contributes to the formation of handwriting. Generally, the tip of solid cursive is often shaved into a conical shape, so the outer shell often has no effect on the handwriting. Therefore, it is common that reversible thermochromic colorants are not added to the outer shell.

Various additives can be added to the outer shell as needed.
Examples of additives include non-thermochromic colorants, fungicides or preservatives, antibacterial agents, ultraviolet absorbers, antioxidants, lubricants, fragrances, and the like.

The solid writing material can be manufactured by a manufacturing method such as extrusion molding or compression molding.
The above-mentioned solid writing body with a core-sheath structure in which an outer shell is provided to cover the outer circumferential surface of the inner core is obtained by, for example, disposing the outer shell on the outer circumferential surface of a lump of the inner core and compression-molding it with a press. It can be manufactured by a manufacturing method such as.

The thickness and length of the solid cursive font are arbitrarily selected depending on the purpose. For example, when solid writing is used as a pencil lead, the general thickness is 2.0 to 5.0 mm, preferably 2.5 to 4.0 mm. Further, the length is 60 to 300 mm, preferably 80 to 200 mm.

Further, when the solid writing body has a core-sheath structure, the thickness of the inner core and the thickness of the outer shell are also arbitrarily selected. A thicker outer shell provides better impact resistance, while a thinner outer shell exposes more of the inner core, making it easier to use. The thickness of the outer shell relative to the radial length of the inner core is preferably in the range of 10 to 100%, more preferably 20 to 50%.
Note that the thickness and length of the solid writing body are appropriately adjusted depending on the use other than pencils, such as mechanical pencil leads, crayons, and the like.

The solid writing material can be written on various writing surfaces, and can be written using a reversible thermochromic coloring agent such as a reversible thermochromic composition, a reversible thermochromic microcapsule pigment, or a resin particle. Therefore, the handwriting obtained by writing on the writing surface can be discolored by rubbing with a finger or by applying the above-mentioned heating or cooling tool. As the heating tool, the above-mentioned friction member is preferable because the color can be changed by a simple method.

Furthermore, a solid writing set can be obtained by combining a solid writing piece and a friction member (friction body) of an arbitrary shape that is separate from the solid writing piece. By providing the body on the exterior of a solid writing instrument housed in an exterior container, it can be made highly portable. Specifically, examples include a form in which a friction member is provided in the shape of a pencil or crayon whose exterior is made of wood or paper.

Furthermore, reversible thermochromic colorants such as reversible thermochromic compositions, reversible thermochromic microcapsule pigments, or resin particles can be melt-blended with thermoplastic resins, thermosetting resins, waxes, etc. to form pellets, powders, etc. Alternatively, it can be made into a paste form and used as a reversible thermochromic molding resin composition.
The reversible thermochromic molding resin composition is processed into three-dimensional objects of arbitrary shapes, films, sheets, plates, filaments, rods, pipes, etc. by general-purpose injection molding, extrusion molding, blow molding, or cast molding. A molded article having the following form can be obtained.
Furthermore, toners and powder coatings can also be obtained by melt-blending them with thermoplastic resins.

In addition, by blending non-thermochromic coloring agents such as general dyes and pigments into the reversible thermochromic liquid composition, the solid molded article for coating, and the resin composition for molding, it is possible to change the color from colored (1) to colored. (2) exhibits discoloration behavior.

On the molded body or laminate, a layer containing a light stabilizer and/or a transparent metallic luster pigment is laminated to improve light resistance, or a top coat layer is provided to improve durability. You can also do that.
Examples of the light stabilizer include ultraviolet absorbers, antioxidants, singlet oxygen quenchers, superoxide anion quenchers, and ozone quenchers.
Examples of transparent metallic luster pigments include pigments in which the surface of a core material of natural mica, synthetic mica, glass pieces, alumina, and transparent film pieces is coated with a metal oxide such as titanium oxide.

Specific examples of products using the reversible thermochromic composition and microcapsule pigments or resin particles containing the same include the following.
(1) Toys Dolls and animal-shaped toys, hair for dolls and animal-shaped toys, doll houses and furniture, clothing, accessories for dolls such as hats, bags, shoes, accessory toys, stuffed animals, drawing toys, picture books for toys , puzzle toys such as jigsaw puzzles, building blocks toys, block toys, clay toys, fluid toys, spinning tops, kites, musical instrument toys, cooking toys, gun toys, capture toys, background toys, vehicles, animals, plants, buildings, food, etc. imitation toys, etc.
(2) Clothing Clothes such as T-shirts, sweatshirts, blouses, dresses, swimsuits, raincoats, ski wear, footwear such as shoes and shoelaces, cloth personal items such as handkerchiefs, towels, and furoshiki, gloves, neckties, hats, and scarves. , muffler etc.
(3) Indoor decorations: carpets, curtains, curtain strings, table hangers, rugs, cushions, carpets, rugs, upholstery, sheets, mats, picture frames, artificial flowers, photo frames, etc.
(4) Furniture Bedding such as futons, pillows, and mattresses, lighting equipment, air conditioning equipment, etc.
(5) Accessories Rings, bangles, tiaras, earrings, hair clips, false nails, ribbons, scarves, watches, glasses, etc.
(6) Stationery writing instruments, stamps, erasers, pads, rulers, notebooks, adhesive tape, etc.
(7) Daily necessities Cosmetics such as lipstick, eye shadow, foundation, eyeliner, eyebrow, nail polish, hair dye, false nails, paint for false nails, toothbrushes, etc.
(8) Kitchen utensils: cups, plates, chopsticks, spoons, forks, pots, frying pans, etc.
(9) Others Calendars, labels, cards, recording materials, various printed materials to prevent forgery, picture books and other books, bags, packaging containers, embroidery thread, exercise equipment, fishing gear, coasters, musical instruments, body warmers, cold storage agents, wallets bags, umbrellas, vehicles, buildings, temperature detection indicators, teaching materials, etc.

Examples are shown below. In addition, parts in Examples indicate parts by mass.
Example 1
Preparation of reversible thermochromic composition (a) 4 parts of 2-(3-trifluoromethylanilino)-6-(dipentylaminofluorane) as component, N-(2-fluorophenyl)-N as component (b) 5 parts of '-phenylurea [compound (109)], 25 parts of myristyl alcohol and 25 parts of butyl stearate as components (c) were mixed to form a reversible thermochromic composition that changes color from black to colorless when heated and dissolved. Obtained.

Example 2
Preparation of reversible thermochromic microcapsule pigment (a) 4 parts of 2-(3-trifluoromethylanilino)-6-(dipentylaminofluorane), (b) component N-(2-chlorophenyl)-N A reversible thermochromic composition was prepared by mixing 5 parts of '-phenylurea [compound (111)] and 50 parts of neopentyl stearate as component (c), and a microcapsule pigment suspension was encapsulated in microcapsules by an interfacial polymerization method. I got the liquid.
The pigment was isolated from the microcapsule pigment suspension by centrifugation to obtain a reversible thermochromic microcapsule pigment having an average particle diameter of 2 μm and changing color from black to colorless.

Example 3
Preparation of reversible thermochromic microcapsule pigment (a) 4 parts of 2-(3-trifluoromethylanilino)-6-(dipentylaminofluorane) as component, (b) component as N-(2-methoxyphenyl)- A reversible thermochromic composition was prepared by mixing 5 parts of N'-phenylurea [compound (135)] and 50 parts of 4-benzyloxyphenylethyl caprate as component (c), and encapsulated in microcapsules by interfacial polymerization. A microcapsule pigment suspension was obtained.
The pigment was isolated from the microcapsule pigment suspension by centrifugation to obtain a reversible thermochromic microcapsule pigment having an average particle diameter of 2 μm and changing color from black to colorless.

Example 4
Preparation of reversible thermochromic microcapsule pigment (a) Component 3',6'-bis[phenyl(3-methylphenyl)amino]-spiro[isobenzofuran-1(3H),9'-[9H]xanthene] 2 parts of -3-one, 5 parts of N-(2-methoxyphenyl)-N'-phenylurea [compound (135)] as the (b) component, and 50 parts of 4-benzyloxyphenylethyl caprate as the (c) component. A reversible thermochromic composition was prepared by mixing, and a microcapsule pigment suspension encapsulated in microcapsules was obtained by an interfacial polymerization method.
The pigment was isolated from the microcapsule pigment suspension by centrifugation to obtain a reversible thermochromic microcapsule pigment having an average particle diameter of 2 μm and changing color from blue to colorless.

Example 5
Preparation of reversible thermochromic microcapsule pigment (a) Component 9-ethyl(3-methylbutyl)amino-spiro[12H-benzo(a)xanthene-12,1'(3'H)isobenzofuran]-3'- 5 parts of N-(2-methoxyphenyl)-N'-phenylurea [compound (135)] as component (b), and 50 parts of 4-benzyloxyphenylethyl caprate as component (c). A reversible thermochromic composition was prepared, and a microcapsule pigment suspension encapsulated in microcapsules was obtained by interfacial polymerization.
The pigment was isolated from the microcapsule pigment suspension by centrifugation to obtain a reversible thermochromic microcapsule pigment with an average particle diameter of 2 μm and a color change from pink to colorless.

Preparation of Measurement Sample The reversible thermochromic composition of Example 1 was sealed in a transparent glass capillary tube with an inner diameter of 1 mm and a length of 78 mm to a height of about 10 mm from the bottom of the capillary tube to obtain a measurement sample.
The entire part of the measurement sample in which the reversible thermochromic composition is encapsulated is immersed in a transparent heating medium, and the state of discoloration of the reversible thermochromic composition is visually observed while changing the temperature of the transparent heating medium. , t ₁ (complete color development temperature), t ₂ (color development start temperature), t3 (color removal start temperature), t ₄ (complete color removal temperature), ΔH (hysteresis width: temperature between t ₃ and t ₄ - t ₁ and _t2 ) was determined.
40 parts of the reversible thermochromic microcapsule pigments of Examples 2 to 5 were mixed with 50 parts of ethylene-vinyl acetate resin emulsion, 1 part of leveling agent, 1 part of antifoaming agent, 0.5 part of viscosity modifier, and 7.5 parts of water. A reversible thermochromic ink was prepared by uniformly dispersing it in an aqueous ink vehicle consisting of:
A measurement sample was obtained by screen printing a solid pattern on high-quality paper using the above ink.
The measurement sample was set in the measurement part of a color difference meter (TC-3600 type color difference meter, manufactured by Tokyo Denshoku Co., Ltd.), and the temperature of the sample part was raised and lowered at a rate of 2°C/min, and the color density at each temperature was measured. The brightness value was measured and a color density-temperature curve was created. From the color density-temperature curve, t ₁ (complete color development temperature), t ₂ (color development start temperature), t ₃ (color discoloration start temperature), t ₄ (complete discoloration temperature), and ΔH (hysteresis width) were determined.
The test results are shown in Table 1 below.

Application example 1
Preparation of ballpoint pen 20 parts of the reversible thermochromic microcapsule pigment prepared in Example 3 (previously cooled to below -18°C to develop a black color), 0.3 parts of xanthan gum, 10 parts of urea, 10 parts of glycerin, A reversible thermochromic ink composition was prepared containing 0.5 part of a nonionic penetrant property imparting agent, 0.1 part of a modified silicone antifoaming agent, 0.2 part of a preservative, and 58.9 parts of water.
The reversible thermochromic ink composition was suction-filled into a polypropylene pipe, and connected to a ballpoint pen tip having a 0.5 mm stainless steel ball held at the tip via a resin holder.
Next, a viscoelastic ink backflow prevention body (liquid plug) containing polybutene as a main component is filled from the rear end of the polyprene pipe, and a tail plug is fitted to the rear part of the pipe to connect the front barrel and rear barrel. After assembling the barrel and fitting the cap, deaeration treatment was performed by centrifugation to obtain a ballpoint pen.
Note that SEBS resin is attached to the rear part of the rear shaft cylinder as a friction body.
Black characters (handwriting) were formed by writing on paper using the ballpoint pen.
The handwriting is black at room temperature (25°C), and when the character is rubbed with a friction body, the character disappears and becomes colorless, and this state must be maintained unless it is cooled to -18°C or lower. was completed.
Note that when the paper surface was placed in a freezer and cooled to -18° C. or lower, the characters showed a discoloration behavior in which they turned black again, and the discoloration behavior could be repeatedly reproduced.

Application example 2
Preparation of marking pen 25.0 parts of the reversible thermochromic microcapsule pigment prepared in Example 4 (previously cooled to below -17°C to develop a blue color), comb-shaped polymer dispersant [Nippon Lubrizol Co., Ltd., product name: Solsperse 43000] 0.5 part, organic nitrogen sulfur compound [Hokuko Chemical Industry Co., Ltd., product name: Hokuside R-150, 2-methyl-4-isothiazolin-3-one and 5- 1.0 part of a mixture of chloro-2-methyl-4-isothiazolin-3-one], 0.5 part of polyvinyl alcohol, 35.0 parts of glycerin, 0.02 part of an antifoaming agent, and 37.98 parts of water were mixed. A reversible thermochromic ink composition was obtained.
The ink composition is impregnated into an ink storage body made of a polyester sliver covered with a synthetic resin film, and the ink composition is housed in a barrel made of polypropylene resin, and a resin-processed pen body (chisel type) made of polyester fiber is held at the tip of the barrel. Assemble it into a connected state through the and put on the cap to get a marking pen.
SEBS resin is attached to the rear end of the shaft cylinder as a friction member.
Blue letters (handwriting) were formed by writing on the paper using the marking pen.
The handwriting has a blue color at room temperature (25°C), and when the characters are rubbed with a friction body, the characters disappear and become colorless, and this state must be maintained unless the writing is cooled to -17°C or lower. was completed.
Note that when the paper surface was placed in a freezer and cooled to -17° C. or lower, the characters showed a discoloration behavior in which they turned blue again, and the discoloration behavior could be repeatedly reproduced.

Application example 3
Preparation of solid cursive 40 parts of the reversible thermochromic microcapsule pigment prepared in Example 4 (previously cooled to below -17°C to develop a blue color), 35 parts of talc (filler), and side chain crystals. 10 parts of polyolefin (excipient) [manufactured by Toyokuni Oil Co., Ltd., product name: HS Crysta 4100] and polyolefin wax (excipient) [manufactured by Sanyo Chemical Industries, Ltd., product name: Sunwax 131-P] (Softening point: 110°C, penetration: 3.5)], 2 parts of styrene-acrylic acid copolymer resin, 2 parts of polyvinyl alcohol resin, and 1 part of hindered amine light stabilizer are kneaded in a kneader. Then, a kneaded material for the inner core was prepared.
Next, 69 parts of talc (filler), 10 parts of sucrose fatty acid ester, 10 parts of polyolefin wax (excipient), and 10 parts of ethylene-vinyl acetate copolymer were kneaded in a kneader to form the outer shell. A kneaded product was prepared.
The kneaded material for the outer shell was wrapped around the outer peripheral surface so that the kneaded material for the inner core became the inner core, and compression molded using a press to obtain an outer diameter of 3 mm and a length of 60 mm (the inner core was 2 mm in diameter, A solid writing body with a core-sheath structure was produced by molding the shell to a coating thickness of 0.5 mm. Note that the above dimensions are set values, and the solid writing material was produced by cooling to −17° C. after compression molding and returning to room temperature.
A pencil was obtained by storing and molding the solid writing body inside a round outer shaft (wooden shaft). Furthermore, a cylindrical friction body made of SEBS resin was fixed to the rear end of the pencil via a metal connecting member to produce a solid writing instrument with a friction body (a pencil with a friction body).
When the solid writing instrument was used to write on paper to form blue letters (handwriting), the handwriting was blue at room temperature (25°C), and when the letters were rubbed with a friction member, the letters were The color disappeared and became colorless, and this state could be maintained as long as it was not cooled to -17°C or lower.
Furthermore, when the paper surface was placed in a freezer and cooled to -17°C or lower, the letters showed a color change behavior in which they turned blue again, and this color change behavior could be reproduced repeatedly.

Application example 4
Preparation of Stamp 20 parts of the reversible thermochromic microcapsule pigment prepared in Example 5 (previously cooled to below -18°C to develop a pink color), 50 parts of glycerin, and an alkali-soluble acrylic emulsion [ 1.5 parts of Primal DR73, manufactured by Rohm & Haas Japan Co., Ltd., 0.9 parts of triethanolamine, 10 parts of a 50% aqueous solution of polyvinylpyrrolidone, and 0.2 parts of a silicone antifoaming agent. A reversible thermochromic stamp ink was prepared by mixing 0.5 parts of a penetrating leveling agent, 0.2 parts of a preservative, and 16.7 parts of water.
A stamp material having continuous pores was impregnated with the stamp ink, fixed to a stamp base material so that the stamp surface of the stamp material was exposed, and a cap was fitted to produce a stamp.
Note that SEBS resin is attached to the rear end of the stamp base material as a friction member.
When the stamp is repeatedly pressed against the surface to be stamped (paper surface), the ink smoothly flows out from the stamp surface of the stamp material and transfers to the surface to be stamped, and a clear stamp image is continuously formed without blurring. I was able to do that.
The printed image is pink at room temperature (25°C), and when rubbed with a friction member, the printed image disappears and becomes colorless, and this state must be maintained unless it is cooled to below -18°C. was completed.
Note that when the paper surface was placed in a freezer and cooled to -18° C. or lower, the printed image showed a discoloration behavior in which it turned pink again, and this discoloration behavior could be repeatedly reproduced.

Application example 5
Preparation of reversible thermochromic printed matter 30 parts of the reversible thermochromic microcapsule pigment prepared in Example 3 (previously cooled to below -18°C to develop a black color), 5 parts of red dye, and linseed oil-based A reversible thermochromic offset ink was prepared by mixing with 65 parts of offset ink vehicle.
Offset printing was performed using the above-mentioned offset ink on both the front and back surfaces of high-quality paper as a printing medium, and the offset printing was dried and hardened to form a date (thermochromic image).
Note that the thermochromic images on the front and back surfaces are formed so as not to overlap.
Next, offset printing was performed using a non-color-changing black offset ink, which was dried and cured to form a frame line (non-color-changing image) to produce a reversible thermochromic printed matter.
The reversible thermochromic printed material is initially a notebook-shaped printed material with a black date, but it turns red due to the frictional heat generated by rubbing the thermochromic image at any location on the surface using a friction member. It was useful for holiday schedule management because it could be changed in color and the discolored state could be maintained at room temperature (25°C).
In addition, the dates marked on the back of the discolored area do not change color due to heat transfer when the thermochromic image on the front surface changes color, making it possible to accurately manage schedules.

Application example 6
Preparation of reversible thermochromic display material An ink prepared by dispersing the reversible thermochromic microcapsule pigment prepared in Example 3 in a vehicle containing a binder resin was used on the surface of a white polyester film (thickness 25 μm) as a support. A reversible color-changing layer was provided by printing, and a transparent polyester film having a thickness of 16 μm was further laminated on the upper surface to obtain a reversible thermochromic display.
The display body was once cooled to −18° C. or lower to completely develop a black color in the reversible thermochromic layer, and then printed using a thermal transfer printer to form white punched characters.
The white cut-out characters are visible as long as the display body is maintained in a temperature range of -18°C to 64°C.
Further, when the display body is cooled to -18° C. or lower again and the reversible thermochromic layer is completely colored black, the white cut-out characters are no longer visible, and the white cut-out characters can be formed using the thermal transfer printer. This allowed it to be used over and over again.

Application example 7
Preparation of Doll 5 parts of the reversible thermochromic microcapsule pigment prepared in Example 2, 1 part of a dispersant, 94 parts of nylon 12 with a melting point of 180°C, and 0.1 part of a general pink pigment, The mixture was melt-mixed in an extruder at 200°C to prepare reversible thermochromic pellets for the core.
The reversible thermochromic pellets were supplied to an extrusion molding machine for forming the core, and the nylon 12 natural pellets were supplied to an extrusion molding machine for forming the sheath, and the core:sheath volume ratio was 6:1 using a composite fiber spinning device. 4, a reversible thermochromic conjugate fiber consisting of 18 single yarns each having an outer diameter of 90 μm was prepared by spinning at 200° C. through 18 discharge holes.
Furthermore, the reversible thermochromic conjugate fibers were implanted on the doll's head using a conventional method to produce a doll with hair made of the reversible thermochromic conjugate fibers.
The doll's hair was once cooled to below 12° C. to develop a completely black color, and then immersed in warm water at 40° C., the color changed from black to pink. Moreover, when it was taken out from hot water and immersed in cold water at 5° C., it turned black again. This change could be repeated.

Application example 8
Preparation of reversible thermochromic miniature car 15 parts of the reversible thermochromic microcapsule pigment prepared in Example 2, 40 parts of 50% acrylic resin/xylene solution, 20 parts of xylene, 20 parts of methyl isobutyl ketone, 5 parts of polyisocyanate curing agent A reversible thermochromic spray paint was obtained by stirring and mixing the mixture into a vehicle consisting of 1.
The reversible thermochromic spray paint was spray-painted onto the entire body of a white miniature car and dried to form a reversible thermochromic layer, thereby obtaining a reversible thermochromic miniature car (toy).
The miniature car was once cooled to 12° C. or lower to completely develop a black color in the reversible thermochromic layer, and then it became white when immersed in 40° C. hot water. When removed from hot water and immersed in cold water at 5°C, it turned black again and the above procedure could be repeated.

Application example 9
Preparation of reversible thermochromic mug 30 parts of reversible thermochromic microcapsule pigment prepared in Example 2, 60 parts of hard liquid epoxy resin, 2 parts of ultraviolet absorber, 2 parts of thixotropy agent, 0.5 part of antifoaming agent. were mixed, and 40 parts of a cold-curable aliphatic polyamine was further added to obtain a reversible thermochromic epoxy ink.
Using the reversible thermochromic epoxy ink, print a polka dot pattern on the side of a ceramic mug using a curved surface printing machine with a stainless steel screen plate, and heat and cure at 70 ° C. for 1 hour to form a reversible thermochromic layer. , a reversible thermochromic mug was obtained.
Once cold water of 12°C or lower is poured into the mug, the reversible thermochromic layer develops a black color and a polka dot pattern is visible, but if the cold water is removed from this state and hot water of 50°C is poured, the reversible thermochromic layer becomes black. The thermochromic layer disappears and becomes colorless. Furthermore, when the hot water is removed from this state and cold water of 5°C is poured, the reversible thermochromic layer develops color and the black polka dot pattern becomes visible again.
Note that this change in appearance could be repeated by changing the temperature.

t1 Complete coloring temperature t2 Coloring start temperature t3 Coloring start temperature t4 Complete coloring temperature ΔH Hysteresis width

Claims (14)

(a) Identification of the electron transfer reaction between the electron-donating color-forming organic compound, (b) the compound represented by formula (1) as the electron-accepting compound, and (c) the components (a) and (b) above. A reversible thermochromic composition comprising a reaction medium that is reversibly generated in a temperature range.

(In the formula, X represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a trihalogenated methyl group, a nitro group, a halogen atom, or a hydrogen atom. Y is a carbon number Represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a hydrogen atom, a halogen atom, or a substituent represented by formula (2). n represents an integer of 1 to 3. However, X and Y are different.

In formula (2), Z represents O, S, a linear or branched alkylene group having 1 to 12 carbon atoms, NH, SO ₂ or C=O. R ₁ and R ₂ represent an alkyl group having 1 to 6 carbon atoms, a nitro group, a halogen atom or a hydrogen atom. ) 2. In formula (1), X represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom, and Y represents a hydrogen atom or a halogen atom. Reversible thermochromic composition. A reversible thermochromic microcapsule pigment comprising the reversible thermochromic composition according to claim 1 or 2. A reversible thermochromic liquid composition comprising the reversible thermochromic microcapsule pigment according to claim 3 and a vehicle. 5. The reversible ink according to claim 4, which is selected from the group consisting of printing ink, writing instrument ink, applicator ink, stamp ink, inkjet ink, paint, ultraviolet curable ink, paint, cosmetic, and textile coloring liquid. Thermochromic liquid composition. A reversibly thermochromic solid molded article for coating, comprising the reversibly thermochromic microcapsule pigment according to claim 3 and an excipient. The reversibly thermochromic solid molded article for application according to claim 6, which is a solid writing material or a solid cosmetic. A reversible thermochromic molding resin composition comprising the reversible thermochromic microcapsule pigment according to claim 3 and a molding resin. A reversible thermochromic molded article formed by molding the reversible thermochromic molding resin composition according to claim 8. A reversible thermochromic laminate comprising a support and a reversible thermochromic layer comprising the reversible thermochromic microcapsule pigment according to claim 3. A writing instrument containing the ink for a writing instrument according to claim 5. The writing instrument according to claim 11, wherein the writing instrument is a ballpoint pen. The writing instrument according to claim 11, wherein the writing instrument is a marking pen. 12. The writing instrument according to claim 11, further comprising a friction member that discolors the handwriting made by the writing instrument due to frictional heat.

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