JP2023097327A - Aqueous ink composition for reversible thermochromic writing instrument, and writing instrument containing the same - Google Patents

Abstract

To provide an aqueous ink composition for a reversible thermochromic writing instrument which enables stable formation of handwriting having thermochromism, and is excellent in overwriting property and dry-up resistance, and a writing instrument containing the ink composition.SOLUTION: There are provided: an aqueous ink composition for a reversible thermochromic writing instrument which includes a reversible thermochromic microcapsule pigment including a reversible thermochromic composition composed of (i) an electron-donating colorable organic compound, (ii) an electron-accepting compound, and (iii) a reaction medium for determining respective temperatures causing the respective color reactions of both of the compounds (i) and (ii), a specific betaine type amphoteric surfactant, a shear viscosity-reducing imparting agent, and water, wherein the shear viscosity-reducing imparting agent is a polysaccharide; and a writing instrument containing the aqueous ink composition for a reversible thermochromic writing instrument.SELECTED DRAWING: Figure 1

Description

TECHNICAL FIELD The present invention relates to a reversible thermochromic water-based ink composition for writing instruments and a writing instrument containing the same.

In recent years, inks for writing instruments, in which microcapsule pigments encapsulating thermochromic compositions are applied as coloring materials, are known and used in ballpoint pens and the like. (For example, see Patent Document 1)
The ink of the prior art is an ink in which the dispersion stability of the thermochromic microcapsule pigment and the ink ejection property during writing are improved by a shear-thinning substance, and clear handwriting having thermochromic property is stably produced. considered to be formable. In addition, the handwriting formed with the ink can be thermally erased by rubbing with an elastic body or the like, and it is possible to correct the characters etc. by rewriting with the ink on the erased handwriting. .
However, it cannot be said that the above ink has good performance in overwriting, in which the handwriting is overwritten with the same ink that formed the handwriting, and it is sometimes difficult to form clear overwriting handwriting by overwriting. rice field.

In addition, the thermochromic microcapsule pigment does not have sufficient coloring power as compared with general coloring agents such as organic pigments and carbon black. In such a case, when the water in the ink evaporates, solids such as microcapsule pigments tend to precipitate. When such precipitation occurs on the tip of the ballpoint pen, the ball sticks to the tip of the ballpoint pen, making it difficult to rewrite (so-called dry-up).

As described above, the conventional inks have problems, and there is still room for further improvement in performance.

JP-A-9-124993

The present invention provides a water-based ink composition for a reversible thermochromic writing instrument, which is an ink capable of stably forming clear handwritings having thermochromic properties and which is excellent in overwriting properties and dry-up resistance, and a writing instrument containing the same. It provides

式中、Ａ_１、Ａ_２は、独立して炭素数１～３のアルキル基であり、Ａ_３は炭素数５～２４のアルキル基または下記一般式（２）で示される官能基である。

式中、Ａ_４は炭素数１～５のアルキル基であり。Ａ_５は炭素数１～１６のアルキル基である。
２．前記ベタイン型両性界面活性剤の含有率が、インキ組成物全質量を基準として０．０１～２．０質量％である、第１項に記載のインキ組成物。
３．インキ組成物全質量を基準として、前記ベタイン型両性界面活性剤の含有率が、前記可逆熱変色性マイクロカプセル顔料の含有率に対して０．２０～３．０％である、第２項に記載のインキ組成物。
４．前記多糖類がキサンタンガム及び／又はサクシノグリカンである、第１項に記載のインキ組成物。
５．第１項～第４項のいずれか１項に記載のインキ組成物を収容してなる、筆記具。
６．ボールペンである、第５項に記載の筆記具。
７．摩擦部材を備えてなる、第６項に記載のボールペン。
８．第１項～第４項のいずれか１項に記載のインキ組成物を収容してなるボールペンレフィル」とする。 The present invention
"1. A reversible reaction medium consisting of (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reaction medium that determines the temperature at which the color reaction of (a) and (b) occurs. A reversible thermochromic microcapsule pigment encapsulating a thermochromic composition, a betaine-type amphoteric surfactant represented by the following general formula (1), a shear-thinning agent, and water, wherein the shear-thinning A reversible thermochromic water-based ink composition for writing instruments, wherein the imparting agent is a polysaccharide.

In the formula, A ₁ and A ₂ are independently alkyl groups having 1 to 3 carbon atoms, and A ₃ is an alkyl group having 5 to 24 carbon atoms or a functional group represented by the following general formula (2).

In the formula, _A4 is an alkyl group having 1 to 5 carbon atoms. A ₅ is an alkyl group having 1 to 16 carbon atoms.
2. 2. The ink composition according to item 1, wherein the content of the betaine-type amphoteric surfactant is 0.01 to 2.0% by mass based on the total mass of the ink composition.
3. Item 2, wherein the content of the betaine-type amphoteric surfactant is 0.20 to 3.0% relative to the content of the reversible thermochromic microcapsule pigment, based on the total mass of the ink composition. The described ink composition.
4. 2. The ink composition of claim 1, wherein said polysaccharide is xanthan gum and/or succinoglycan.
5. A writing instrument containing the ink composition according to any one of items 1 to 4.
6. 6. The writing instrument according to Item 5, which is a ballpoint pen.
7. 7. Ballpoint pen according to item 6, comprising a friction member.
8. A ballpoint pen refill containing the ink composition according to any one of items 1 to 4”.

INDUSTRIAL APPLICABILITY According to the present invention, a reversible thermochromic water-based ink composition for writing instruments, which is an ink capable of stably forming clear handwritings having thermochromic properties and is excellent in overwriting properties and dry-up resistance, and a writing instrument containing the same. is provided.

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

The water-based ink composition for reversible thermochromic writing instruments according to the present invention (hereinafter sometimes referred to as "ink composition") comprises a reversible thermochromic microcapsule pigment, water, and a specific betaine-type amphoteric surfactant. contains at least Each component constituting the ink composition according to the present invention will be described below.
In this specification, overwriting may be referred to as overwriting to overwrite the handwriting with the same ink as that used to form the handwriting.

式中、Ａ_１、Ａ_２は、独立して炭素数１～３のアルキル基であり、Ａ_３は炭素数５～２４のアルキル基または下記一般式（２）で示される官能基である。

式中、Ａ_４は炭素数１～５のアルキル基であり。Ａ_５は炭素数１～１６のアルキル基である。
前記ベタイン型両性界面活性剤は、可逆熱変色性マイクロカプセル顔料を含有するインキで重ね書きを行う際、上書き筆跡を掠れや途切れが抑制された鮮明な筆跡にできる。これは、理由は定かではないが、前記ベタイン型両性界面活性剤は、可逆熱変色性マイクロカプセル顔料を含有するインキの濡れ性や、可逆熱変色性マイクロカプセル顔料を含有するインキで形成された筆跡へのインキの乗りを向上させることができ、重ね書きの際、上書きによる筆跡形成性が高まるためであると推測される。 (Betaine type amphoteric surfactant)
The ink composition contains a betaine-type amphoteric surfactant represented by the following general formula (1).

In the formula, A ₁ and A ₂ are independently alkyl groups having 1 to 3 carbon atoms, and A ₃ is an alkyl group having 5 to 24 carbon atoms or a functional group represented by the following general formula (2).

In the formula, _A4 is an alkyl group having 1 to 5 carbon atoms. A ₅ is an alkyl group having 1 to 16 carbon atoms.
The betaine-type amphoteric surfactant can make clear handwritings with less blurring and discontinuities when overwriting with an ink containing a reversible thermochromic microcapsule pigment. Although the reason is not clear, the betaine-type amphoteric surfactant is formed with the ink containing the reversible thermochromic microcapsule pigment and the wettability of the ink containing the reversible thermochromic microcapsule pigment. It is presumed that this is because the spread of ink on the handwriting can be improved, and when overwriting, the handwriting formability due to overwriting is enhanced.

In addition, the betaine-type amphoteric surfactant can also improve the dry-up resistance of the ink. It is possible to prevent rewriting from being hindered due to sticking of the ball during the process of depositing the solid content such as the imparting agent. Furthermore, the betaine-type amphoteric surfactant has the effect of increasing lubricity, smoothing the rotation of the ball and providing good ink ejection from the tip of the ball-point pen.

Considering the above-mentioned overwriting handwriting to be a clear handwriting with suppressed blurring and interruption and to improve dry-up resistance, A ₃ in the general formula (1) has 8 to 24 carbon atoms. An alkyl group or a functional group of general formula (2) having an alkyl group having 2 to 4 carbon atoms as A ₄ and an alkyl group having 3 to 14 carbon atoms as A ₅ is preferable, and A ₃ has 8 to 4 carbon atoms. 22, or a functional group of general formula (2) having an alkyl group of 2 to 4 carbon atoms as A ₄ and an alkyl group of 6 to 13 carbon atoms as A ₅ . More preferably, A ₃ is an alkyl group having 10 to 20 carbon atoms, or a functional group represented by general formula (2) having an alkyl group having 2 to 4 carbon atoms as A ₄ and an alkyl group having 8 to 13 carbon atoms as A ₅ is the base. Betaine-type amphoteric surfactants having such functional groups are excellent in the effect of making overwritten handwriting clear and improving dry-up resistance, and exhibiting excellent affinity for microcapsule pigments and reversible thermochromic properties. It is also possible to further enhance the dispersibility of the microcapsule pigment.

The content of the betaine amphoteric surfactant is preferably 0.01 to 2.0% by mass, more preferably 0.02 to 1.5% by mass, more preferably 0.02 to 1.0% by mass, based on the total mass of the ink composition. 0% by weight is more preferred, 0.05 to 1.0% by weight is more preferred, and 0.05 to 0.5% by weight is particularly preferred. When the content is within the above range, it is easy to make the overwritten handwriting clear, and it is easy to improve the dry-up resistance.

In addition, in consideration of improving the dry-up resistance of the ink, the content of the betaine-type amphoteric surfactant, based on the total mass of the ink composition, is equal to the content of the reversible thermochromic microcapsule pigment. It is preferably 0.20 to 3.0%, more preferably 0.20 to 2.5%, even more preferably 0.20 to 2.0%, and 0.25 to 2.0% is particularly preferred.

The ink composition according to the present invention contains a reversible thermochromic microcapsule pigment (hereinafter sometimes referred to as "microcapsule pigment") as a colorant.

The microcapsule pigment used in the ink composition according to the present invention encloses the reversible thermochromic composition. As the reversible thermochromic composition, (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, (c) the temperature at which the color reaction of the component (a) and the component (b) occurs is It can be used for a reversible thermochromic composition of a heat decoloring type (discoloring by heating and developing color by cooling) containing at least three essential components of the reaction medium to be determined.

Examples of reversible thermochromic compositions to which such microcapsule pigments can be applied are described in JP-B-51-44706, JP-B-51-44707, JP-B-1-29398, etc. In addition, it changes color before and after a predetermined temperature (color change point) as a boundary, exhibits a discolored state in a temperature range above the high temperature side color change point, and a color development state in a temperature range below the low temperature side color change point. Only one particular state exists in a region and the other state is maintained as long as the heat or cold required to bring about the state is applied, but when the application of heat or cold is removed A composition having a relatively small hysteresis width (ΔH) (ΔH=1 to 7° C.) that returns to the state exhibited in the normal temperature range can be mentioned (see FIG. 1).

Further, other examples of reversible thermochromic compositions to which such microcapsule pigments can be applied include JP-B-4-17154, JP-A-7-179777 and JP-A-7-33997. , JP-A-8-39936, JP-A-2005-1369, etc. show characteristics with a large hysteresis width (ΔH = 8 to 70 ° C.), and a curve plotting changes in color density due to temperature changes. When the temperature is raised from the lower temperature side than the color change temperature range, and when the temperature is lowered from the higher temperature side than the color change temperature range, the color changes along a significantly different path, and the color changes when the complete color temperature t is ₁ or less. The color development state in the temperature range or the color disappearance state in the high temperature range of the complete color disappearance temperature t ₄ or higher is the specific temperature range [the temperature range between the color development start temperature t ₂ and the color disappearance start temperature t ₃ (substantially two-phase (holding temperature range)] can also be used (see FIG. 2).

[Microcapsule pigment]
Each (a) component, (b) component, and (c) component will be specifically described below.
Component (a), that is, an electron-donating color-developing organic compound is a component that determines color, and is a compound that provides electrons to component (b), which is a color developer, to develop color.

Electron-donating color-developing organic compounds include phthalide compounds, fluoran compounds, stilinoquinoline compounds, diazarhodamine lactone compounds, pyridine compounds, quinazoline compounds, and bisquinazoline compounds. preferable.
Examples of phthalide compounds include diphenylmethanephthalide compounds, phenylindolylphthalide compounds, indolylphthalide compounds, diphenylmethaneazaphthalide compounds, phenylindolylazaphthalide compounds, and derivatives thereof. Among them, phenylindolylazaphthalide compounds and derivatives thereof are preferred.
Examples of fluoran compounds include aminofluoran compounds, alkoxyfluoran compounds, derivatives thereof, and the like.

Compounds that can be used as the component (a) are exemplified below.
3,3-bis(4-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-n-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-propyl-2-methylindol-3-yl)-4-azaphthalide,
3,6-bis(diphenylamino)fluorane,
3,6-bis(N-phenyl-Np-tolylamino)fluorane,
3,6-dimethoxyfluorane,
3,6-di-n-butoxyfluorane,
2-methyl-6-(N-ethyl-Np-tolylamino)fluorane,
3-chloro-6-cyclohexylaminofluorane,
2-methyl-6-cyclohexylaminofluorane,
2-chloroamino-6-di-n-butylaminofluorane,
2-(2-chloroanilino)-6-di-n-butylaminofluorane,
2-(3-trifluoromethylanilino)-6-diethylaminofluorane,
2-(3-trifluoromethylanilino)-6-di-n-pentylaminofluorane,
2-dibenzylamino-6-diethylaminofluorane,
2-(N-methylanilino)-6-(N-ethyl-Np-tolylamino)fluorane,
1,3-dimethyl-6-diethylaminofluorane,
2-chloro-3-methyl-6-diethylaminofluorane,
2-anilino-3-methyl-6-diethylaminofluorane,
2-anilino-3-methoxy-6-diethylaminofluorane,
2-anilino-3-methyl-6-di-n-butylaminofluorane,
2-anilino-3-methoxy-6-di-n-butylaminofluorane,
2-xylidino-3-methyl-6-diethylaminofluorane,
2-anilino-3-methyl-6-(N-ethyl-Np-tolylamino)fluorane,
6-diethylamino-1,2-benzofluorane,
6-(N-ethyl-N-isobutylamino)-1,2-benzofluorane,
6-(N-ethyl-N-isopentylamino)-1,2-benzofluorane,
2-(3-methoxy-4-dodecoxystyryl)quinoline,
2-diethylamino-8-diethylamino-4-methylspiro[5H-[1]benzopyrano[2,3-d]pyrimidine-5,1′(3′H)-isobenzofuran]-3′-one,
2-di-n-butylamino-8-di-n-butylamino-4-methylspiro[5H-[1]benzopyrano[2,3-d]pyrimidine-5,1′(3′H)-isobenzofuran] -3′-on,
2-di-n-butylamino-8-diethylamino-4-methylspiro[5H-[1]benzopyrano[2,3-d]pyrimidine-5,1′(3′H)-isobenzofuran]-3′-one ,
2-di-n-butylamino-8-(N-ethyl-N-isoamylamino)-4-methylspiro[5H-[1]benzopyrano[2,3-d]pyrimidine-5,1′(3′H) -isobenzofuran]-3'-one,
2-di-n-butylamino-8-di-n-pentylamino-4-methylspiro[5H-[1]benzopyrano[2,3-d]pyrimidine-5,1′(3′H)-isobenzofuran] -3′-on,
4,5,6,7-tetrachloro-3-(4-dimethylamino-2-methoxyphenyl)-3-(1-n-butyl-2-methylindol-3-yl)-1(3H)-iso benzofuranone,
4,5,6,7-tetrachloro-3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-1(3H)-isobenzofuranone,
4,5,6,7-tetrachloro-3-(4-diethylamino-2-ethoxyphenyl)-3-(1-n-pentyl-2-methylindol-3-yl)-1(3H)-isobenzo Furanones,
4,5,6,7-tetrachloro-3-(4-diethylamino-2-methylphenyl)-3-(1-ethyl-2-methylindol-3-yl)-1(3H)-isobenzofuranone,
3′,6′-bis[phenyl(2-methylphenyl)amino]spiro[isobenzofuran-1(3H),9′-[9H]xanthen]-3-one,
3′,6′-bis[phenyl(3-methylphenyl)amino]spiro[isobenzofuran-1(3H),9′-[9H]xanthen]-3-one,
3′,6′-bis[phenyl(3-ethylphenyl)amino]spiro[isobenzofuran-1(3H),9′-[9H]xanthen]-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-methoxyquinazoline,
4,4'-ethylenedioxy-bis[2-(4-diethylaminophenyl)quinazoline]

As the fluoranes, in addition to compounds having a substituent on the phenyl group forming the xanthene ring, a substituent on the phenyl group forming the xanthene ring and a substituent on the phenyl group forming the lactone ring (e.g. , an alkyl group such as a methyl group, a halogen atom such as a chlorine atom, etc.) and exhibiting a blue or black color.

Component (b), ie, an electron-accepting compound, is a compound that receives electrons from component (a) and functions as a color developer for component (a).
The electron-accepting compounds include a group of compounds having an active proton, a group of pseudo-acidic compounds [a group of compounds that are not acids but act as acids in the reversible thermochromic composition to develop the color of component (a)], and electron A compound selected from a group of compounds having vacancies and the like can be mentioned. Among the components (b) above, compounds selected from the group of compounds having an active proton are preferred.

Compounds having an active proton include compounds having a phenolic hydroxyl group and derivatives thereof, carboxylic acids and derivatives thereof, acidic phosphoric acid esters and derivatives thereof, azole compounds and derivatives thereof, 1,2,3-triazoles and derivatives thereof, cyclic carbosulfimides, halohydrins having 2 to 5 carbon atoms, sulfonic acid and its derivatives, inorganic acids and the like. Preferred carboxylic acids and derivatives thereof are aromatic carboxylic acids and derivatives thereof, or aliphatic carboxylic acids having 2 to 5 carbon atoms and derivatives thereof.
Pseudo-acidic compounds include 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, and aliphatic carboxylic acid anhydrides. , mixed anhydrides of aromatic carboxylic acids and sulfonic acids, cycloolefin dicarboxylic anhydrides, urea and its derivatives, thiourea and its derivatives, guanidine and its derivatives, and halogenated alcohols.
Examples of compounds having electron vacancies include borates, borate esters, and inorganic salts.

Among the above components (b), a compound having a phenolic hydroxyl group is preferable because it can more effectively exhibit thermochromic properties.
Compounds having a phenolic hydroxyl group include a wide range of monophenol compounds to polyphenol compounds, and further include bisphenol compounds, trisphenol compounds, phenol-aldehyde condensed resins, and the like. A compound having a phenolic hydroxyl group preferably has at least two benzene rings. Moreover, 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 carboxy group and its ester or amide group, and a halogen atom.

Examples of metals contained in metal salts of compounds having phenolic hydroxyl groups include sodium, potassium, calcium, zinc, zirconium, aluminum, magnesium, nickel, cobalt, tin, copper, iron, vanadium, titanium, lead, and molybdenum. etc. can be exemplified.

The compounds of component (b) are exemplified 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)decan-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,
4-hydroxybenzoate-p-propylbenzyl,
4-hydroxybenzoate-p-tert-butylbenzyl,
phenylethyl 4-hydroxybenzoate,
4-hydroxybenzoate-o-methylphenylethyl,
4-hydroxybenzoate-m-methylphenylethyl,
p-methylphenylethyl 4-hydroxybenzoate,
p-ethylphenylethyl 4-hydroxybenzoate,
4-hydroxybenzoate-p-propylphenylethyl,
4-Hydroxybenzoic acid-p-tert-butylphenylethyl and the like can be exemplified.

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,
β-methyl resorcinate,
β-benzyl resorcinate,
2-chloro-4-pentanoylresorcin,
6-chloro-4-pentanoylresorcin,
2-chloro-4-hexanoylresorcin,
6-chloro-4-hexanoylresorcin,
2-chloro-4-propanoylresorcin,
6-chloro-4-propanoylresorcin,
2,6-dichloro-4-propanoylresorcin,
6-fluoro-4-propanoylresorcin,
2-chloro-4-phenylacetylresorcinol,
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,
methyl hydroquinone,
trimethylhydroquinone,
catechol,
4-tert-butyl catechol,
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 a bisphenol compound, 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)butyl propionate,
2,2-bis(4-hydroxy-3-methylphenyl)methylpropionate,
2,2-bis(4-hydroxyphenyl)ethyl propionate,
2,2-bis(4-hydroxyphenyl)-4-methylpentane,
2,2-bis(4-hydroxyphenyl)-4-methylhexane,
2,2-bis(4-hydroxyphenyl)hexafluoropropane,
2,2-bis(3,5-dihydroxymethyl-4-hydroxyphenyl)hexafluoropropane,
2,2-bis(4-hydroxy-3-methylphenyl)propane,
2,2-bis(4-hydroxy-3-methylphenyl)butane,
2,2-bis(4-hydroxy-3-isopropylphenyl)propane,
2,2-bis(3-sec-butylphenyl-4-hydroxy)propane,
2,2-bis(4-hydroxy-3-phenylphenyl)propane,
2,2-bis(3-tert-butyl-4-hydroxyphenyl)propane,
2,2-bis(3-fluoro-4-hydroxyphenyl)propane,
2,2-bis(3,5-dihydroxymethyl-4-hydroxyphenyl)propane,
9,9-bis(4-hydroxy-3-methylphenyl)fluorene,
1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene,
1,4-bis[2-(4-hydroxyphenyl)-2-propyl]benzene,
3,3-bis(4-hydroxyphenyl)oxindole,
3,3-bis(4-hydroxy-3-methylphenyl)oxindole,
bis(2-hydroxyphenyl)methane,
bis(2-hydroxy-5-methylphenyl)methane,
bis(2-hydroxy-3-hydroxymethyl-5-methyl)methane,
4,4′-[1,4-phenylenebis(1-methylethylidene)]bis(2-methylphenol),
1,1-bis(4-hydroxy-3-phenylphenyl)cyclohexane,
3,3-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-hydroxydiphenyl sulfone,
4-methyl-4'-hydroxyphenylsulfone,
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′-trihydroxydiphenyl sulfone,
bis(3,4-dihydroxyphenyl)sulfone,
2,3,4-trihydroxydiphenyl sulfone,
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 compounds 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″-methylidyne trisphenol,
4,4′,4″-methylidynetris(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″-ethylidine trisphenol,
4,4′,4″-ethylidine 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-hydroxyphenyl)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″-methylidyne trisphenol,
4,4′-[(2-hydroxyphenyl)methylene]bis(3-methylphenol),
4,4′-[4-(4-hydroxyphenyl)-sec-butylidene]bis(4-hydroxyphenol),
2,2′-[(3-hydroxyphenyl)methylene]bis(3,5-dimethylphenol),
4,4′-[(2-hydroxy-3-methoxyphenyl)methylene]bis(2,5-dimethylphenol),
4,4′-[(2-hydroxy-3-methoxyphenyl)methylene]bis(2,6-dimethylphenol),
2,2′-[(2-hydroxy-3-methoxyphenyl)methylene]bis(3,5-dimethylphenol),
2,2′-[(3-hydroxy-4-methoxyphenyl)methylene]bis(3,5-dimethylphenol),
2,2′-[(4-hydroxy-3-methoxyphenyl)methylene]bis(3,5-dimethylphenol),
4,4′-[(2-hydroxyphenyl)methylene]bis(2-isopropylphenol),
4,4′-[(3-hydroxyphenyl)methylene]bis(2-isopropylphenol),
4,4′-[(4-hydroxyphenyl)methylene]bis(2-isopropylphenol),
2,2′-[(3-hydroxyphenyl)methylene]bis(3,5,6-trimethylphenol),
2,2′-[(4-hydroxyphenyl)methylene]bis(3,5,6-trimethylphenol),
2,2′-[(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″-methylidinetris(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,
4,4′,4″,4′″-(1,1,2,2-ethanetetrayl)tetrakis(2-methylphenol),
4,4′,4″,4′″-(1,1,2,2-ethanetetrayl)tetrakis(2,6-dimethylphenol),
4,4′,4″,4′″-(1,4-phenylene)bis(methylidine)tetrakis(2,6-dimethylphenol),
2,2-bis[4,4-bis(4-hydroxy-3-methylphenyl)cyclohexyl]propane,
2,2′-[(3,4-dihydroxyphenyl)methylene]bis(3,5-dimethylphenol),
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[4-hydroxy-3-(2-hydroxybenzyl)-5-methylphenyl]methane,
bis[4-hydroxy-3-(3-hydroxybenzyl)-5-methylphenyl]methane,
bis[4-hydroxy-3-(4-hydroxybenzyl)-5-methylphenyl]methane,
bis[2-hydroxy-3-(2-hydroxybenzyl)-5-methylphenyl]methane,
bis[2-hydroxy-3-(3-hydroxybenzyl)-5-methylphenyl]methane,
bis[2-hydroxy-3-(4-hydroxybenzyl)-5-methylphenyl]methane,
bis[2-hydroxy-3-(3-hydroxy-4-methylbenzyl)-5-methylphenyl]methane,
bis[2-hydroxy-3-(4-hydroxy-3-methylbenzyl)-5-methylphenyl]methane,
bis[2-hydroxy-3-(3-hydroxy-2-methylbenzyl)-5-methylphenyl]methane,
bis[2-hydroxy-3-(2-hydroxy-3-methylbenzyl)-5-methylphenyl]methane,
α,α′,α″,α′″-tetrakis(4-hydroxyphenyl)-p-xylene,
bis[2-hydroxy-3-(4-hydroxy-2,3,5-trimethylbenzyl)-5-methylphenyl]methane,
bis[2-hydroxy-3-(2,5-dimethyl-3-hydroxybenzyl)-5-methylphenyl]methane,
bis[2-hydroxy-3-(2,5-dimethyl-4-hydroxybenzyl)-5-methylphenyl]methane,
bis[2-hydroxy-3-(2,5-dimethyl-5-hydroxybenzyl)-5-methylphenyl]methane,
bis[2-hydroxy-3-(3,5-dimethyl-4-hydroxybenzyl)-5-methylphenyl]methane,
bis[2-hydroxy-3-(2-hydroxy-3,4,6-trimethylbenzyl)-5-methylphenyl]methane,
bis[2-hydroxy-3-(4-hydroxy-2,3,6-trimethylbenzyl)-5-methylphenyl]methane,
4,4,4′,4′-tetrakis(4-hydroxyphenyl)bicyclohexyl,
bis[4-hydroxy-3-(5-cyclohexyl-4-hydroxy-2-methylbenzyl)-5-methylphenyl]methane,
4,4,4′,4′-tetrakis(4-hydroxy-3-methylphenyl)bicyclohexyl,
4,6-bis(3,5-dimethyl-4-hydroxyphenyl)-1,2-benzenediol,
4,4,4′,4′-tetrakis(3,5-dimethyl-4-hydroxyphenyl)bicyclohexyl,
1,1-bis[5-cyclohexyl-4-hydroxy-3-(2-hydroxy-5-methylbenzyl)phenyl]cyclohexane,
1,1-bis[5-cyclohexyl-4-hydroxy-3-(3,5-dimethyl-4-hydroxybenzyl)phenyl]cyclohexane,
1,1-bis[5-cyclohexyl-4-hydroxy-3-(5-cyclohexyl-4-hydroxy-2-methylbenzyl)phenyl]cyclohexane,
4,6-bis[1-(4-hydroxyphenyl)ethyl]-1,3-benzenediol,
2,2-bis[4-hydroxy-3-(4-hydroxy-3-methylbenzyl)-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(3-isopropyl-4-hydroxyphenyl)bicyclohexyl,
4,4′-bis[(3,4-dihydroxyphenyl)methylene]bis(2-isopropylphenol),
2,2′-bis[4,4-bis(4-hydroxyphenyl)cyclohexyl]propane,
2,4,6-tris(4-hydroxybenzyl)-1,3-benzenediol,
4,6-bis(3,5-dimethyl-4-hydroxybenzyl)-1,2,3-benzenetriol,
3,3′-[(2-hydroxyphenyl)methylene]bis(5-methyl-1,2-benzenediol),
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)-1,2-benzenediol,
2,4,6-tris(3,5-dimethyl-2-hydroxybenzyl)-1,2-benzenediol,
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)-1,2,3-benzenetriol,
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″-ethylidinetris{[2-(2-hydroxy-5-methyl)benzyl]-6-methylphenol},
2,2-bis[3,5-bis(2-hydroxy-5-methylphenylmethyl)phenyl]propane,
bis[3-(α,α-bis(2,5-dimethyl-4-hydroxyphenyl)methyl-4-hydroxyphenyl]methane,
bis[5-(3,5-dimethyl-4-hydroxybenzyl)-2,3,4-trihydroxyphenyl]methane,
bis[3-(2,3,4-trihydroxybenzyl)-2,5-dimethyl-4-hydroxyphenyl]methane,
1,1-bis[3-(2,3,4-trihydroxybenzyl)-5-cyclohexyl-4-hydroxyphenyl]cyclohexane,
1,8,15,22-tetranonyl-3,5,10,12,17,19,24,26-octahydroxy[1,1,1,1]-metacyclophane,
4,4′-[1-{4-[1-(3,5-bis(4-hydroxy-2-methylbenzyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}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″-ethylidinetris[2,6-bis(2-hydroxybenzyl)phenol],
4,4′,4″-ethylidinetris[2,6-bis(4-hydroxybenzyl)phenol],
2,2-bis[3,5-bis(4-hydroxy-3-methylbenzyl)-4-hydroxyphenyl]propane,
1,8,15,22-tetraethyl-3,5,10,12,17,19,24,26-octahydroxy[1,1,1,1]-metacyclophane,
α,α′,α″,α′″-tetrakis(3,5-dimethyl-4-hydroxyphenyl)-1,4-dimethylbenzene,
4,4′-[1-{4-[1-(3,5-bis(2-hydroxy-5-isopropylphenyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[2, 6-bis(2-hydroxy-5-isopropylphenyl)phenol],
4,4′-[1-{4-[1-(3,5-bis(4-hydroxy-2,3,5-trimethylphenyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene] bis[2,6-bis(4-hydroxy-2,3,5-trimethylphenyl)phenol],
4,4′-[1-{4-[1-(3,5-bis(3-sec-butyl-4-hydroxyphenyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}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,
2,2-bis[4,4',4″,4′″-tetrakis(3,5-dihydroxymethyl-4-hydroxyphenyl)cyclohexyl]propane and the like can be exemplified.

Carboxylic acids and derivatives thereof include, for example,
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-(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 and the like.

Acidic phosphoric ester compounds include, for example, 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, tetracosylate. Examples include luacid phosphate, monobutyl phosphate, dibutyl phosphate, monoisodecyl phosphate, bis(2-ethylhexyl) phosphate and the like.

As the component (b), a compound having a phenolic hydroxyl group is preferable because it can more effectively express the heat discoloration property. , acidic phosphates and metal salts thereof, and 1,2,3-triazoles and derivatives thereof.

The (c) component of the reaction medium that reversibly causes the electron transfer reaction by the (a) component and the (b) component in a specific temperature range will be described.
Component (c) includes alcohols, esters, ketones, ethers, and acid amides.

When the reversible thermochromic composition is encased in microcapsules and applied to secondary processing, low molecular weight substances evaporate out of the capsules when subjected to high heat treatment. Compounds of several tens or more are preferably used.

As alcohols, aliphatic monohydric saturated alcohols having 10 or more carbon atoms are effective. Examples include heptadecyl alcohol, octadecyl alcohol, eicosyl alcohol, and docosyl alcohol.

Esters having 10 or more carbon atoms are effective as esters, and any combination of a monohydric carboxylic acid having an aliphatic, alicyclic or aromatic ring and a monohydric alcohol having an aliphatic, alicyclic or aromatic ring. Esters obtained from any combination of polycarboxylic acids having aliphatic and alicyclic or aromatic rings and monohydric alcohols having aliphatic and alicyclic or aromatic rings, aliphatic and alicyclic Alternatively, esters obtained from any combination of a monovalent carboxylic acid having an aromatic ring and a polyhydric alcohol having an aliphatic, alicyclic or 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, stearic acid n -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, 4-tert-butyl stearyl benzoate, dimyristyl phthalate, distearyl phthalate, dimyristyl oxalate, dicetyl oxalate, dicetyl malonate, dilauryl succinate, dilauryl glutarate, diundecyl adipate , dilauryl azelate, di-(n-nonyl) sebacate, dineopentyl 1,18-octadecylmethylenedicarboxylate, ethylene glycol dimyristate, propylene glycol dilaurate, propylene glycol distearate, hexylene glycol dipalmitate, 1, 5-pentanediol distearate, 1,2,6-hexanetriol trimyristate, 1,4-cyclohexanediol didecyl, 1,4-cyclohexanedimethanol dimyristate, xylene glycol dicaprinate, xylene glycol distearate A rate etc. can be illustrated.

Esters of saturated fatty acids and branched fatty alcohols, and ester compounds of unsaturated fatty acids or branched or substituted saturated fatty acids with branched or C 16 or more fatty alcohols are also effective. be.

Examples of ester compounds include 2-ethylhexyl butyrate, 2-ethylhexyl behenate, 2-ethylhexyl myristate, 2-ethylhexyl caprate, 3,5,5-trimethylhexyl laurate, and 3,5,5-trimethyl palmitate. Hexyl, 3,5,5-trimethylhexyl stearate, 2-methylbutyl caproate, 2-methylbutyl caprylate, 2-methylbutyl caprate, 1-ethylpropyl palmitate, 1-ethylpropyl stearate, 1-ethyl behenate Propyl, 1-ethylhexyl laurate, 1-ethylhexyl myristate, 1-ethylhexyl palmitate, 2-methylpentyl caproate, 2-methylpentyl caprylate, 2-methylpentyl caprate, 2-methylpentyl laurate, stearic acid 2-methylbutyl, 2-methylbutyl stearate, 3-methylbutyl stearate, 1-methylheptyl stearate, 2-methylbutyl behenate, 3-methylbutyl behenate, 1-methylheptyl stearate, 1-methylheptyl behenate, capron 1-ethylpentyl acid, 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, stearic acid 3,7-dimethyloctyl, 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 can be exemplified.

Furthermore, in order to discolor with a large hysteresis characteristic with respect to the color density-temperature curve and to provide color memory depending on temperature change, a temperature of 5 ° C. or more and less than 50 ° C. described in JP-B-4-17154 is used. Carboxylic acid ester compounds exhibiting a ΔT value (melting point - clouding point), for example, a carboxylic acid ester containing a substituted aromatic ring in the molecule, a carboxylic acid containing an unsubstituted aromatic ring, and an aliphatic alcohol 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 aromatics dibenzyl cinnamate, heptyl stearate, didecyl adipate, dilauryl adipate, dimyristyl adipate, dicetyl adipate, distearyl adipate, trilaurin, trimyristin, tristearin, di Examples include myristine and distearin.

Further, a fatty acid ester compound obtained from an odd aliphatic monohydric alcohol having 9 or more carbon atoms and an even aliphatic carboxylic acid having an even number of carbon atoms, n-pentyl alcohol or n-heptyl alcohol, and an even number having 10 to 16 carbon atoms A fatty acid ester compound having a total carbon number of 17-23 obtained from an aliphatic carboxylic acid is also effective.

Examples of 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 n caprylate. -undecyl, n-tridecyl caprylate, n-pentadecyl caprylate, n-heptyl caprate, n-nonyl caprate, n-undecyl caprate, n-tridecyl caprate, n-pentadecyl caprate, n-pentyl laurate , n-heptyl laurate, n-nonyl laurate, n-undecyl laurate, n-tridecyl laurate, n-pentadecyl laurate, n-pentyl myristate, n-heptyl myristate, n-nonyl myristate, myristic n-undecyl acid, n-tridecyl myristate, n-pentadecyl myristate, n-pentyl palmitate, n-heptyl palmitate, n-nonyl palmitate, n-undecyl palmitate, n-tridecyl palmitate, n-palmitate -Pentadecyl, n-nonyl stearate, n-undecyl stearate, n-tridecyl stearate, n-pentadecyl stearate, n-nonyl eicosanoate, n-undelsi eicosanoate, n-tridecyl eicosanoate, n-pentadecyl eicosanoate , n-nonyl behenate, n-undecyl behenate, n-tridecyl behenate, n-pentadecyl behenate and the like.

Effective ketones are aliphatic ketones having a total carbon number of 10 or more, such as 2-decanone, 3-decanone, 4-decanone, 2-undecanone, 3-undecanone, 4-undecanone, and 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, cyclohexylphenyl ketone, benzyl-n-butyl ketone, 4-n-butylacetophenone, n-hexanophenone, 4-isobutylacetophenone, 1-acetonaphtone, 2-acenaphthone, cyclopentylphenyl A ketone etc. can be illustrated.

Aliphatic ethers having a total carbon number of 10 or more are effective as ethers. , 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, propionamide, 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, olein Acid amide, erucamide, benzamide, caproic acid anilide, caprylic acid anilide, capric acid anilide, lauric acid anilide, myristate 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, myristate N-methylamide, palmitic acid N-methylamide, stearic acid N-methylamide, behenic acid N-methylamide, oleic acid N -methylamide, erucic acid N-methylamide, lauric acid N-ethylamide, myristate N-ethylamide, palmitic acid N-ethylamide, stearic acid N-ethylamide, oleic acid N-ethylamide, lauric acid N-butylamide, myristate N-butylamide , N-butylamide palmitate, N-butylamide stearate, N-butylamide oleate, N-octylamide laurate, N-octylamide myristate, N-octylamide palmitate, N-octylamide stearate, N-oleic acid - octylamide, lauric acid N-dodecylamide, myristate N-dodecylamide, palmitic acid N-dodecylamide, stearic acid N-dodecylamide, oleic acid N-dodecylamide, dilauric acid amide, dimyristate amide, dipalmitin Acid amide, distearic amide, dioleic amide, trilauric amide, trimyristic amide, tripalmitic amide, tristearic amide, trioleic amide, succinic amide, adipic amide, glutaric amide, malonic 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, adipate N-butylamide, glutaric acid N-butylamide, malonic acid N-butylamide, adipate N-octylamide, Examples include adipic acid N-dodecylamide.

〔式中、Ｒ_１は水素原子またはメチル基を示し、ｍは０～２の整数を示し、Ｘ_１およびＸ_２のいずれか一方は－（ＣＨ_２）_ｎＯＣＯＲ_２または（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以上のアルキル基またはアルケニル基を示し、Ｙ_１および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およびｐはそれぞれ独立して、１～３の整数を示す。〕 Moreover, the compound represented by the following formula (3) may be used as the component (c).

[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, a carbon represents an alkyl group, a methoxy group or a halogen atom of numbers 1 to 4; r and p each independently represents an integer of 1 to 3; ]

Among the compounds represented by formula (3), when R ₁ is a hydrogen atom, it is preferable because a reversible thermochromic composition having a wider hysteresis width can be obtained, and further R ₁ is a hydrogen atom and m is 0 is more preferred.

（式中、Ｒは炭素数８以上のアルキル基また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。） Among the compounds represented by the formula (3), the compounds represented by the following formula (4) are more preferable.

(In the formula, R represents an alkyl group or alkenyl group having 8 or more carbon atoms, preferably an alkyl group having 10 to 24 carbon atoms, more preferably an alkyl group having 12 to 22 carbon atoms.)

Examples of compounds represented by formula (4) include 4-benzyloxyphenylethyl octanoate, 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, 4-benzyloxyphenylethyl octadecanoate, and the like.

（式中、Ｒは炭素数８以上のアルキル基またはアルケニル基を示し、ｍおよびｎはそれぞれ独立して、１～３の整数を示し、Ｘおよび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。） Furthermore, a compound represented by the following formula (5) may be used as the component (c).

(Wherein, R represents an alkyl group or alkenyl group having 8 or more carbon atoms, m and n each independently represents an integer of 1 to 3, X and Y each independently represent a hydrogen atom, a carbon number 1 to 4 alkyl groups, C 1 to 4 alkoxy groups, or halogen atoms.)

Examples of compounds represented by formula (5) include 1,1-diphenylmethyl octanoate, 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, 1,1-diphenylmethyl octadecanoate, and the like.

（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。） Furthermore, a compound represented by the following formula (6) may be used as the component (c).

(Wherein, 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 succinic acid and 2-(4-benzyloxyphenyl)ethanol. Diesters, diesters of succinic acid and 2-[4-(3-methylbenzyloxy)phenyl]ethanol, diesters of glutaric acid and 2-(4-benzyloxyphenyl)ethanol, glutaric acid and 2-[4-( 4-chlorobenzyloxy)phenyl]ethanol, diesters of adipic acid and 2-(4-benzyloxyphenyl)ethanol, diesters of pimelic acid and 2-(4-benzyloxyphenyl)ethanol, suberic acid and 2-(4-benzyloxyphenyl)ethanol diester, diester of suberic acid with 2-[4-(3-methylbenzyloxy)phenyl]ethanol, suberic acid with 2-[4-(4-chlorobenzyloxy ) phenyl] ethanol, diester of suberic acid with 2-[4-(2,4-dichlorobenzyloxy)phenyl]ethanol, diester of azelaic acid with 2-(4-benzyloxyphenyl)ethanol, sebacine diester of acid with 2-(4-benzyloxyphenyl)ethanol, diester of 1,10-decanedicarboxylic acid with 2-(4-benzyloxyphenyl)ethanol, 1,18-octadecanedicarboxylic acid with 2-(4 -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のアルキル基またはアルケニル基を示し、ｎは１～３の整数を示す。） Furthermore, a compound represented by the following formula (7) may be used as the component (c).

(Wherein, R represents an alkyl 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. , a diester of 1,3-bis(2-hydroxyethoxy)benzene and lauric acid, a diester of 1,3-bis(2-hydroxyethoxy)benzene and myristic acid, a diester of 1,4-bis(hydroxymethoxy)benzene and Diesters of butyric acid, diesters of 1,4-bis(hydroxymethoxy)benzene with isovaleric acid, diesters of 1,4-bis(2-hydroxyethoxy)benzene with acetic acid, 1,4-bis(2-hydroxy ethoxy)benzene with propionic acid, 1,4-bis(2-hydroxyethoxy)benzene with valeric acid, 1,4-bis(2-hydroxyethoxy)benzene with caproic acid, 1, Diesters of 4-bis(2-hydroxyethoxy)benzene and caprylic acid, diesters 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。） Furthermore, a compound represented by the following formula (8) may be used as the component (c).

(Wherein, X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom; m represents an integer of 1 to 3; n represents 1 to 20 indicates an integer of

Examples of the compound represented by formula (8) include a diester of succinic acid and 2-phenoxyethanol, a diester of suberic acid and 2-phenoxyethanol, a diester of sebacic acid and 2-phenoxyethanol, and 1,10-decanedicarboxylic acid. and 2-phenoxyethanol, and diesters of 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または１を示す。） Furthermore, a compound represented by the following formula (9) may be used as the component (c).

(wherein R is 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, X is a hydrogen atom, 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 is 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, 4- 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, 4-biphenylhexylacetate, 4-biphenylacetate cyclohexylmethyl and the like.

（式中、Ｒは炭素数３～１８のアルキル基または炭素数３～１８の脂肪族アシル基を示し、Ｘは水素原子、炭素数１～３のアルキル基、炭素数１または２のアルコキシ基、ハロゲン原子のいずれかを示し、Ｙは水素原子またはメチル基を示し、Ｚは水素原子、炭素数１～４のアルキル基、炭素数１または２のアルコキシ基、ハロゲン原子のいずれかを示す。）
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。 Further, the component (c) may be a compound represented by the following formula (10).

(Wherein, R represents an alkyl group having 3 to 18 carbon atoms or an aliphatic acyl group having 3 to 18 carbon atoms, X represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 or 2 carbon atoms , a halogen atom, Y is a hydrogen atom or a methyl group, and Z is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 or 2 carbon atoms, or a halogen atom. )
Examples of compounds 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または１を示す。） Furthermore, a compound represented by the following formula (11) may be used as the component (c).

(Wherein, 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, a halogen atom, Y is a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom, and n is 0 or 1.)

Examples of the compound represented by formula (11) include benzoate of octyl 4-hydroxybenzoate, decyl 4-hydroxybenzoate, 4-methoxy benzoate of heptyl 4-hydroxybenzoate, 4 2-methoxybenzoate of dodecyl-hydroxybenzoate, benzoate of cyclohexylmethyl-4-hydroxybenzoate, and the like can be exemplified.

（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。） Furthermore, a compound represented by the following formula (12) may be used as the component (c).

(Wherein, R represents 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, or an alkenyl group having 3 to 18 carbon atoms, X is 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; Y is 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. Phenoxyethyl ether etc. can be illustrated.

（式中、Ｒは炭素数３～８のシクロアルキル基または炭素数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。） Further, the component (c) may be a compound represented by the following formula (13).

(Wherein, 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 diesters of 1,3-bis(2-hydroxyethoxy)benzene and cyclohexanecarboxylic acid, and 1,4-bis(2-hydroxyethoxy)benzene and cyclohexanepropionic acid. and 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。） Further, the component (c) may be a compound represented by the following formula (14).

(Wherein, R represents either 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 alkyl group, methoxy group, ethoxy group, or halogen atom, and n is an integer of 1 to 3.)

Examples of the compound represented by formula (14) include diesters of 4-phenylphenol ethylene glycol ether and cyclohexanecarboxylic acid, diesters of 4-phenylphenol diethylene glycol ether and lauric acid, and 4-phenylphenol triethylene glycol ether. Diesters of cyclohexanecarboxylic acid, diesters of 4-phenylphenol ethylene glycol ether and octanoic acid, diesters of 4-phenylphenol ethylene glycol ether and nonanoic acid, diesters of 4-phenylphenol ethylene glycol ether and decanoic acid, 4 - A diester of phenylphenol ethylene glycol ether and myristic acid can be exemplified.

Furthermore, as an electron-accepting compound, a specific alkoxyphenol compound having a linear or side-chain alkyl group having 3 to 18 carbon atoms is used (JP-A-11-129623, JP-A-11-5973), or a specific Using a hydroxybenzoic acid ester (JP-A-2001-105732), using a gallic acid ester (JP-B-51-44706, JP-A-2003-253149) heat coloring type (coloring by heating, It is also possible to apply a reversible thermochromic composition that decolorizes by cooling (see FIG. 3).

The above reversible thermochromic composition is a compatible body containing the above (a) component, (b) component, and (c) component as essential components, and the ratio of each component is the concentration, color change temperature, color change form Although it depends on the type of each component, generally the component ratio at which the desired properties 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 proportions are parts by mass).

Furthermore, various light stabilizers may be added to the reversible thermochromic composition, if necessary.
The light stabilizer is contained to prevent photodegradation of the reversible thermochromic composition consisting of (a) component, (b) component, and (c) component. 0.3 to 24 mass %, preferably 0.3 to 16 mass %. Among the light stabilizers, the ultraviolet absorber effectively blocks ultraviolet rays contained in sunlight and the like, and prevents photodegradation caused by the excited state caused by the photoreaction of the component (a). In addition, antioxidants, singlet oxygen quenchers, superoxide anion quenchers, ozone quenchers and the like suppress the oxidation reaction caused by light.
The light stabilizer may be used alone, or two or more of them may be used in combination.

Microencapsulation is performed 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 dispersion cooling. method, air suspension coating method, spray drying method, etc., depending on the application. Furthermore, depending on the purpose, the surface of the microcapsules may be further provided with a secondary resin film to impart durability, or the surface characteristics may be modified for practical use.

Materials for the microcapsules include organic resins such as epoxy resins, urea resins, urethane resins, and isocyanate resins.

Durability can be imparted by providing a secondary resin film on the surface of the microcapsules according to the purpose, and the surface characteristics can be modified for practical use.

The mass ratio of the microcapsules (that is, the microcapsule wall portion not enclosing the reversible thermochromic composition) and the reversible thermochromic composition is 1 part by mass of the microcapsules, and the reversible thermochromic composition is , preferably 1 part by mass or more, more preferably 1 part by mass or more, preferably 7 parts by mass or less, more preferably 6 parts by mass or less. By using 7 parts by mass or less of the reversible thermochromic composition with respect to 1 part by mass of the microcapsules, it is easy to obtain an appropriate wall thickness without the microcapsule walls becoming too thin. It becomes easy to improve the heat resistance and pressure resistance of the pigment. Moreover, by adding 1 part by mass or more of the reversible thermochromic composition to 1 part by mass of the microcapsules, it becomes easy to increase the color density and vividness when the microcapsule pigment develops color.

The average particle size of the microcapsules is, for example, 0.01 to 50 μm, preferably 0.1 to 30 μm, more preferably 0.5 to 20 μm, which satisfies practical use.
In the present invention, an average particle size (median size) based on volume is used as the average particle size.
As an optimum method for measuring the average particle size, a laser diffraction/scattering particle size distribution measuring device calibrated by a direct measurement method, for example, a laser diffraction particle size distribution measuring device LA-300 (trade name, Horiba Co., Ltd. manufactured by Seisakusho).

As a direct measurement method used for calibration,
(i) an image analysis method in which the area (two-dimensional) of individual particles is measured from an image taken with a microscope to measure the equivalent diameter;
(ii) Coulter method (Electrical sensing band The laser measurement method is calibrated based on the values obtained by these methods.

Measurement of the average particle size by the image analysis method, for example, using the image analysis type particle size distribution measurement software "Macview" (trade name, manufactured by Mountec Co., Ltd.) to determine the particle area, projected from the area of the particle area The area circle equivalent diameter (Heywood diameter) can be calculated, and the average particle diameter of particles equivalent to a sphere of equal volume can be measured.
In addition, the measurement of the average particle size by the Coulter method can be applied when the particle size of all particles or most of the particles exceeds 0.2 μm. It can be measured using "Multisizer 4e".

By encapsulating the reversible thermochromic composition in microcapsules, a chemically and physically stable pigment can be constructed, and the reversible thermochromic composition can be maintained at the same composition under various conditions of use. The same action and effect can be obtained.

The content of the microcapsule pigment is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, even more preferably 10 to 25% by mass, relative to the total mass of the ink composition. When the content is within the above range, it is possible to form a handwriting rich in color development, and it becomes easy to suppress dry-up.

(Shear thinning agent)
The ink composition contains a polysaccharide as a shear thinning agent. Specific examples of polysaccharides include xanthan gum, welan gum, succinoglycan, guar gum, locust bean gum, λ-carrageenan, cellulose derivatives, zeta sea gum, diutan gum, glucomannan, macrohomopsis gum, extracts from seaweed such as agar and carrageenan. Carbohydrates and the like having a gelling ability are mentioned, and these bring about dispersion stability of the microcapsule pigment in the stationary state of the ink and good ink ejection during writing.

Among the polysaccharides described above, succinoglycan and xanthan gum are preferred, and these can increase the viscosity of the composition at rest and lower the viscosity of the composition during writing than other polysaccharides. It is easy to achieve both dispersion stability and good ink ejection during writing, and the viscosity of the ink can be adjusted by adding a relatively small amount, so when the water in the ink evaporates from the pen tip, the shear thinning agent It is easy to suppress dry-up of the pen tip due to the film.

Succinoglycan is a natural product in which glucose, galactose, succinic acid, and pyruvic acid are polymerized, and although its molecular weight is difficult to specify, it is generally considered to have a weight average molecular weight of about 1,000,000. There are various commercially available succinoglycans, for example, Leozan (trade name, manufactured by Sansho Co., Ltd.).

In order to obtain a sufficient effect, the content of the polysaccharide is preferably 0.01 to 1.0% by mass with respect to the total mass of the ink composition, and more preferably 0.1 to 0.5% by mass. preferable.

The ink composition may contain dextrin. The dextrin is preferably, for example, a sugar mixture containing starch saccharification products with 8 or more sugars and/or reduced products thereof. The saccharide mixture preferably contains 30% by mass or more, more preferably 50% by mass or more, and even more preferably 70% by mass or more of starch saccharification products having 8 or more sugars. As a result, the dry-up resistance can be further improved, and the ability to prevent sagging from the tip of the ballpoint pen can be imparted.

As the octahedral or higher sugars, saccharified starch obtained by enzymatic decomposition of starch or the like, and reduced saccharified starch obtained by reducing the terminal group of the saccharified starch can be used. In addition, when starch is decomposed, saccharides with various degrees of polymerization are produced. Therefore, it is technically difficult to completely isolate only saccharides having octasaccharides or more, and the production cost is high. Therefore, in the sugar mixture in which saccharides of 7 saccharides or less are present, it is possible to use a mixture containing 30% by mass or more of the saccharides of 8 saccharides or more, thereby sufficiently obtaining the performance in the ink, Dry-up resistance and anti-sagging performance can be imparted. Sugar mixtures include products obtained by degrading (eg, enzymatically degrading) starch.

The content of dextrin in the ink composition is preferably 0.5 to 10% by mass. If it is 0.5% by mass or more, the dry-up resistance can be effectively improved, and if it is 10% by mass or less, the viscosity of the ink composition will increase due to blending, causing bleeding and bloating. It is possible to easily avoid problems such as the deterioration of the conformability and hindrance of followability, and furthermore, there is no adverse effect on good drying resistance. The content of dextrin is more preferably 1-8% by mass.

The ink composition may contain known components as long as the effects of the present invention are not impaired. For example, polyvinylpyrrolidone, polyvinyl alcohol, etc. may be included as necessary. Also, N-vinyl-2-pyrrolidone oligomer, N-vinyl-2-piperidone oligomer, N-vinyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, ε-caprolactam, N-vinyl-ε-caprolactam By adding an oligomer or the like, the dry-up resistance can be improved, and the function in the retractable form can be further enhanced.

Furthermore, if necessary, various additives may be included. Additives include higher fatty acids such as oleic acid, nonionic surfactants having long-chain alkyl groups, polyether-modified silicone oils, tri(alkoxycarbonylmethyl) thiophosphite, tri(alkoxycarbonyl) thiophosphite, thiophosphite triesters such as ethyl esters), phosphoric acid monoesters of polyoxyethylene alkyl ethers or polyoxyethylene alkylaryl ethers, phosphoric acid diesters of polyoxyethylene alkyl ethers or polyoxyethylene alkylaryl ethers, or their Lubricants such as metal salts, ammonium salts, amine salts and alkanolamine salts are included.

In addition, inorganic salts such as sodium carbonate, sodium phosphate, and sodium acetate, pH adjusters such as organic basic compounds such as water-soluble amine compounds, benzotriazole, tolyltriazole, dicyclohexylammonium nitrite, diisopropylammonium nitrite, and saponin. Antirust agents such as phenolic acid, sodium salt of 1,2-benzthiazolin-3-one, sodium benzoate, sodium dehydroacetate, potassium sorbate, propyl parahydroxybenzoate, 2,3,5,6-tetrachloro-4 - Preservatives or fungicides such as (methylsulfonyl)pyridine, ascorbic acid, ascorbic acid derivatives, natural or synthetic polyphenols, N-vinylpyrrolidone oligomers, kojic acid, hydroxylamines, oxime derivatives, α-glucosylrutin, phosphones acid, phosphinate, sulfite, sulfoxylate, dithionite, thiosulfate, thiourea dioxide, formamidine sulfinic acid, glutathione, n-butyraldehyde and aniline reactants, etc. Foaming agents, dispersing agents, etc. may also be included.

The ink composition contains water, but may contain a water-soluble organic solvent in addition to water. When a water-soluble organic solvent is contained, it is preferably contained within a range that does not cause various problems such as poor ink followability due to an increase in ink viscosity, poor drying of handwriting, bleeding of handwriting, or a water-soluble organic solvent. It may be solvent-free. Examples of water-soluble organic solvents include glycol-based water-soluble organic solvents, and specific examples include ethylene glycol, diethylene glycol, thiodiethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol isopropyl methyl ether, triethylene glycol, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol mono Ethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, 1,3-butylene glycol, glycerin, furfuryl alcohol and the like can be mentioned.

The ink composition preferably has a viscosity of 300 to 1500 mPa·s measured at a shear rate of 3.84 sec ⁻¹ and a viscosity of 10 to 100 mPa·s measured at a shear rate of 384 sec ⁻¹ . . A more preferable viscosity of the ink composition is 500 to 1000 mPa·s at a shear rate of 3.84 sec ⁻¹ and 20 to 50 mPa·s at a shear rate of 384 sec ⁻¹ . When the viscosity of the ink composition is within the above range, sedimentation, aggregation, and the like of the microcapsule pigment in the ink composition in a still state are sufficiently suppressed, and the ink ejection property from the tip of the ballpoint pen during writing tends to be good. .
The viscosity of the ink composition is measured at 20.degree.

Further, the water-based ink composition preferably has a shear thinning index n represented by the following general formula (15) measured at 20° C. of 0.4 to 0.9, more preferably 0.5 to 0.8. It is more preferable to have
T=KJn (15)
Here, T is the shear stress [N/m ² ], K is the viscosity coefficient (constant), and J is the shear rate [sec ⁻¹ ].
As a result, sedimentation, aggregation, etc. of the microcapsule pigment in the ink composition in a stationary state are sufficiently suppressed, and the ink of the ballpoint pen tip is discharged without accumulating in the gap between the ball and the ball gripping portion during writing. , it becomes easy to form clear handwriting.

The shear thinning index n can be measured, for example, using a rheometer "DHR-2" manufactured by TE Instruments Co., Ltd., and shear rates of 3.84 sec ^-1 and 384 sec ^-1 and The shear stress (shear stress) obtained at each shear rate is applied to the above general formula (15) to obtain n.

The surface tension of the ink composition is preferably 25-45 mN/m in an environment of 20°C. When the surface tension is within the above numerical range, the wettability of the ink composition is improved, the handwriting formability of the overwritten handwriting is improved, and the bleeding of the writing line and the strike-through to the paper surface are suppressed. Writability can be further improved. In consideration of overwriting performance and writability, the surface tension of the water-based ink composition is more preferably 25 to 35 mN/m, further preferably 25 to 30 mN/m.
The surface tension is measured by the vertical plate method using a platinum plate at 20°C. As a measuring device, for example, a surface tensiometer (trade name: DY-300) manufactured by Kyowa Interface Science Co., Ltd. can be used.

The ink composition is prepared by adding microcapsule pigments and, if necessary, various additives into an aqueous medium containing water and a water-soluble organic solvent, and stirring them. is prepared by directly adding a dispersion or a shear thinning agent and stirring.

The ink composition can be used as ink for writing instruments such as marking pens and ballpoint pens.

The ink composition can be applied to a writing instrument comprising a barrel containing the ink composition and a pen body for leading out the ink composition contained in the barrel. The ink composition can be contained in, for example, an ink occluding body composed of a bundle of fibers, or can be directly contained in an ink containing tube and contained in a barrel. Also, the pen body can be, for example, a marking pen body or a ballpoint pen body.

The writing instrument may be a marking pen. The structure and shape of the marking pen itself are not particularly limited. As a marking pen, for example, an ink occluding body made of a bundle of fibers is built in a barrel, and a marking pen body made of a fiber processed body in which a capillary gap is formed is attached directly or via a relay member to the barrel. The ink occluding body and the marking pen body are connected to each other through a structure in which the ink occluding body is impregnated with the ink composition. A structure in which ink is directly stored in the ink storage tube can be exemplified.

The marking pen body is a porous member with continuous pores selected from the range of about 30% to 70% in porosity, which has been widely used in the past, such as a resin processed body of fibers, a fusion processed body of heat-fusible fibers, and a felt body. Alternatively, it is an extruded body of synthetic resin having a plurality of ink outlet holes extending in the axial direction. The ink occlusion body is made by bundling crimped fibers in the longitudinal direction, and is incorporated in a covering such as a plastic cylinder or a film, and is configured so that the porosity is adjusted to a range of approximately 40% to 90%. be done. Further, the valve body may be of a pumping type that has been widely used in the past, but it is preferable that the valve body has a spring pressure that can be released by the writing pressure.

The writing instrument may be a ballpoint pen. The structure and shape of the ballpoint pen itself are not particularly limited. A ballpoint pen, for example, has an ink storage tube filled with an ink composition in a barrel, the ink storage tube communicates with a ballpoint pen tip having a ball attached to the tip, and is further stored in the ink storage tube. A structure in which a liquid plug for preventing backflow is in close contact with the end surface of the ink composition can be exemplified. A ball-point pen constructed using the ink composition having the constitution described above has good ink ejection properties from the writing tip and excellent handwriting formation properties.

As a ball-point pen tip, for example, a ball-point pen tip is formed by cutting a metal material with a drill or the like, in which a ball is held in a ball-holding portion in which the vicinity of the tip of a metal pipe is pressed and deformed inward from the outer surface. A ball-point pen tip that holds a ball in a ball-holding part, a ball-point pen tip that has a resin ball receiving seat inside a metal or plastic tip, and a spring that urges the ball held by the ball-point pen tip forward. can be applied. The ball is made of cemented carbide, stainless steel, ruby, ceramic, resin, rubber, or the like, and has a diameter of, for example, 0.3 mm or more and 2.0 mm or less, preferably 0.3 mm or more and 1.5 mm or less, more preferably 0.3 mm or more and 2.0 mm or less. A thickness of about 3 mm or more and 1.0 mm or less can be applied.

For the ink storage tube that stores the ink composition, for example, a molding made of thermoplastic resin such as polyethylene, polypropylene, polyethylene terephthalate, nylon, or a metal tubular body is used. In addition to directly connecting the tip to the ink containing tube, the ink containing tube and the tip may be connected via a connection member (tip holder).

The ball-point pen may have an ink storage tube in the form of a ball-point pen refill, and the ball-point pen refill may be stored in a barrel made of resin, metal, or the like, or the barrel itself with the ball-point pen body attached to the tip portion may be used as the ink reservoir. Alternatively, ink may be filled directly into the barrel.

When the ink storage tube is in the form of a ballpoint pen refill, the ballpoint pen refill includes the ink storage tube that stores the ink composition and the ballpoint pen body that is attached to the ink storage tube directly or via a connecting member and holds the ball rotatably. and

When the ink composition is applied to 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 has a structure in which the tip of the writing tip protrudes from the opening of the barrel by the operation of the retraction mechanism. Methods of operating the retractable mechanism include, for example, a knock type, a rotating type, a sliding type, and the like. The knock type has a knock portion on the rear end of the barrel or on the side surface of the barrel, and by pressing the knock portion, the writing tip is retracted from the front end opening of the barrel, or a clip portion provided on the barrel. A configuration can be exemplified in which the writing tip portion is protruded and retracted from the barrel front end opening portion by pressing. The rotary type can be exemplified by a configuration in which a rotating portion is provided at the rear portion of the barrel, and the writing tip portion is projected and retracted from the front end opening portion of the barrel by rotating the rotating portion. The slide type has a slide part on the side surface of the barrel, and by operating the slide, the writing tip part can be retracted from the front end opening of the barrel, or by sliding a clip part provided on the barrel, writing can be performed. A configuration can be exemplified in which the tip portion is projected and retracted from the front end opening of the barrel. The retractable ballpoint pen is a composite type retractable ballpoint pen in which a plurality of ballpoint pen refills are accommodated 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 the retractable mechanism. good too.

The rear end of the ink composition contained in the ink containing tube is filled with an ink backflow preventer. The ink backflow preventer consists of a non-volatile liquid or a low-volatility liquid. Specifically, petrolatum, spindle oil, castor oil, olive oil, refined mineral oil, liquid paraffin, polybutene, α-olefin, α-olefin oligomer or co-oligomer, dimethyl silicone oil, methylphenyl silicone oil, amino-modified silicone oil, Polyether-modified silicone oil, fatty acid-modified silicone oil, and the like can be mentioned, and one kind can be used alone or two or more kinds can be used in combination. At least one of the non-volatile liquid and the hardly volatile liquid is preferably thickened to a suitable viscosity by adding a thickening agent. As a thickener, silica whose surface is hydrophobically treated, fine particle silica whose surface is methylated, aluminum silicate, swelling mica, bentonite with hydrophobic treatment, clay-based thickeners such as montmorillonite, magnesium stearate, calcium stearate , fatty acid metal soaps such as aluminum stearate and zinc stearate, tribenzylidene sorbitol, fatty acid amides, amide-modified polyethylene waxes, hydrogenated castor oil, dextrin compounds such as fatty acid dextrin, and cellulose compounds. Furthermore, a liquid ink backflow prevention member and a solid ink backflow prevention member can be used together.

The forms of marking pens and ballpoint pens are not limited to those described above, and they may be double-headed writing instruments equipped with pen bodies of different forms or pen bodies that lead out ink compositions of different colors. .

A handwriting obtained by writing on a surface to be written with a writing instrument containing a reversible thermochromic water-based ink composition can be discolored by a heating tool or a cooling tool. Examples of the heating tool include an electric heating discoloring tool equipped with a resistance heating element, a heating discoloring tool filled with hot water, etc., and a hair dryer. Preferably, a friction member is used as a means capable of discoloring by a simple method. be done. That is, the writing instrument may further include a friction member.

As the friction member, an elastic body such as a plastic foam or a viscoelastic body, which is rich in elasticity and capable of generating moderate friction and generating frictional heat when rubbed, is suitable. An eraser can also be used to rub the handwriting, but since eraser shavings are generated at the time of rubbing, the above-described friction member that hardly generates erasing scum is preferably used. Silicone resin, SEBS resin (styrene-ethylene-butadiene-styrene block copolymer), polyester-based resin, α-olefin-based copolymer, etc. are used as the material of the friction member.

The friction member may be a member (friction body) of any shape separate from the writing instrument, and may be combined with the writing instrument to constitute a writing instrument set.
In the case of a writing instrument having a cap, the place where the friction member is provided is not particularly limited. The clip itself can be formed of a friction member, or a friction member can be provided at the cap front end (top) or barrel rear end (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 when a clip is provided, the clip itself may be made of a friction member. A friction member may be provided in the knock portion.

Examples of the cooling device include a cold-heat discoloring device using a Peltier element, a cold-heat discoloring device filled with a refrigerant such as cold water or ice chips, and a refrigerator or freezer.

A ball-point pen filled with the ink composition according to the present invention can write on conventionally used paper, as well as synthetic paper and waterproof paper. Handwritings formed on synthetic paper or water-resistant paper with a ballpoint pen have high density and are free from writing defects such as line skipping.

Synthetic paper and water-resistant paper are different from conventional paper whose main raw material is wood pulp, but have appearance and physical properties similar to those of conventional paper. Synthetic paper and waterproof paper have superior durability, tear resistance, water resistance, chemical resistance, heat resistance, oil resistance, etc., compared to conventional paper.
The synthetic paper may have a structure having a base layer and a surface layer disposed on the base layer. Here, the base layer is made of, for example, polyethylene, polypropylene, high-density polyethylene, polyester, or the like. The surface layer has the effect of brightening the synthetic paper surface, imparting high opacity, smooth texture, etc., and is made of, for example, calcium carbonate.
The water-resistant paper is obtained by applying a water-resistant resin such as synthetic rubber or acrylic resin to a water-resistant base paper produced by internally adding an appropriate amount of a water-resistant agent such as a modified rosin emulsion to pulp.

Synthetic papers include, for example, Polyart®, Appvion Appleton Digital®, Parax® stone paper, RockStock® stone paper, Nekoosa® XM, Nekoosa® OM , HopSynDLgrade (registered trademark), Yupo (registered trademark) FPG80, and the like.

The handwriting formed on synthetic paper or waterproof paper using the ballpoint pen according to the present invention can be decolored by heat from a heating tool such as the friction member. It can also be removed from synthetic paper or waterproof paper by wiping with a medium. As a result, the synthetic paper or water-resistant paper can be returned to a blank state (initial state), and the ballpoint pen can be used to write again. That is, after writing on synthetic paper or waterproof paper, the operation of removing the handwriting using the medium impregnated with the liquid can be repeated, and the synthetic paper or waterproof paper can be reused. .

Examples of the medium include cloth, sponge, paper towel, tissue paper, and the like.

Content written on synthetic or water-resistant paper with a ballpoint pen according to the present invention can be saved in a suitable format by scanning before being erased by heat or removed with a medium impregnated with said liquid, and stored. It may be saved in a predetermined format so that OCR (Optical Character Recognition) is performed on the captured content. As a scanning method, for example, a method using a digital scanner, or a method of taking a digital photograph and performing digital signal processing on the digital photograph can be exemplified. Synthetic paper and waterproof paper can be restored to their initial state and reused by erasing with heat or removing with a medium impregnated with the liquid after scanning the content and storing it in an appropriate place. It becomes possible to

The synthetic or waterproof paper may be part of a bound notebook, or may be separate and unbound. Notebooks with synthetic paper pages include, for example, ROCKET INNOVATIONS, INK. The ROCKET BOOK (registered trademark) manufactured by

It is also possible to combine a notebook with pages of synthetic or water-resistant paper and a ball-point pen according to the invention to obtain a writing instrument set (package kit).
The writing instrument set may further comprise a medium such as cloth.

EXAMPLES The present invention will be specifically described below by way of examples, but the present invention is not limited to these examples. "Parts" are based on mass unless otherwise specified.
In this example, the average particle size of the microcapsule pigment was measured by the laser diffraction/scattering particle size distribution measuring device (device name: LA-300, stock (manufactured by Horiba, Ltd.) was used to measure the average particle size (median size) on a volume basis.

Preparation of microcapsule pigment (1) Spiro[5H-(1)benzopyrano[2,3-d]pyrimidine-5,1'(3'H)isobenzofuran]-3'- as an electron-donating color-forming organic compound On, 2-(diethylamino)-8-(diethylamino)-4-methyl 1.0 parts, 1,1-bis(4-hydroxyphenyl)-2-ethylhexane 3.0 parts as an electron-accepting compound, 2, 5.0 parts of 2-bis(4'-hydroxyphenyl)-hexafluoropropane and 50.0 parts of 4-benzyloxyphenylethyl caprate as a reaction medium, comprising a reversible thermochromic composition having color memory properties. Microcapsule pigment 1 was prepared by encapsulating reversible thermochromic composition a having color memory properties in microcapsules. The complete coloring temperature (t1) was −20° C., and the color changed from pink to colorless with temperature change.

Preparation of microcapsule pigment (2) 1.0 parts of 3,6-bis(diphenylamino)fluorane as an electron-donating color-developing organic compound and 1,1-bis(4-hydroxyphenyl) as an electron-accepting compound -Color memory consisting of 3.0 parts of 2-ethylhexane, 5.0 parts of 2,2-bis(4'-hydroxyphenyl)-hexafluoropropane, and 50.0 parts of 4-benzyloxyphenylethyl caprate as a reaction medium A microcapsule pigment 2 was prepared by encapsulating the reversible thermochromic composition b having properties in microcapsules.
The microcapsule pigment 2 had an average particle diameter of 1.8 μm, a complete discoloration temperature (t4) of 55° C., a complete color development temperature (t1) of −20° C., and changed color from blue to colorless with temperature change.

Preparation of Ink Composition Ink Composition No. 1 having the composition shown in Table 1 below. 1 to No. 15 was prepared. The numerical values of the composition in the table represent % by mass, and "-" indicates no addition. In addition, No. 1 to No. 8, and no. 12 to No. No. 15 corresponds to an example. 9 to No. 11 corresponds to the comparative example.

The viscosity of the ink composition was measured at 20° C. using a rheometer “DHR-2” manufactured by TE Instruments.

The surface tension of the ink composition was measured by the vertical plate method using a platinum plate at 20° C. using a surface tensiometer (trade name: DY-300) manufactured by Kyowa Interface Science Co., Ltd.

The details of each component in the table are described below.
(1) Xanthan gum (trade name: Kelzan, manufactured by Sansho Co., Ltd.)
(2) Succinoglycan (trade name: Leozan, manufactured by Sansho Co., Ltd.)
(3) Product name: Sundec 70 (containing 70% by mass or more of starch saccharification product with 8 or more sugars and/or reduced product thereof) manufactured by Sanwa Starch Kogyo Co., Ltd. (4) Polyoxyethylene styrylphenyl phosphate ( Product name: Plysurf AL, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
(5) A 1 in general formula ( ₁ ): methyl group, A ₂ : methyl group, A ₃ : lauryl group (trade name: NIKKOL AM-301, active ingredient: 35% by mass, manufactured by Nikko Chemicals Co., Ltd.)
(6) A 1 in general formula (1): methyl group, A ₂ : methyl group, A ₃ : stearyl group (trade name: Amphithol 86B, active ingredient: 26% by _mass , manufactured by Kao Corporation)
(7) A 1 in general formula ( ₁ ): methyl group, A ₂ : methyl group, A ₃ : myristyl group (trade name: Lykavion A-200, active ingredient: 29-32% by mass, manufactured by Shin Nippon Rika Co., Ltd. )
(8) A 1 in general formula (1): methyl group, A _{2 :} methyl group, A ₃ : general formula (2) [A ₄ : propyl group, A ₅ : undecyl group] (trade name: NIKKOL AM-3130N , Active ingredient: 30% by mass, manufactured by Nikko Chemicals Co., Ltd.)
(9) 1,2-benzisothiazol-3(2H)-one (trade name: Proxel XL-2; manufactured by Lonza Japan)

Preparation of ballpoint pen refill Each ink composition thus obtained was filled into an ink storage tube made of polypropylene resin, the tip of which was equipped with a ballpoint pen tip that rotatably held a cemented carbide ball with an outer diameter of 0.5 mm. It was filled with an ink backflow preventer made of a viscous liquid. A tail plug was then fitted to the rear of the pipe to obtain each ballpoint refill.
Also, No. 1 to No. Each of the 15 ink compositions is filled in a stainless steel ink storage tube having the tip of the ballpoint pen at the tip, and the back end is filled with an ink backflow prevention member. A ball-point pen refill equipped with an ink storage tube manufactured by

Preparation of Ballpoint Pen The obtained ballpoint pen refill was attached to the exterior of a ballpoint pen (trade name: FriXion Ball 05, manufactured by Pilot Corporation). The following tests were performed using the obtained ballpoint pen. The results are shown in the table below.
Writing paper A conforming to old JIS P3201 was used as test paper for writing.

(Evaluation of overwriting property)
A square with a side of 1 cm is painted on the test paper with the ballpoint pen, and the square is erased by rubbing it with a rubbing material attached to the rear end of the ballpoint pen. A ballpoint pen was used to write (writing character: #), and the handwriting was visually observed.
◯: No blurring or discontinuity is observed in the characters. Alternatively, although characters are slightly blurred or interrupted, there is no practical problem.
x: Blurred or discontinuous characters are clearly visible. There are practical problems.

(Evaluation of dry-up resistance)
The ball-point pen was placed horizontally with the tip exposed and stored in an environment of 50° C. and 30% RH for 30 days. After that, at room temperature, 12 spiral circles were continuously written in one line on the test paper by hand, and the handwriting was visually observed.
◯: Handwriting without blurring or discontinuity can be formed from the start of writing to the end of writing.
Alternatively, although slight blurring or discontinuity was confirmed in the handwriting immediately after the start of writing, they were not found in the handwriting after the end of writing.
×: Not writable.

(Evaluation of continuous writing property)
A ball-point pen was attached to the automatic writing tester, and a spiral circle was continuously written on the test paper until the ink was completely consumed, and the handwriting was visually observed.
A: A clear handwriting is formed from the start to the end of writing.
x: The ink was not completely consumed, and writing became impossible.

同種のインキを充填して得られた、ポリプロピレン樹脂製のインキ収容管を備えるボールペンレフィルとステンレス製のインキ収容管を備えるボールペンレフィルとからは同等の評価結果が得られた。
また、耐ドライアップ性の評価において、Ｎｏ．１～Ｎｏ．８、およびＮｏ．１５については、５０℃３０％ＲＨ環境下で３０日間保管後の筆記で、掠れや途切れのない筆跡を筆記開始時から筆記終了時まで形成できた。また、Ｎｏ．１２～１４については、筆記開始直後の筆跡には若干の掠れまたは途切れが確認されたものの、筆記終了時の筆跡にはそれらが確認されなかった。

Equivalent evaluation results were obtained from a ball-point pen refill provided with a polypropylene resin ink storage tube and a ball-point pen refill provided with a stainless steel ink storage tube, which were filled with the same type of ink.
In addition, in the evaluation of dry-up resistance, No. 1 to No. 8, and no. As for No. 15, by writing after storage for 30 days in an environment of 50° C. and 30% RH, a handwriting without blurring or discontinuity could be formed from the start of writing to the end of writing. Also, No. Regarding Nos. 12 to 14, slight blurring or discontinuity was confirmed in the handwriting immediately after the start of writing, but they were not confirmed in the handwriting at the end of writing.

t1 complete color development temperature t2 color development start temperature t3 color change start temperature t4 complete color change temperature T1 complete color change temperature T2 color change start temperature T3 color change start temperature T4 complete color change temperature

Claims (8)

Reversible thermochromic properties comprising (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reaction medium that determines the temperature at which the color reaction of (a) and (b) occurs. A reversible thermochromic microcapsule pigment encapsulating a composition, a betaine amphoteric surfactant represented by the following general formula (1), a shear thinning agent, and water, wherein the shear thinning agent is A water-based ink composition for a reversible thermochromic writing instrument, which is a polysaccharide.

In the formula, A ₁ and A ₂ are independently alkyl groups having 1 to 3 carbon atoms, and A ₃ is an alkyl group having 5 to 24 carbon atoms or a functional group represented by the following general formula (2).

In the formula, _A4 is an alkyl group having 1 to 5 carbon atoms. A ₅ is an alkyl group having 1 to 16 carbon atoms. 2. The ink composition according to claim 1, wherein the content of said betaine-type amphoteric surfactant is 0.01 to 2.0% by mass based on the total mass of the ink composition. Based on the total mass of the ink composition, the content of the betaine-type amphoteric surfactant is 0.20 to 3.0% with respect to the content of the reversible thermochromic microcapsule pigment, according to claim 2 The described ink composition. 2. An ink composition according to claim 1, wherein said polysaccharide is xanthan gum and/or succinoglycan. A writing instrument containing the ink composition according to any one of claims 1 to 4. 6. The writing instrument according to claim 5, which is a ballpoint pen. 7. The ballpoint pen of claim 6, comprising a friction member. A ballpoint pen refill containing the ink composition according to any one of claims 1 to 4.

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