Aqueous ink composition for reversible thermochromic writing instrument, and writing instrument containing the same

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]

[0001] The present invention relates to a reversible thermochromic aqueous ink composition for writing instruments and a writing instrument containing the same. [Background technology]

[0002] In recent years, inks for writing instruments that use microcapsule pigments containing thermochromic compositions as colorants have become known and are used in ballpoint pens and the like. (See, for example, Patent Document 1) The aforementioned conventional ink is an ink in which the dispersion stability of the thermochromic microcapsule pigment and the ink ejection performance during writing are improved by a shear-thinning substance, and it is possible to stably form vivid lines with thermochromic properties. Furthermore, the lines formed with the ink can be heat-decolorized by rubbing them with an elastic material, and it is possible to correct letters and other characters by rewriting on the decolorized lines with the ink. However, the aforementioned ink does not perform well in so-called overwriting, where the same ink is used to create the handwriting, and it was sometimes difficult to form a clear overwritten handwriting when using this method.

[0003] Furthermore, since the heat-changeable microcapsule pigment does not have sufficient coloring power compared to common colorants such as organic pigments and carbon black, it is necessary to increase the concentration of the microcapsule pigment in order for the ink to obtain sufficient color density. In such cases, when the water in the ink evaporates, solid components such as the microcapsule pigment tend to precipitate. When such precipitation occurs in the ballpoint pen tip, the ball may stick, making it difficult to write again (so-called dry-up).

[0004] As described above, the conventional ink technology had its limitations, and there was room for further performance improvement. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 9-124993 [Overview of the project] [Problems that the invention aims to solve]

[0006] The present invention provides a reversible thermochromic aqueous ink composition for writing instruments that can stably form vivid, thermochromic lines, and that exhibits excellent overwriting properties and resistance to drying up, as well as a writing instrument containing the same. [Means for solving the problem]

[0007] The present invention "1. A reversible thermochromic aqueous ink composition for writing instruments comprising: (a) an electron-donating color-developing organic compound; (b) an electron-accepting compound; (c) a reaction medium that determines the temperature at which the color reactions of (a) and (b) occur; a betaine-type amphoteric surfactant represented by the following general formula (1); a shear viscosity-reducing agent; and water, wherein the shear viscosity-reducing agent is a polysaccharide." [ka] In the formula, A1 and A2 are independently alkyl groups having 1 to 3 carbon atoms, and A3 is an alkyl group having 5 to 24 carbon atoms or a functional group represented by the following general formula (2). [ka] In the formula, A4 is an alkyl group having 1 to 5 carbon atoms, and A5 is an alkyl group having 1 to 16 carbon atoms. 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. The ink composition according to paragraph 2, wherein the content of the betaine-type amphoteric surfactant is 0.20 to 3.0% of the total mass of the ink composition relative to the content of the reversible thermochromic microcapsule pigment. 4. The ink composition according to item 1, wherein the polysaccharide is xanthan gum and / or succinoglycan. 5. 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 according to claim 6, comprising a friction member. 8. It is defined as a "ballpoint pen refill" containing the ink composition according to any one of claims 1 to 4.

Advantages of the Invention

[0008] According to the present invention, there are provided an aqueous ink composition for a reversible thermochromic writing instrument, which can stably form a clear handwriting having thermochromic properties and is excellent in overwriting property and anti-drying-up property, and a writing instrument containing the same.

Brief Description of the Drawings

[0009] [Figure 1] It is a graph for explaining the hysteresis characteristics in the color density - temperature curve of a heat-decoloring type reversible thermochromic composition. [Figure 2] It is a graph for explaining the hysteresis characteristics in the color density - temperature curve of a heat-decoloring type reversible thermochromic composition having color memory property. [Figure 3] It is a graph for explaining the hysteresis characteristics in the color density - temperature curve of a heat-coloring type reversible thermochromic composition.

Embodiments for Carrying Out the Invention

[0010] The aqueous ink composition for a reversible thermochromic writing instrument according to the present invention (hereinafter sometimes referred to as "ink composition") contains at least a reversible thermochromic microcapsule pigment, water, and a specific betaine-type amphoteric surfactant. Hereinafter, each component constituting the ink composition according to the present invention will be described. In addition, in this specification, overwriting the handwriting with the same ink as the ink that formed the handwriting may be referred to as overwriting.

[0011] (Betaine-type amphoteric surfactant) The ink composition contains a betaine-type amphoteric surfactant represented by the following general formula (1). [Chemical formula] In the formula, A1 and A2 are each independently an alkyl group having 1 to 3 carbon atoms, and A3 is an alkyl group having 5 to 24 carbon atoms or a functional group represented by the following general formula (2). [Chemical formula] In the formula, A4 is an alkyl group having 1 to 5 carbon atoms, and A5 is an alkyl group having 1 to 16 carbon atoms. When overwriting is performed with an ink containing the betaine-type amphoteric surfactant and a reversible thermochromic microcapsule pigment, a clear handwriting with suppressed streaking and interruption of the overwritten handwriting can be obtained. Although the reason is not clear, it is presumed that the betaine-type amphoteric surfactant can improve the wettability of the ink containing the reversible thermochromic microcapsule pigment and the ink transfer to the handwriting formed with the ink containing the reversible thermochromic microcapsule pigment, and thus the handwriting formation property by overwriting is enhanced during overwriting.

[0012] In addition, the betaine-type amphoteric surfactant can also improve the dry-up resistance of the ink, and when moisture evaporates from the ink in the ballpoint pen tip, it can suppress the process in which solids such as the reversible thermochromic microcapsule pigment and the shear-thinning viscosity-imparting agent in the ink precipitate and the ball becomes fixed, inhibiting re-writing. Furthermore, the betaine-type amphoteric surfactant has an effect of enhancing lubricity and can also smooth the rotation of the ball, resulting in good ink ejection from the ballpoint pen tip.

[0013] To further consider the above-mentioned requirements for producing clear handwriting with suppressed smudging and breaks in overwritten text, and for improving resistance to drying up, it is preferable that A3 of general formula (1) be an alkyl group having 8 to 24 carbon atoms, or a functional group of general formula (2) having an alkyl group having 2 to 4 carbon atoms as A4 and an alkyl group having 3 to 14 carbon atoms as A5. More preferable is a functional group of general formula (2) having an alkyl group having 8 to 22 carbon atoms as A3, or an alkyl group having 2 to 4 carbon atoms as A4 and an alkyl group having 6 to 13 carbon atoms as A5. A more preferable A3 is a functional group of general formula (2) having an alkyl group having 10 to 20 carbon atoms, or an alkyl group having 2 to 4 carbon atoms as A4 and an alkyl group having 8 to 13 carbon atoms as A5. Betaine-type amphoteric surfactants possessing such functional groups are excellent at making overwritten strokes clearer and improving resistance to drying up. They also exhibit excellent affinity for microcapsule pigments, further enhancing the dispersibility of reversible thermochromic microcapsule pigments.

[0014] The content of the betaine-type amphoteric surfactant is preferably 0.01 to 2.0% by mass, more preferably 0.02 to 1.5% by mass, even more preferably 0.02 to 1.0% by mass, even more preferably 0.05 to 1.0% by mass, and particularly preferably 0.05 to 0.5% by mass, based on the total mass of the ink composition. When the content is within the above range, it is easier to make overwritten lines clearer and to improve the resistance to drying up.

[0015] Furthermore, considering the need to improve the ink's resistance to drying up, the content of the betaine-type amphoteric surfactant is preferably 0.20 to 3.0%, more preferably 0.20 to 2.5%, even more preferably 0.20 to 2.0%, and particularly preferably 0.25 to 2.0%, relative to the total mass of the ink composition and the content of the reversible thermochromic microcapsule pigment.

[0016] The ink composition according to the present invention contains a reversible thermochromic microcapsule pigment (hereinafter sometimes referred to as "microcapsule pigment") as a coloring agent.

[0017] The microcapsule pigment used in the ink composition according to the present invention contains a reversible thermochromic composition. This reversible thermochromic composition can be used as a heat-decolorizing type (decolorizes when heated and develops color when cooled) reversible thermochromic composition containing at least three essential components of a reaction medium that determines the temperature at which the color reaction of components (a) and (b) occurs.

[0018] Examples of reversible thermochromic compositions to which such microcapsule pigments can be applied include compositions described in Japanese Patent Publication No. 51-44706, Japanese Patent Publication No. 51-44707, Japanese Patent Publication No. 1-29398, etc., which change color before and after a predetermined temperature (color change point), exhibiting a decolorized state in the temperature range above the high-temperature color change point and a colored state in the temperature range below the low-temperature color change point, with only one of the two states existing in the room temperature range, and the other state being maintained as long as the heat or cold required to bring about that state is applied, but returning to the state exhibited in the room temperature range when the application of heat or cold is stopped, and which have a relatively small hysteresis width (ΔH) (ΔH = 1 to 7°C) (see Figure 1).

[0019] Furthermore, other examples of reversible thermochromic compositions to which such microcapsule pigments can be applied include compositions that exhibit a large hysteresis width (ΔH = 8 to 70°C) as described in Japanese Patent Publication No. 4-17154, Japanese Patent Application Publication No. 7-179777, Japanese Patent Application Publication No. 7-33997, Japanese Patent Application Publication No. 8-39936, Japanese Patent Application Publication No. 2005-1369, etc., in which the shape of the curve plotted for the change in color intensity due to temperature changes follows a significantly different path when the temperature is increased from a temperature below the color change temperature range compared to when it is decreased from a temperature above the color change temperature range, and in which the colored state at temperatures below the complete color development temperature t1, or the decolorized state at high temperatures above the complete decolorization temperature t4, have color memory properties in a specific temperature range [a temperature range between the color development start temperature t2 and the decolorization start temperature t3 (essentially a two-phase retention temperature range)] (see Figure 2).

[0020] [Microencapsulated pigments] The following provides a detailed explanation of each component (a), (b), and (c). (a) Component, i.e., the electron-donating chromogenic organic compound, is the component that determines the color, and is a compound that produces color by donating electrons to component (b), which is a color developer.

[0021] Examples of electron-donating colorimetric organic compounds include phthalide compounds, fluorane compounds, styrinoquinoline compounds, diazalodamine lactone compounds, pyridine compounds, quinazoline compounds, and bisquinazoline compounds, among which phthalide compounds and fluorane compounds are preferred. Examples of phthalide compounds include diphenylmethane phthalide compounds, phenylindolyl phthalide compounds, indolyl phthalide compounds, diphenylmethane azaphthalide compounds, phenylindolyl azaphthalide compounds, and their derivatives. Among these, phenylindolyl azaphthalide compounds and their derivatives are preferred. Examples of fluorane compounds include aminofluorane compounds, alkoxyfluorane compounds, and their derivatives.

[0022] The following are examples of compounds that can be used in component (a). 3,3-bis(4-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindole-3-yl)phthalide, 3,3-Bis(1-n-butyl-2-methylindole-3-yl)phthalide, 3,3-Bis(2-ethoxy-4-diethylaminophenyl)-4-azaphthalide, 3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methylindole-3-yl)-4-azaphthalide, 3-(2-n-hexyloxy-4-diethylaminophenyl)-3-(1-ethyl-2-methylindole-3-yl)-4-azaphthalide, 3-[2-ethoxy-4-(N-ethylanilino)phenyl]-3-(1-ethyl-2-methylindole-3-yl)-4-azaphthalide, 3-(2-acetamido-4-diethylaminophenyl)-3-(1-propyl-2-methylindole-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′-one, 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′-one, 4,5,6,7-Tetrachloro-3-(4-dimethylamino-2-methoxyphenyl)-3-(1-n-butyl-2-methylindole-3-yl)-1(3H)-isobenzofuranone, 4,5,6,7-Tetrachloro-3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindole-3-yl)-1(3H)-isobenzofuranone, 4,5,6,7-Tetrachloro-3-(4-diethylamino-2-ethoxyphenyl)-3-(1-n-pentyl-2-methylindole-3-yl)-1(3H)-isobenzofuranone, 4,5,6,7-Tetrachloro-3-(4-diethylamino-2-methylphenyl)-3-(1-ethyl-2-methylindole-3-yl)-1(3H)-isobenzofuranone, 3′,6′-bis[phenyl(2-methylphenyl)amino]spiro[isobenzofuran-1(3H),9′-[9H]xanthene]-3-one, 3′,6′-bis[phenyl(3-methylphenyl)amino]spiro[isobenzofuran-1(3H),9′-[9H]xanthene]-3-one, 3′,6′-bis[phenyl(3-ethylphenyl)amino]spiro[isobenzofuran-1(3H),9′-[9H]xanthene]-3-one, 2,6-bis(2′-ethyloxyphenyl)-4-(4′-dimethylaminophenyl)pyridine, 2,6-Bis(2′,4′-diethyloxyphenyl)-4-(4′-dimethylaminophenyl)pyridine, 2-(4′-dimethylaminophenyl)-4-methoxyquinazoline, 4,4′-Ethylenedioxy-bis[2-(4-diethylaminophenyl)quinazoline]

[0023] In addition to compounds having substituents on the phenyl group forming the xanthene ring, fluoranes may also be compounds that exhibit a blue or black color, having substituents on the phenyl group forming the xanthene ring as well as substituents (for example, alkyl groups such as methyl groups, halogen atoms such as chlorine atoms) on the phenyl group forming the lactone ring.

[0024] (b) Component, i.e., the electron-accepting compound, is a compound that accepts electrons from component (a) and functions as a color developer for component (a). Examples of electron-accepting compounds include compounds selected from the group of compounds having active protons, the group of pseudoacidic compounds (compounds that are not acids but act as acids in a reversible thermochromic composition to cause the color of component (a)), and the group of compounds having electron vacancies. Among the above components (b), compounds selected from the group of compounds having active protons are preferred.

[0025] Examples of compounds having active protons include compounds having phenolic hydroxyl groups and their derivatives, carboxylic acids and their derivatives, acidic phosphate esters and their derivatives, azole compounds and their derivatives, 1,2,3-triazoles and their derivatives, cyclic carbosulfimides, C2-C5 halohydrins, sulfonic acids and their derivatives, and inorganic acids. Preferred carboxylic acids and their derivatives are aromatic carboxylic acids and their derivatives, or C2-C5 aliphatic carboxylic acids and their derivatives. Examples of pseudoacidic compounds include metal salts of compounds having phenolic hydroxyl groups, metal salts of carboxylic acids, metal salts of acidic phosphate esters, metal salts of sulfonic acids, aromatic carboxylic acid anhydrides, aliphatic carboxylic acid anhydrides, mixed anhydrides of aromatic carboxylic acids and sulfonic acids, cycloolefin dicarboxylic acid anhydrides, urea and its derivatives, thiourea and its derivatives, guanidine and its derivatives, and halogenated alcohols. Examples of compounds containing electron vacancies include borates, borate esters, and inorganic salts.

[0026] Among the components of (b) above, compounds having phenolic hydroxyl groups are preferred because they can more effectively exhibit thermal discoloration properties. Compounds having phenolic hydroxyl groups broadly include monophenol compounds to polyphenol compounds, and further include bisphenol compounds, trisphenol compounds, phenol-aldehyde condensation resins, etc. It is preferable that compounds having phenolic hydroxyl groups have at least two benzene rings. Furthermore, compounds having phenolic hydroxyl groups may have substituents such as alkyl groups, aryl groups, acyl groups, alkoxycarbonyl groups, carboxyl groups and their esters or amide groups, halogen atoms, etc.

[0027] 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.

[0028] Examples of compounds of component (b) are given 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, Timor, 3-methyl-4-methylthiophenol, 2-tert-butyl-5-methylphenol, 2,6-bis(hydroxymethyl)-4-methylphenol, 2,3,5-trimethylphenol, 2,6-bis(hydroxymethyl)-4-tert-octylphenol, 6-hydroxy-1,3-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-Heptadecafluorooctylethane hydroxybenzoate, 4-Benzyl hydroxybenzoate, 4-Benzyl hydroxybenzoate, 4-hydroxybenzoate-o-methylbenzyl 4-m-methylbenzyl hydroxybenzoate, 4-hydroxybenzoate-p-methylbenzyl 4-Hydroxybenzoate-p-ethylbenzyl 4-Hydroxybenzoate-p-propylbenzyl 4-Hydroxybenzoate-p-tert-butylbenzyl Phenylate 4-hydroxybenzoate, 4-hydroxybenzoate-o-methylphenylethyl, 4-M-methylphenylethyl hydroxybenzoate, 4-hydroxybenzoate-p-methylphenylethyl, 4-hydroxybenzoate-p-ethylphenylethyl, 4-Hydroxybenzoate-p-propylphenylethyl, 4-Hydroxybenzoate-p-tert-butylphenylethyl Examples include the following.

[0029] Examples of compounds having two phenolic hydroxyl groups include, Resorcinol, 2-methylresorcinol, 4-n-hexylresorcinol, 4-n-octylresorcinol, 4-tert-octylresorcinol, 4-benzoylresorcinol, 4-nitroresorcinol, Methyl β-resorcinate, Benzyl β-resorcinate, 2-Chloro-4-pentanoylresorcinol, 6-Chloro-4-pentanoylresorcinol, 2-Chloro-4-hexanoylresorcinol, 6-Chloro-4-hexanoylresorcinol, 2-Chloro-4-propanoylresorcinol, 6-Chloro-4-propanoylresorcinol, 2,6-Dichloro-4-propanoylresorcinol, 6-Fluoro-4-propanoylresorcinol, 2-Chloro-4-phenylacetylresorcinol, 6-Chloro-4-phenylacetylresorcinol, 2-Chloro-4-β-phenylpropanoylresorcinol, 6-Chloro-4-β-phenylpropanoylresorcinol, 2-Chloro-4-phenoxyacetylresorcinol, 6-Chloro-4-phenoxyacetylresorcinol, 4-benzoyl-2-chlororesorcinol, 6-Chloro-4-m-methylbenzoylresorcinol, 4-[1′,3′,4′,9′a-tetrahydro-6′-hydroxyspiro(cyclohexane-1,9′-[9H]-xanthene)-4′a-[2H]-yl]-1,3-benzenediol, Hydroquinone, Methylhydroquinone, Trimethylhydroquinone, Catechol, 4-tert-butylcatechol, 1,6-Dihydroxynaphthalene, 2,7-Dihydroxynaphthalene, 1,5-Dihydroxynaphthalene, 2,6-Dihydroxynaphthalene, 2,4-dihydroxybenzophenone, 4,4′-Dihydroxybenzophenone, 2,4-dihydroxy-2′-methylbenzophenone, 2,4-dihydroxy-3′-methylbenzophenone, 2,4-dihydroxy-4′-methylbenzophenone, 2,4-dihydroxy-4′-ethylbenzophenone, 2,4-dihydroxy-4′-n-propylbenzophenone, 2,4-dihydroxy-4′-isopropylbenzophenone, 2,4-dihydroxy-4′-n-butylbenzophenone, 2,4-dihydroxy-4′-isobutylbenzophenone, 2,4-dihydroxy-4′-tert-butylbenzophenone, 2,4-dihydroxy-4′-n-pentylbenzophenone, 2,4-dihydroxy-4′-n-hexylbenzophenone, 2,4-dihydroxy-4′-n-heptylbenzophenone, 2,4-dihydroxy-4′-n-octylbenzophenone, 2,4-dihydroxy-4′-n-decylbenzophenone, 2,4-dihydroxy-2′,3′-dimethylbenzophenone, 2,4-dihydroxy-2′,4′-dimethylbenzophenone, 2,4-dihydroxy-2′,5′-dimethylbenzophenone, 2,4-dihydroxy-2′,6′-dimethylbenzophenone, 2,4-dihydroxy-3′,4′-dimethylbenzophenone, 2,4-dihydroxy-3′,5′-dimethylbenzophenone, 2,4-dihydroxy-2′,4′,6′-trimethylbenzophenone, 2,4-dihydroxy-2′-methoxybenzophenone, 2,4-dihydroxy-3′-methoxybenzophenone, 2,4-dihydroxy-4′-methoxybenzophenone, 2,4-dihydroxy-2′-ethoxybenzophenone, 2,4-dihydroxy-4′-ethoxybenzophenone, 2,4-dihydroxy-4′-n-propoxybenzophenone, 2,4-dihydroxy-4′-isopropoxybenzophenone, 2,4-dihydroxy-4′-n-butoxybenzophenone, 2,4-dihydroxy-4′-isobutoxybenzophenone, 2,4-dihydroxy-4′-n-pentyloxybenzophenone, 2,4-dihydroxy-4′-n-hexyloxybenzophenone, 2,4-dihydroxy-4′-n-heptyloxybenzophenone, 2,4-dihydroxy-4′-n-octyloxybenzophenone, 2,4-dihydroxy-4′-n-nonyloxybenzophenone, 2,4-dihydroxy-2′,3′-dimethoxybenzophenone, 2,4-dihydroxy-2′,4′-dimethoxybenzophenone, 2,4-dihydroxy-2′,5′-dimethoxybenzophenone, 2,4-dihydroxy-2′,6′-dimethoxybenzophenone, 2,4-dihydroxy-3′,4′-dimethoxybenzophenone, 2,4-dihydroxy-3′,5′-dimethoxybenzophenone, 2,4-dihydroxy-3′,4′-diethoxybenzophenone, 2,4-dihydroxy-2′,3′,4′-trimethoxybenzophenone, 2,4-dihydroxy-2′,3′,6′-trimethoxybenzophenone, 2,4-dihydroxy-3′,4′,5′-trimethoxybenzophenone, 2,4-Dihydroxy-3′,4′,5′-Triethoxybenzophenone Examples include the following.

[0030] Furthermore, examples of bisphenol compounds include, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-Bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)n-butane, 1,1-bis(4-hydroxyphenyl)n-pentane, 1,1-Bis(4-hydroxyphenyl)n-hexane, 1,1-Bis(4-hydroxyphenyl)n-heptane, 1,1-bis(4-hydroxyphenyl)n-octane, 1,1-bis(4-hydroxyphenyl)n-nonane, 1,1-bis(4-hydroxyphenyl)n-decane, 1,1-Bis(4-hydroxy-3-methylphenyl)decane, 1,1-bis(4-hydroxyphenyl)n-dodecane, 1,1-bis(4-hydroxyphenyl)-2-methylpropane, 1,1-Bis(4-hydroxyphenyl)-3-methylbutane, 1,1-bis(4-hydroxyphenyl)-3-methylpentane, 1,1-bis(4-hydroxyphenyl)-2,3-dimethylpentane, 1,1-Bis(4-hydroxyphenyl)-2-ethylbutane, 1,1-Bis(4-hydroxyphenyl)-2-ethylhexane, 1,1-bis(4-hydroxyphenyl)-3,7-dimethyloctane, 1,1-Bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-Bis(4-hydroxy-3-methyl)cyclohexane, Diphenolic acid, 1-phenyl-1,1-bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)n-butane, 2,2-bis(4-hydroxyphenyl)n-pentane, 2,2-bis(4-hydroxyphenyl)n-hexane, 2,2-bis(4-hydroxyphenyl)n-heptane, 2,2-bis(4-hydroxyphenyl)n-octane, 2,2-bis(4-hydroxyphenyl)n-nonane, 2,2-bis(4-hydroxyphenyl)n-decane, 2,2-bis(4-hydroxyphenyl)n-dodecane, 2,2-bis(4-hydroxyphenyl)-6,10,14-trimethylpentadecane, 1-phenyl-1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)methylpropionate, 2,2-bis(4-hydroxyphenyl)butylpropionate, 2,2-bis(4-hydroxy-3-methylphenyl)methylpropionate, 2,2-bis(4-hydroxyphenyl)ethylpropionate, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 2,2-bis(4-hydroxyphenyl)-4-methylhexane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 2,2-Bis(3,5-dihydroxymethyl-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)butane, 2,2-bis(4-hydroxy-3-isopropylphenyl)propane, 2,2-bis(3-sec-butylphenyl-4-hydroxy)propane, 2,2-bis(4-hydroxy-3-phenylphenyl)propane, 2,2-bis(3-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(3-fluoro-4-hydroxyphenyl)propane, 2,2-Bis(3,5-dihydroxymethyl-4-hydroxyphenyl)propane, 9,9-Bis(4-hydroxy-3-methylphenyl)fluorene, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, 1,4-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, 3,3-bis(4-hydroxyphenyl)oxyindole, 3,3-bis(4-hydroxy-3-methylphenyl)oxyindole, 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′-hydroxydiphenyl sulfone, 4-(4-ethylbenzyloxy)-4′-hydroxydiphenyl sulfone, 4-(4-n-propylbenzyloxy)-4′-hydroxydiphenyl sulfone, 4-(4-isopropylbenzyloxy)-4′-hydroxydiphenylsulfone, 4-(4-n-butylbenzyloxy)-4′-hydroxydiphenylsulfone, 4-(4-isobutylbenzyloxy)-4′-hydroxydiphenylsulfone, 4-(4-sec-butylbenzyloxy)-4′-hydroxydiphenylsulfone, 4-(4-tert-butylbenzyloxy)-4′-hydroxydiphenylsulfone, 4-(3-methylbenzyloxy)-4′-hydroxydiphenyl sulfone, 4-(3-ethylbenzyloxy)-4′-hydroxydiphenyl sulfone, 4-(3-n-propylbenzyloxy)-4′-hydroxydiphenyl sulfone, 4-(3-isopropylbenzyloxy)-4′-dihydroxyphenylsulfone, 4-(3-n-butylbenzyloxy)-4′-hydroxydiphenyl sulfone, 4-(3-isobutylbenzyloxy)-4′-hydroxydiphenylsulfone, 4-(3-sec-butylbenzyloxy)-4′-hydroxydiphenylsulfone, 4-(3-tert-butylbenzyloxy)-4′-hydroxydiphenyl sulfone, 4-(2-methylbenzyloxy)-4′-hydroxydiphenylsulfone, 4-(2-ethylbenzyloxy)-4′-hydroxydiphenylsulfone, 4-(2-n-propylbenzyloxy)-4′-hydroxydiphenylsulfone, 4-(2-isopropylbenzyloxy)-4′-hydroxydiphenyl sulfone, 4-(2-n-butylbenzyloxy)-4′-hydroxydiphenylsulfone, 4-(2-isobutylbenzyloxy)-4′-hydroxydiphenylsulfone, 4-(2-sec-butylbenzyloxy)-4′-hydroxydiphenylsulfone, 4-(2-tert-butylbenzyloxy)-4′-hydroxydiphenyl sulfone, 2,4′-Dihydroxydiphenylsulfone, 3,4′-Dihydroxydiphenylsulfone, 4-Hydroxydiphenylsulfone, 4-methyl-4′-hydroquidisiphenyl sulfone, 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′-hydroxydiphenyl sulfone, 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-dihydroxydiphenylsulfone, 3′,4′-dihydroxy-4-methyldiphenylsulfone, 3,4,4′-trihydroxydiphenylsulfone, Bis(3,4-dihydroxyphenyl)sulfone, 2,3,4-trihydroxydiphenylsulfone, 4-Isopropoxy-4′-Hydroxydiphenylsulfone, 4-n-propoxy-4′-hydroxydiphenylsulfone, 4-allyloxy-4′-hydroxydiphenylsulfone, 4-benzyloxy-4′-hydroxydiphenylsulfone, 4-(2-propenyloxy)-4′-hydroxydiphenylsulfone, 3-benzyl-4-benzyloxy-4′-hydroxydiphenyl sulfone, 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′-hydroxydiphenyl sulfone, 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-octylphenyl) sulfide, Bis(5-chloro-2-hydroxyphenyl) sulfide, Bis(3-cyclohexyl-4-hydroxyphenyl) sulfide, Bis(4-hydroxyphenylthioethoxy)methane, 1,5-(4-hydroxyphenylthio)-3-oxypentane, 1,8-Bis(4-hydroxyphenylthio)-3,6-dioxaoctane Examples include the following.

[0031] Examples of compounds having three phenolic hydroxyl groups include pyrogallol, phloroglucinol, phloroglucinol carboxylic acid, gallic acid, octyl gallate, and dodecyl gallate.

[0032] Furthermore, examples of trisphenol compounds include, 4,4′,4″-methylidinetrisphenol, 4,4′,4″-methylidinetris(2-methylphenol), 4,4′-[(2-hydroxyphenyl)methylene]bis(2,3,5-trimethylphenol), 4,4′-[(4-hydroxyphenyl)methylene]bis(2-methylphenol), 4,4′-[(4-hydroxyphenyl)methylene]bis(2,6-dimethylphenol), 4,4′-[(4-hydroxy-3-methoxyphenyl)methylene]bisphenol, 4,4′-[(4-hydroxyphenyl)methylene]bis(2-cyclohexyl-5-methylphenol), 4,4′,4″-ethyridinetrisphenol, 4,4′,4″-Ethyridinetris(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}propyridene]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)propyridene]bis(2-cyclohexyl-5-methylphenol), 4,4′-[(2-hydroxyphenyl)methylene]bis(2-methylphenol), 2,4′,4″-methylidinetrisphenol, 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-biphenylpropylenene]bis(5-cyclohexyl-2-methylphenol), 4,4′-[3-(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropyridene]bis(2,5-dimethylphenol), 2,4-bis[(2,5-dimethyl-4-hydroxyphenyl)methyl]-6-methylphenol, 1,1,2-Tris(4-hydroxyphenyl)ethane, 1,1,3-Tris(4-hydroxyphenyl)propane, 1,1,4-Tris(4-hydroxyphenyl)butane, 1,2,2-Tris(4-hydroxyphenyl)propane, 1,2,2-Tris(4-hydroxyphenyl)butane, 1,2,2-Tris(4-hydroxyphenyl)pentane, 1,2,2-Tris(4-hydroxyphenyl)hexane, 1,2,2-Tris(4-hydroxyphenyl)heptane, 1,2,2-Tris(4-hydroxyphenyl)octane, 1,2,2-Tris(4-hydroxyphenyl)-3-methylbutane 1,2,2-Tris(4-hydroxyphenyl)-3,3-dimethylbutane, 1,2,2-Tris(4-hydroxyphenyl)-4,4-dimethylpentane, 1,3,3-Tris(4-hydroxyphenyl)butane, 1,3,3-Tris(4-hydroxyphenyl)pentane, 1,3,3-Tris(4-hydroxyphenyl)hexane, 1,3,3-Tris(4-hydroxyphenyl)heptane, 1,3,3-Tris(4-hydroxyphenyl)octane, 1,3,3-Tris(4-hydroxyphenyl)nonane, 1,4,4-Tris(4-hydroxyphenyl)pentane, 1,4,4-Tris(4-hydroxyphenyl)hexane, 1,4,4-Tris(4-hydroxyphenyl)heptane, 1,4,4-Tris(4-hydroxyphenyl)octane, 1,4,4-Tris(4-hydroxyphenyl)nonane, 1,4,4-Tris(4-hydroxyphenyl)decane, 1,2,2-Tris(2-hydroxyphenyl)propane, 1,1,2-Tris(3-hydroxyphenyl)propane, 1-(4-hydroxyphenyl)-2,2-bis(2-hydroxyphenyl)propane, 1,2,2-Tris(3-fluoro-4-hydroxyphenyl)propane, 1,2,2-Tris(3-chloro-4-hydroxyphenyl)propane, 1,2,2-Tris(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3-ethyl-4-hydroxyphenyl)-1-(4-hydroxyphenyl)propane, 2,2-Bis(3-tert-butyl-4-hydroxyphenyl)-1-(4-hydroxyphenyl)propane, 2,2-bis(2-hydroxy-3-biphenylyl)-1-(4-hydroxyphenyl)propane, 2,2-Bis(3-trifluoromethyl-4-hydroxyphenyl)-1-(4-hydroxyphenyl)propane, 2-(3-methyl-4-hydroxyphenyl)-1,2-bis(4-hydroxyphenyl)propane, 1-(3-methyl-4-hydroxyphenyl)-2,2-bis(4-hydroxyphenyl)propane, 3-(3-methyl-4-hydroxyphenyl)-1,3-bis(4-hydroxyphenyl)butane, 1-(3-methyl-4-hydroxyphenyl)-3,3-bis(4-hydroxyphenyl)butane, 4-(3-methyl-4-hydroxyphenyl)-1,4-bis(4-hydroxyphenyl)pentane, 1-(3-methyl-4-hydroxyphenyl)-4,4-bis(4-hydroxyphenyl)pentane, 1,2-bis(3-methyl-4-hydroxyphenyl)-2-(4-hydroxyphenyl)propane, 3,3-bis(3-methyl-4-hydroxyphenyl)-1-(4-hydroxyphenyl)butane, 1,3-bis(3-methyl-4-hydroxyphenyl)-3-(4-hydroxyphenyl)butane, 4,4-bis(3-methyl-4-hydroxyphenyl)-1-(4-hydroxyphenyl)pentane, 1,4-bis(3-methyl-4-hydroxyphenyl)-4-(4-hydroxyphenyl)pentane, 1,1,2-Tris(3-methyl-4-hydroxyphenyl)ethane, 1,2,2-Tris(3-methyl-4-hydroxyphenyl)propane, 1,1,3-Tris(3-methyl-4-hydroxyphenyl)propane, 1,3,3-Tris(3-methyl-4-hydroxyphenyl)butane, 1,1,4-Tris(3-methyl-4-hydroxyphenyl)butane, 1,4,4-Tris(3-methyl-4-hydroxyphenyl)pentane, 4,4′-[4-(4-hydroxyphenyl)-sec-butylidene]bis(2-methylphenol) Examples include the following.

[0033] 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″-Ethyridinetris{[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]-methacyclophane, 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″-Ethyridinetris[2,6-bis(2-hydroxybenzyl)phenol], 4,4′,4″-Ethyridinetris[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]-methacyclophane, 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 Examples include the following.

[0034] Examples of carboxylic acids and their derivatives include, 3,5-di(α-methylbenzyl)salicylic acid, 4-(2-p-methoxyphenyloxyethoxy)salicylic acid, 4-Hydroxyphenylbenzoic acid, 4-chlorobenzoic acid, 4-[2-(p-methoxyphenoxy)ethyloxy] salicylic acid, 4-[3-(p-tolylsulfonyl)propyloxy]salicylic acid, 5-[p-(2-p-methoxyphenoxyethoxy)cumyl] salicylic acid, 4-Octyloxycarbonylaminosalicylic acid, 3,5-Distyreminated salicylic acid, N-(p-toluenesulfonyl)-glycine, N-(p-toluenesulfonyl)-alanine, N-(p-toluenesulfonyl)-β-alanine, N-phenylaminocarbonylglycine, 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, 2-O-(Phenethylaminocarbonyl)-lactic acid etc. can be exemplified.

[0035] Examples of the acidic phosphate compound include methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, isodecyl acid phosphate, isotridecyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, monobutyl phosphate, dibutyl phosphate, monoisodecyl phosphate, bis(2-ethylhexyl) phosphate, and the like.

[0036] (B) As a component, a compound having a phenolic hydroxyl group is preferable because the thermochromic characteristics can be more effectively exhibited. However, a compound selected from aromatic carboxylic acids, aliphatic carboxylic acids having 2 to 5 carbon atoms, metal carboxylates, acidic phosphate esters and their metal salts, and 1,2,3-triazole and its derivatives may also be used.

[0037] (C) The component (c) of the reaction medium that causes the electron transfer reaction between the component (A) and the component (B) to occur reversibly in a specific temperature range will be described. (C) Examples of the component (c) include alcohols, esters, ketones, ethers, and acid amides.

[0038] When the reversible thermochromic composition is encapsulated in microcapsules and applied to secondary processing, low molecular weight compounds will evaporate outside the capsules when subjected to high heat treatment. Therefore, compounds having 10 or more carbon atoms are preferably used to stably retain them inside the capsules.

[0039] As the alcohols, aliphatic monohydric saturated alcohols having 10 or more carbon atoms are effective. Examples thereof include decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, heptadecyl alcohol, octadecyl alcohol, eicosyl alcohol, docosyl alcohol, and the like.

[0040] As for esters, esters with 10 or more carbon atoms are effective, and esters obtained from any combination of a monocarboxylic acid having an aliphatic and alicyclic or aromatic ring and a monohydric alcohol having an aliphatic and alicyclic or aromatic ring, esters obtained from any combination of a polycarboxylic acid having an aliphatic and alicyclic or aromatic ring and a monohydric alcohol having an aliphatic and alicyclic or aromatic ring, and any combination of a monocarboxylic acid having an aliphatic and alicyclic or aromatic ring and a polyhydric alcohol having an aliphatic and alicyclic or aromatic ring Examples of esters obtained from various combinations include ethyl caprylate, octyl caprylate, stearyl caprylate, myristyl caprate, docosyl caprate, 2-ethylhexyl laurate, n-decyl laurate, 3-methylbutyl myristate, cetyl myristate, isopropyl palmitate, neopentyl palmitate, nonyl palmitate, cyclohexyl palmitate, n-butyl stearate, 2-methylbutyl stearate, 3,5,5-trimethylhexyl stearate, and 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 azelaate, di-(n-nonyl sebacate) Examples include 1,18-octadecylmethylenedicarboxylic acid dineopentyl, 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, etc.

[0041] Furthermore, esters of saturated fatty acids and branched aliphatic alcohols, as well as ester compounds of unsaturated fatty acids or branched or substituted saturated fatty acids with branched or carbon-16 or more aliphatic alcohols, are also effective.

[0042] Examples of ester compounds include 2-ethylhexyl butyrate, 2-ethylhexyl behenate, 2-ethylhexyl myristate, 2-ethylhexyl caprate, 3,5,5-trimethylhexyl laurate, 3,5,5-trimethylhexyl palmitate, 3,5,5-trimethylhexyl stearate, 2-methylbutyl caproate, 2-methylbutyl caprylate, 2-methylbutyl caprate, 1-ethylpropyl palmitate, 1-ethylpropyl stearate, 1-ethylpropyl behenate, and laurin. 1-Ethylhexyl Acid, 1-Ethylhexyl Myristate, 1-Ethylhexyl Palmitate, 2-Methylpentyl Caproate, 2-Methylpentyl Caprylate, 2-Methylpentyl Caprate, 2-Methylpentyl Laurate, 2-Methylbutyl Stearate, 2-Methylbutyl Stearate, 3-Methylbutyl Stearate, 1-Methylheptyl Stearate, 2-Methylbutyl Behenate, 3-Methylbutyl Behenate, 1-Methylheptyl Stearate, 1-Methylheptyl Behenate, 1-Ethyl Caproate Pentyl, 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, 3,7-dimethyloctyl stearate, 3,7-behenate Examples include dimethyloctyl oleate, 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, etc.

[0043] Furthermore, in order to exhibit large hysteresis characteristics with respect to the color density-temperature curve and change color, thereby providing color memory depending on temperature changes, examples include carboxylic acid ester compounds that exhibit a ΔT value (melting point-cloud point) of 5°C or more and less than 50°C as described in Japanese Patent Publication No. 4-17154, such as carboxylic acid esters containing substituted aromatic rings in the molecule, esters of carboxylic acids containing unsubstituted aromatic rings with aliphatic alcohols having 10 or more carbon atoms, carboxylic acid esters containing cyclohexyl groups in the molecule, esters of fatty acids having 6 or more carbon atoms with unsubstituted aromatic alcohols or phenols, esters of fatty acids having 8 or more carbon atoms with branched aliphatic alcohols, esters of dicarboxylic acids with aromatic alcohols or branched aliphatic alcohols, dibenzyl cinnamate, heptyl stearate, didecyl adipate, dilauryl adipate, dimyristyl adipate, dicetyl adipate, distearyl adipate, trilaurin, trimiristine, tristearin, dimyristine, distearin, etc.

[0044] Furthermore, fatty acid ester compounds obtained from an odd-numbered aliphatic monohydric alcohol with 9 or more carbon atoms and an even-numbered aliphatic carboxylic acid, as well as fatty acid ester compounds with a total of 17 to 23 carbon atoms obtained from an n-pentyl alcohol or n-heptyl alcohol and an even-numbered aliphatic carboxylic acid with 10 to 16 carbon atoms, are also effective.

[0045] 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, n-undecyl caprylate, n-tridecyl caprylate, n-pentadecyl caprylate, n-heptyl caprate, n-nonyl caprate, n-undecyl caprate, n-tridecyl caprate, n-pentadecyl caprate, n-pentyl laurate, n-heptyl laurate, n-nonyl laurate, n-undecyl laurate, n-tridecyl laurate, n-pentadecyl laurate, n-pentyl myristate, and n-heptyl myristate. Examples include n-nonyl myristate, n-undecyl myristate, n-tridecyl myristate, n-pentadecyl myristate, n-pentyl palmitate, n-heptyl palmitate, n-nonyl palmitate, n-undecyl palmitate, n-tridecyl palmitate, n-pentadecyl palmitate, n-nonyl stearate, n-undecyl stearate, n-tridecyl stearate, n-pentadecyl stearate, n-nonyl eicosanoate, n-undersi eicosanoate, n-tridecyl eicosanoate, n-pentadecyl eicosanoate, n-nonyl behenate, n-undecyl behenate, n-tridecyl behenate, and n-pentadecyl behenate.

[0046] As for ketones, aliphatic ketones with a total of 10 or more carbon atoms are effective, and examples include 2-decanone, 3-decanone, 4-decanone, 2-undecanone, 3-undecanone, 4-undecanone, 5-undecanone, 2-dodecanone, 3-dodecanone, 4-dodecanone, 5-dodecanone, 2-tridecanone, 3-tridecanone, 2-tetradecanone, 2-pentadecanone, 8-pentadecanone, 2-hexadecanone, 3-hexadecanone, 9-heptadecanone, 2-pentadecanone, 2-octadecanone, 2-nonadecanone, 10-nonadecanone, 2-eicosanone, 11-eicosanone, 2-heneicosanone, 2-docosanone, laurone, stearone, etc.

[0047] Furthermore, arylalkyl ketones with a total carbon number of 12 to 24, such as n-octadecanophenone, n-heptadecanophenone, n-hexadecanophenone, n-pentadecanophenone, n-tetradecanophenone, 4-n-dodecacetophenone, n-tridecanophenone, 4-n-undecanoacetophenone, n-laurophenone, 4-n-decanoacetophenone, n-undecanophenone, 4-n-nonylacetophenone, n-decanophenone, 4-n-octylacetophenone, n-nonylacetophenone Examples include nophenone, 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-acetonaphthone, 2-acetonaphthone, and cyclopentylphenyl ketone.

[0048] As for ethers, aliphatic ethers with a total of 10 or more carbon atoms are effective, and examples include dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, dinonyl ether, didecyl ether, diundecyl ether, didodecyl ether, ditridecyl ether, ditetradecyl ether, dipentadecyl ether, dihexadecyl ether, dioctadecyl ether, decanediol dimethyl ether, undecanediol dimethyl ether, dodecanediol dimethyl ether, tridecanediol dimethyl ether, decanediol diethyl ether, undecanediol diethyl ether, etc.

[0049] Examples of acid amides include acetamide, propionic acid amide, butyrate 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, oleic acid amide, erucic acid amide, benzamide, caproic acid anilide, caprylic acid anilide, capric acid anilide, lauric acid anilide, myristic acid anilide, palmitic acid anilide, stearic acid anilide, behenic acid anilide, oleic acid anilide, erucic acid anilide, and N-methyl caproic acid. N-methylamide caprylic acid, N-methylamide capric acid, N-methylamide laurate, N-methylamide myristate, N-methylamide palmitate, N-methylamide stearate, N-methylamide behenate, N-methylamide oleate, N-methylamide erucate, N-ethylamide laurate, N-ethylamide myristate, N-ethylamide palmitate, N-ethylamide stearate, N-ethylamide oleate, N-butylamide laurate, N-butylamide myristate, N-butylamide palmitate, S N-butylamide thearate, N-butylamide oleate, N-octylamide laurate, N-octylamide myristate, N-octylamide palmitate, N-octylamide stearate, N-octylamide oleate, N-dodecylamide laurate, N-dodecylamide myristate, N-dodecylamide palmitate, N-dodecylamide stearate, N-dodecylamide oleate, dilauric acid amide, dimyristate acid amide, dipalmitic acid amide, distearic acid amide, dioleic acid amide, trilauric acid amide, Limyristate, tripalmitic acid, tristearate, trioleamide, succinamide, adipic acid, glutaramide, malonamide, azelaic acid, maleamide, succinate N-methylamide, adipic acid N-methylamide, glutarate N-methylamide, malonate N-methylamide, azelaic acid N-methylamide, succinate N-ethylamide, adipic acid N-ethylamide, glutarate N-ethylamide, malonate N-ethylamide, azelaic acid N-ethylamide, succinate N-butylamide,Examples include N-butylamide adipic acid, N-butylamide glutarate, N-butylamide malonate, N-octylamide adipic acid, and N-dodecylamide adipic acid.

[0050] Furthermore, component (c) may be a compound represented by the following formula (3). [ka] [In the formula, R1 represents a hydrogen atom or a methyl group, m represents an integer from 0 to 2, and either X1 or X2 is -(CH2)] n OCOR2 or (CH2) n COOR2, the other side represents a hydrogen atom, n is an integer from 0 to 2, R2 represents an alkyl or alkenyl group with 4 or more carbon atoms, Y1 and Y2 each independently represent one of the following: a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, a methoxy group, or a halogen atom, and r and p each independently represent an integer from 1 to 3.

[0051] Among the compounds represented by formula (3), when R1 is a hydrogen atom, a reversible thermochromic composition with a wider hysteresis width is obtained, which is preferable, and it is even more preferable when R1 is a hydrogen atom and m is 0.

[0052] Furthermore, among the compounds represented by formula (3), the compounds represented by the following formula (4) are more preferable. [ka] (In the formula, R represents an alkyl or alkenyl group having 8 or more carbon atoms, preferably an alkyl group having 10 to 24 carbon atoms, and more preferably an alkyl group having 12 to 22 carbon atoms.)

[0053] Examples of the compound represented by the formula (4) include 4-benzyloxyphenyl ethyl octanoate, 4-benzyloxyphenyl ethyl nonanoate, 4-benzyloxyphenyl ethyl decanoate, 4-benzyloxyphenyl ethyl undecanoate, 4-benzyloxyphenyl ethyl dodecanoate, 4-benzyloxyphenyl ethyl tridecanoate, 4-benzyloxyphenyl ethyl tetradecanoate, 4-benzyloxyphenyl ethyl pentadecanoate, 4-benzyloxyphenyl ethyl hexadecanoate, 4-benzyloxyphenyl ethyl heptadecanoate, 4-benzyloxyphenyl ethyl octadecanoate, and the like.

[0054] Furthermore, the component (c) may be a compound represented by the following formula (5).

Chemical formula

[0055] Examples of the compound represented by the formula (5) include 1,1-diphenylmethyl octanoate, 1,1-diphenylmethyl nonanoate, 1,1-diphenylmethyl decanoate, 1,1-diphenylmethyl undecanoate, 1,1-diphenylmethyl dodecanoate, 1,1-diphenylmethyl tridecanoate, 1,1-diphenylmethyl tetradecanoate, 1,1-diphenylmethyl pentadecanoate, 1,1-diphenylmethyl hexadecanoate, 1,1-diphenylmethyl heptadecanoate, 1,1-diphenylmethyl octadecanoate, and the like.

[0056] Furthermore, the component (c) may be a compound represented by the following formula (6).

Chemical formula

[0057] Examples of compounds represented by formula (6) include diesters of malonic acid and 2-[4-(4-chlorobenzyloxy)phenyl]ethanol, diesters of succinic acid and 2-(4-benzyloxyphenyl)ethanol, diesters of succinic acid and 2-[4-(3-methylbenzyloxy)phenyl]ethanol, diesters of glutaric acid and 2-(4-benzyloxyphenyl)ethanol, diesters of 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, diesters of suberic acid and 2-(4-benzyloxyphenyl)ethanol, and suberic acid and 2-[4-(3-methylbenzyloxy)phenyl]ethanol. Examples include diesters of rubenzyloxy)phenyl]ethanol, suberic acid and 2-[4-(4-chlorobenzyloxy)phenyl]ethanol, suberic acid and 2-[4-(2,4-dichlorobenzyloxy)phenyl]ethanol, azelaic acid and 2-(4-benzyloxyphenyl)ethanol, sebacic acid and 2-(4-benzyloxyphenyl)ethanol, 1,10-decanedicarboxylic acid and 2-(4-benzyloxyphenyl)ethanol, 1,18-octadecanedicarboxylic acid and 2-(4-benzyloxyphenyl)ethanol, and 1,18-octadecanedicarboxylic acid and 2-[4-(2-methylbenzyloxy)phenyl]ethanol.

[0058] Furthermore, component (c) may be the compound shown in formula (7) below. [ka] (In the formula, R represents an alkyl or alkenyl group having 1 to 21 carbon atoms, and n represents an integer from 1 to 3.)

[0059] Examples of compounds represented by formula (7) include: diesters of 1,3-bis(2-hydroxyethoxy)benzene and capric acid, diesters of 1,3-bis(2-hydroxyethoxy)benzene and undecanoic acid, diesters of 1,3-bis(2-hydroxyethoxy)benzene and lauric acid, diesters of 1,3-bis(2-hydroxyethoxy)benzene and myristic acid, diesters of 1,4-bis(hydroxymethoxy)benzene and butyric acid, diesters of 1,4-bis(hydroxymethoxy)benzene and isovaleric acid, and diesters of 1,4-bis(2-hydroxyethoxy)benzene and acetic acid. Examples include diesters of 1,4-bis(2-hydroxyethoxy)benzene with propionic acid, diesters of 1,4-bis(2-hydroxyethoxy)benzene with valeric acid, diesters of 1,4-bis(2-hydroxyethoxy)benzene with caproic acid, diesters of 1,4-bis(2-hydroxyethoxy)benzene with caprylic acid, diesters of 1,4-bis(2-hydroxyethoxy)benzene with capric acid, diesters of 1,4-bis(2-hydroxyethoxy)benzene with lauric acid, and diesters of 1,4-bis(2-hydroxyethoxy)benzene with myristic acid.

[0060] Furthermore, component (c) may be a compound represented by the following formula (8). [ka] (In the formula, X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom; m represents an integer from 1 to 3; and n represents an integer from 1 to 20.)

[0061] Examples of compounds represented by formula (8) include diesters of succinic acid and 2-phenoxyethanol, diesters of suberic acid and 2-phenoxyethanol, diesters of sebacic acid and 2-phenoxyethanol, diesters of 1,10-decanedicarboxylic acid and 2-phenoxyethanol, and diesters of 1,18-octadecanedicarboxylic acid and 2-phenoxyethanol.

[0062] Furthermore, component (c) may be a compound represented by the following formula (9). [ka] (In the formula, R represents any of the following: 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 represents any of the following: 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; and n represents 0 or 1.)

[0063] Examples of compounds represented by formula (9) include decyl phenylbenzoate, lauryl phenylbenzoate, myristyl phenylbenzoate, cyclohexylethyl phenylbenzoate, octyl 4-biphenylacetate, nonyl 4-biphenylacetate, decyl 4-biphenylacetate, lauryl 4-biphenylacetate, myristyl 4-biphenylacetate, tridecyl 4-biphenylacetate, pentadecyl 4-biphenylacetate, cetyl 4-biphenylacetate, cyclopentyl 4-biphenylacetate, cyclohexylmethyl 4-biphenylacetate, hexyl 4-biphenylacetate, and cyclohexylmethyl 4-biphenylacetate.

[0064] Furthermore, component (c) may be a compound represented by the following formula (10). [ka] (In the formula, R represents an alkyl group having 3 to 18 carbon atoms or an aliphatic acyl group having 3 to 18 carbon atoms; X represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 or 2 carbon atoms, or a halogen atom; Y represents a hydrogen atom or a methyl group; and Z represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 or 2 carbon atoms, or a halogen atom.) Examples of compounds represented by formula (10) include phenoxyethyl 4-butoxybenzoate, phenoxyethyl 4-pentyloxybenzoate, phenoxyethyl 4-tetradecyloxybenzoate, esters of phenoxyethyl 4-hydroxybenzoate and dodecanoic acid, and dodecyl ether of phenoxyethyl vanillate.

[0065] Furthermore, component (c) may be a compound represented by the following formula (11). [ka] (In the formula, R represents any of the following: 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; X represents any of the following: a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom; Y represents any of the following: a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom; and n represents 0 or 1.)

[0066] Examples of compounds represented by formula (11) include benzoic acid esters of octyl 4-hydroxybenzoate, decyl 4-hydroxybenzoate, 4-methoxybenzoic acid ester of heptyl 4-hydroxybenzoate, 2-methoxybenzoic acid ester of dodecyl 4-hydroxybenzoate, and cyclohexylmethyl 4-hydroxybenzoate.

[0067] Furthermore, component (c) may be a compound represented by the following formula (12). [ka] (In the formula, R represents any of the following: 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 represents any of the following: a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a halogen atom; and Y represents any of the following: a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, an ethoxy group, or a halogen atom.)

[0068] Examples of compounds represented by formula (12) include phenoxyethyl ether of nonyl 4-hydroxybenzoate, phenoxyethyl ether of decyl 4-hydroxybenzoate, phenoxyethyl ether of undecyl 4-hydroxybenzoate, and phenoxyethyl ether of dodecyl vanillate.

[0069] Furthermore, component (c) may be a compound represented by the following formula (13). [ka] (In the formula, R represents a cycloalkyl group having 3 to 8 carbon atoms or a cycloalkylalkyl group having 4 to 9 carbon atoms, and n represents an integer from 1 to 3.)

[0070] Examples of compounds represented by formula (13) include diesters of 1,3-bis(2-hydroxyethoxy)benzene and cyclohexanecarboxylic acid, diesters of 1,4-bis(2-hydroxyethoxy)benzene and cyclohexanepropionic acid, and diesters of 1,3-bis(2-hydroxyethoxy)benzene and cyclohexanepropionic acid.

[0071] Furthermore, component (c) may be a compound represented by the following formula (14). [ka] (In the formula, R represents one of the alkyl groups having 3 to 17 carbon atoms, cycloalkyl groups having 3 to 8 carbon atoms, or cycloalkylalkyl groups having 5 to 8 carbon atoms; X represents one of the hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a methoxy group, an ethoxy group, or a halogen atom; and n represents an integer from 1 to 3.)

[0072] Examples of compounds 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, diesters of 4-phenylphenol triethylene glycol ether and 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, and diesters of 4-phenylphenol ethylene glycol ether and myristic acid.

[0073] Furthermore, it is also possible to use reversible thermochromic compositions that change color upon heating and disappear upon cooling, using specific alkoxyphenol compounds having a linear or side-chain alkyl group with 3 to 18 carbon atoms as electron-accepting compounds (Japanese Patent Publication No. 11-129623, Japanese Patent Publication No. 11-5973), specific hydroxybenzoic acid esters (Japanese Patent Publication No. 2001-105732), or gallic acid esters, etc. (Japanese Patent Publication No. 51-44706, Japanese Patent Publication No. 2003-253149) as heat-color-developing compounds (see Figure 3).

[0074] The above-mentioned reversible thermochromic composition is a compatible mixture comprising the above-mentioned components (a), (b), and (c) as essential components. The proportion of each component depends on the concentration, discoloration temperature, discoloration form, and type of each component, but generally, the component ratios that yield the desired properties are in the range of 1 part of component (a), 0.1 to 100 parts of component (b), preferably 0.1 to 50 parts, more preferably 0.5 to 20 parts, and 5 to 200 parts of component (c), preferably 5 to 100 parts, more preferably 10 to 100 parts (all proportions are in parts by mass).

[0075] Furthermore, various light stabilizers may be added to the reversible thermochromic composition as needed. Light stabilizers are included to prevent photodegradation of the reversible thermochromic composition consisting of components (a), (b), and (c), and are blended in a ratio of 0.3 to 24% by mass, preferably 0.3 to 16% by mass, per 1% by mass of component (a). Among the light stabilizers, ultraviolet absorbers effectively cut ultraviolet rays contained in sunlight, etc., and prevent photodegradation caused by the excitation state due to the photoreaction of component (a). In addition, antioxidants, singlet oxygen quenchers, superoxide anion quenchers, ozone quenchers, etc., suppress oxidation reactions caused by light. Light stabilizers may be used alone or in combination of two or more types.

[0076] Microencapsulation can be appropriately selected from conventionally known manufacturing methods such as isocyanate-based interfacial polymerization, melamine-formaldehyde-based in situ polymerization, liquid curing coating, phase separation from aqueous solutions, phase separation from organic solvents, melt-dispersion cooling, air suspension coating, and spray drying, depending on the application. Furthermore, depending on the purpose, a secondary resin coating can be applied to the surface of the microcapsules to provide durability or modify the surface properties for practical use.

[0077] Examples of materials for microcapsules include organic resins, such as epoxy resins, urea resins, urethane resins, and isocyanate resins.

[0078] By applying a secondary resin coating to the surface of the microcapsules according to the purpose, durability can be enhanced, and the surface properties can be modified to make them suitable for practical use.

[0079] The mass ratio of the reversible thermochromic composition to the microcapsule (i.e., the microcapsule wall portion that does not contain 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, and more preferably 6 parts by mass or less, of the reversible thermochromic composition per 1 part by mass of the microcapsule. By using 7 parts by mass or less of the reversible thermochromic composition per 1 part by mass of the microcapsule, it becomes easy to achieve an appropriate wall thickness without making the microcapsule wall too thin, thereby making it easy to improve the heat resistance and pressure resistance of the microcapsule pigment. Furthermore, by using 1 part by mass or more of the reversible thermochromic composition per 1 part by mass of the microcapsule, it becomes easy to improve the color density and vividness when the microcapsule pigment develops color.

[0080] For example, the average particle size of the microcapsules satisfies practical requirements when it is in the range of 0.01 to 50 μm, preferably 0.1 to 30 μm, and more preferably 0.5 to 20 μm. In this invention, the average particle diameter is the average particle diameter (median diameter) based on volume. The optimal method for measuring the average particle size is to use a laser diffraction / scattering particle size distribution analyzer that has been calibrated using a direct measurement method, such as the LA-300 laser diffraction particle size distribution analyzer (product name, manufactured by Horiba, Ltd.).

[0081] As for direct measurement methods used for calibration, (i) An image analysis method that measures the area (2D) of individual particles from images taken with a microscope to determine the equivalent diameter. (ii) Examples include the Coulter method (electrical detection band method), which uses a Coulter counter to pass a constant current through a tiny hole (aperture) in the detector and measures the equivalent diameter from the change in impedance that occurs when a particle passes through the hole. The calibration of the laser measurement method is performed based on the values ​​obtained by these methods.

[0082] Average particle diameter can be measured using image analysis methods, for example, by using the image analysis particle size distribution measurement software "MacView" (product name, manufactured by Mountec Co., Ltd.) to determine the particle area, calculating the projected area circle equivalent diameter (Heywood diameter) from the area of ​​the particle area, and measuring it as the average particle diameter of particles equivalent to an equivolute sphere based on that value. Furthermore, the Coulter method for measuring the average particle size is applicable when the particle size of all or most of the particles exceeds 0.2 μm, and can be measured using, for example, the Beckman Coulter Multisizer 4e particle size distribution analyzer.

[0083] By encapsulating a reversible thermochromic composition in microcapsules, a chemically and physically stable pigment can be constructed. Furthermore, the reversible thermochromic composition maintains the same composition and exerts the same effects under various usage conditions.

[0084] The content of microcapsule pigments is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, and even more preferably 10 to 25% by mass, based on the total mass of the ink composition. When the content is within the above range, it is possible to form highly colored lines and it becomes easier to suppress drying up.

[0085] (Shear viscosity reducing agent) The ink composition contains polysaccharides as shear-thickening agents. Specific examples of polysaccharides include xanthan gum, gellan gum, succinoglycan, guar gum, locust bean gum, λ-carrageenan, cellulose derivatives, zeta citrate gum, dieutan gum, glucomannan, macrophomopsis gum, and gelling carbohydrates extracted from seaweed such as agar and carrageenan. These contribute to the stable dispersion of microcapsule pigments in the ink's static state and to good ink ejection during writing.

[0086] Among the polysaccharides mentioned above, succinoglycans and xanthan gum are preferred. These can increase the composition viscosity at rest and decrease the composition viscosity during writing compared to other polysaccharides, making it easier to achieve both stable dispersion of microcapsule pigments and good ink discharge during writing. Furthermore, the viscosity of the ink can be adjusted with relatively small amounts of additives, which helps to suppress the drying up of the pen tip due to the film of the shear viscosity reducing agent when moisture in the ink evaporates from the pen tip.

[0087] Succinoglycans are natural products formed by the polymerization of glucose, galactose, succinic acid, and pyruvic acid. While their molecular weight is difficult to determine precisely, it is generally believed that their mass-average molecular weight is around 1 million. Various commercially available succinoglycans exist; for example, Leozan (trade name, manufactured by Sansho Co., Ltd.) is one such example.

[0088] To obtain sufficient effects, the content of the polysaccharide is preferably 0.01 to 1.0% by mass, and more preferably 0.1 to 0.5% by mass, relative to the total mass of the ink composition.

[0089] The ink composition may contain dextrin. Preferably, the dextrin is a sugar mixture containing, for example, a starch syrup of 8 or more sugars and / or its reduced form. The sugar mixture preferably contains 30% by mass or more of starch syrup of 8 or more sugars, more preferably 50% by mass or more, and even more preferably 70% by mass or more. This further improves resistance to drying up and provides the ability to prevent dripping from the ballpoint pen tip.

[0090] As sugars with 8 or more saccharides, starch syrups obtained by enzymatic hydrolysis of starch, etc., and reduced starch syrups obtained by reducing the terminal groups of said starch syrups can be used. Furthermore, since sugars with various degrees of polymerization are produced when starch is decomposed, it is technically difficult to completely isolate only sugars with 8 or more saccharides, and this also increases manufacturing costs. Therefore, a sugar mixture containing sugars with 7 or fewer saccharides, and containing 30% or more by mass of the aforementioned sugars with 8 or more saccharides, can be used, thereby sufficiently obtaining the aforementioned performance in the ink and providing resistance to drying up and preventing sagging. Examples of sugar mixtures include products obtained by decomposing starch (for example, by enzymatic hydrolysis).

[0091] The dextrin content in the ink composition is preferably 0.5 to 10% by mass. If it is 0.5% by mass or more, an improvement in drying resistance can be effectively obtained, and if it is 10% by mass or less, problems such as an increase in the viscosity of the ink composition due to the addition, causing splashing or blotting, or hindering followability can be easily avoided, and furthermore, it does not adversely affect good drying resistance. The dextrin content is more preferably 1 to 8% by mass.

[0092] The ink composition may contain known components as long as they do not impair the effects of the present invention. For example, it may contain polyvinylpyrrolidone, polyvinyl alcohol, etc., as needed. Furthermore, by adding oligomers of N-vinyl-2-pyrrolidone, N-vinyl-2-piperidone, N-vinyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, ε-caprolactam, oligomers of N-vinyl-ε-caprolactam, etc., the resistance to drying up can be improved and the function in the retractable form can be further enhanced.

[0093] Furthermore, various additives may be included as needed. Examples of additives include higher fatty acids such as oleic acid, nonionic surfactants having long-chain alkyl groups, polyether-modified silicone oils, thiophosphite triesters such as tri(alkoxycarbonylmethyl) thiophosphite and tri(alkoxycarbonylethyl) thiophosphite, monophosphate esters of polyoxyethylene alkyl ethers or polyoxyethylene alkylaryl ethers, diphosphate esters of polyoxyethylene alkyl ethers or polyoxyethylene alkylaryl ethers, or lubricants such as metal salts, ammonium salts, amine salts, and alkanolamine salts thereof.

[0094] Furthermore, pH adjusters such as inorganic salts like sodium carbonate, sodium phosphate, and sodium acetate, and organic basic compounds such as water-soluble amine compounds; rust inhibitors such as benzotriazole, tolyltriazole, dicyclohexylammonium nitride, diisopropylammonium nitride, and saponins; carbolic acid, sodium salt of 1,2-benzthiazolin 3-one, sodium benzoate, sodium dehydroacetate, potassium sorbate, propyl parahydroxybenzoate, and 2,3,5,6-tetrachloro-4-(methyl) It may also contain preservatives or fungicides such as sulfonyl pyridine, ascorbic acid, ascorbic acid derivatives, natural or synthetic polyphenols, N-vinylpyrrolidone oligomers, kojic acid, hydroxylamines, oxime derivatives, α-glucosylrutin, phosphonates, phosphinates, sulfites, sulfoxylates, dithionites, thiosulfates, thiourea dioxide, formamidine sulfinate, glutathione, oxygen absorbers such as reaction products of n-butyraldehyde and aniline, defoamers, dispersants, etc.

[0095] The ink composition contains water, but may also contain a water-soluble organic solvent. If a water-soluble organic solvent is included, it is preferable to include it in an amount that does not cause various problems such as poor ink followability due to increased ink viscosity, poor drying of the ink, or bleeding of the ink, or the water-soluble organic solvent may not be included at all. Examples of water-soluble organic solvents include glycol-based water-soluble organic solvents, specifically 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 monoethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, 1,3-butylene glycol, glycerin, furfuryl alcohol, etc.

[0096] The ink composition has a shear rate of 3.84 sec. -1 The viscosity measured is 300-1500 mPa·s, and the shear rate is 384 sec. -1 The viscosity measured is preferably 10 to 100 mPa·s. A more preferred viscosity for the ink composition is a shear rate of 3.84 sec. -1 The pressure is 500-1000 mPa·s, and the shear rate is 384 sec. -1 The viscosity is 20-50 mPa·s. When the viscosity of the ink composition is within this range, the sedimentation and aggregation of microcapsule pigments in the ink composition in a static state are sufficiently suppressed, and the ink ejection from the ballpoint pen tip during writing tends to be good. The viscosity is measured at 20 °C for the ink composition. For the measuring instrument, for example, the rheometer "DHR-2" manufactured by TA Instruments can be used.

[0097] Further, for the aqueous ink composition, the shear thinning index n represented by the following general formula (15) measured at 20 °C is preferably from 0.4 to 0.9, more preferably from 0.5 to 0.8. 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 . Thereby, while sedimentation, aggregation, etc. of the microcapsule pigment in the ink composition in the stationary state are sufficiently suppressed, the ink at the ballpoint pen tip is discharged without accumulating in the gap between the ball and the ball holding part during writing, so that it becomes easy to form a clear handwriting.

[0098] The measurement of the shear thinning index n can be performed, for example, using the rheometer "DHR-2" manufactured by TA Instruments, at 3.84 sec -1 , and 384 sec -1 of the shear rate, and applying the shear stress (shear stress) obtained at each of these shear rates to the above general formula (15) to obtain n.

[0099] The surface tension of the ink composition is preferably 25 to 45 mN / m in a 20 °C environment. When the surface tension is within the above numerical range, the wettability of the ink composition is improved, the handwriting formation property of the overwritten handwriting during overwriting is improved, bleeding of the writing line and penetration through the paper are suppressed, and the writing property can be further improved. Considering the overwriting performance and writing property more, the surface tension of the aqueous ink composition is more preferably 25 to 35 mN / m, and even more preferably 25 to 30 mN / m. The surface tension is measured by the vertical plate method using a platinum plate under the condition of 20 °C. As the measuring instrument, for example, the surface tensiometer (trade name: DY-300) manufactured by Kyowa Interface Science Co., Ltd. can be used.

[0100] The ink composition is prepared by adding microcapsule pigments and, if necessary, various additives to an aqueous medium containing water and a water-soluble organic solvent, stirring, and then adding a dispersion of a shear viscosity reducing agent in a separately prepared solvent, or by directly adding the shear viscosity reducing agent, and stirring.

[0101] The ink composition can be used as ink for writing instruments such as marking pens and ballpoint pens.

[0102] The ink composition can be applied to a writing instrument comprising a barrel for containing the ink composition and a pen body for dispensing the ink composition contained within the barrel. The ink composition can be contained within the barrel, for example, by being embedded in an ink-absorbing body made of a fiber bundle, or by being directly contained in an ink-containing tube. The pen body can be, for example, a marking pen body or a ballpoint pen body.

[0103] The writing instrument may be a marking pen. The structure and shape of the marking pen itself are not particularly limited. Examples of marking pens include a structure in which an ink-absorbing body made of a fiber bundle is built into the barrel, and a marking pen body made of a fiber processed body with capillary gaps is attached to the barrel directly or via an intermediate member, connecting the ink-absorbing body and the marking pen body, and the ink composition is impregnated into the ink-absorbing body; and a structure in which the marking pen body and an ink storage tube are arranged via a valve body that is opened by pressing the marking pen body, and the ink is directly stored in the ink storage tube.

[0104] The marking pen body is a porous material with interconnected pores selected from conventionally used materials such as resin-processed fibers, fused heat-meltable fibers, and felt, with a porosity generally ranging from 30% to 70%, or an extruded synthetic resin body having multiple ink outlets extending in the axial direction. One end is processed into a shape such as a bullet shape, rectangle, or chisel shape according to the purpose for practical use. The ink-absorbing body is made of crimped fibers bundled in the longitudinal direction, and is contained within a covering such as a plastic cylinder or film, with the porosity adjusted to a range of approximately 40% to 90%. The valve body can be a conventional pumping type, but one set to a spring pressure that can be released by pen pressure is preferable.

[0105] The writing instrument may be a ballpoint pen. The structure and shape of the ballpoint pen itself are not particularly limited. An example of a ballpoint pen is one having an ink reservoir filled with an ink composition inside the barrel, the ink reservoir communicating with a ballpoint pen tip with a ball attached to its end, and a backflow prevention stopper tightly fitted to the end face of the ink composition contained in the ink reservoir. A ballpoint pen constructed using the above-described ink composition has good ink discharge from the writing tip and excellent handwriting formation.

[0106] Examples of ballpoint pen tips include those in which a ball is held in a ball-holding portion formed by pressing the tip of a metal pipe inward from the outer surface; those in which a ball is held in a ball-holding portion formed by cutting a metal material with a drill or the like; those in which a resin ball seat is provided inside a metal or plastic tip; and those in which the ball held in the ballpoint pen tip is biased forward by a spring. The ball can be made of cemented carbide, stainless steel, ruby, ceramic, resin, rubber, etc., and has a diameter of, for example, 0.3 mm to 2.0 mm, preferably 0.3 mm to 1.5 mm, and more preferably 0.3 mm to 1.0 mm.

[0107] The ink container tube for holding the ink composition may be a molded body made of a thermoplastic resin such as polyethylene, polypropylene, polyethylene terephthalate, or nylon, or a metal tubular body. The tip may be directly connected to the ink container tube, or it may be connected to the ink container tube and the tip via a connecting member (tip holder).

[0108] A ballpoint pen may have an ink reservoir tube in the form of a ballpoint pen refill, with the refill housed inside a barrel made of resin, metal, or it may have a barrel with a ballpoint pen body attached to the tip that serves as the ink reservoir, with ink directly filled into the barrel.

[0109] When the ink reservoir is in the form of a ballpoint pen refill, the ballpoint pen refill comprises an ink reservoir that contains an ink composition, and a ballpoint pen body that is attached to the ink reservoir either directly or via a connecting member and rotatably holds a ball.

[0110] Furthermore, when applying an ink composition to a retractable ballpoint pen, the structure and shape of the retractable ballpoint pen are not particularly limited. Any structure in which the writing tip provided on the ballpoint pen refill is housed inside the barrel while exposed to the outside air, and the writing tip protrudes from the barrel opening by the operation of the retractable mechanism, can be used. Examples of operating methods for the retractable mechanism include a knock type, a twist type, and a slide type. A knock type has a knock part at the rear end or side of the barrel, and the writing tip is extended and retracted from the front end opening of the barrel by pressing the knock part, or by pressing a clip part provided on the barrel. A twist type has a rotating part at the rear of the barrel, and the writing tip is extended and retracted from the front end opening of the barrel by rotating the rotating part. A sliding type may have a sliding part on the side of the barrel, and by operating the slide, the writing tip can be extended and retracted from the opening at the front of the barrel. Alternatively, a clip part provided on the barrel can be slid to extend and retract the writing tip from the opening at the front of the barrel. A retractable ballpoint pen may be a composite type that houses multiple ballpoint pen refills inside the barrel, and the writing tip of any of the ballpoint pen refills extends and retracts from the opening at the front of the barrel by operating the retractable mechanism.

[0111] An ink backflow prevention body is filled at the rear end of the ink composition contained in the ink storage tube. The ink backflow prevention body consists of a non-volatile liquid or a low-volatility liquid. Specifically, examples include 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, etc., and one of these can be used alone or two or more in combination. It is preferable to add a thickening agent to at least one of the non-volatile liquid and the low-volatility liquid to increase its viscosity to a suitable level. Examples of thickening agents include clay-based thickening agents such as silica with a hydrophobic surface treatment, fine silica particles with a methylated surface treatment, aluminum silicate, swellable mica, hydrophobic treated bentonite, and montmorillonite; fatty acid metal soaps such as magnesium stearate, calcium stearate, aluminum stearate, and zinc stearate; dextrin-based compounds such as triphenzylidene sorbitol, fatty acid amides, amide-modified polyethylene wax, hydrogenated castor oil, and fatty acid dextrin; and cellulose-based compounds. Furthermore, a liquid ink backflow preventative and a solid ink backflow preventative can be used in combination.

[0112] The form of the marking pen and ballpoint pen is not limited to those described above; they may also be double-ended writing instruments that have pen bodies of different shapes or pen bodies that dispense ink compositions of different colors.

[0113] The writing produced by writing on a surface using a writing instrument containing a reversible thermochromic aqueous ink composition can be discolored by a heating or cooling device. Examples of heating devices include electrically heated discoloring devices equipped with resistance heating elements, heated discoloring devices filled with hot water, etc., and the use of a hair dryer. Preferably, a friction member is used as a means of discoloration by a simple method. That is, the writing instrument may further include a friction member.

[0114] Suitable friction materials include elastic materials such as plastic foams, which are highly elastic and can generate appropriate friction and frictional heat when rubbed. Although it is also possible to rub the ink marks with an eraser, eraser residue is generated during friction, so the aforementioned friction materials that generate almost no residue are preferred. Suitable materials for the friction material include silicone resin, SEBS resin (styrene-ethylene-butadiene-styrene block copolymer), polyester resin, and α-olefin copolymer.

[0115] The friction element can be a separate component (friction body) of any shape from the writing instrument, and it can be combined with the writing instrument to form a writing instrument set. However, attaching the friction element to the writing instrument improves portability. In the case of writing instruments equipped with a cap, the location where the friction member is provided is not particularly limited, but for example, the cap itself may be formed from the friction member, the barrel itself may be formed from the friction member, the clip itself may be formed from the friction member if a clip is provided, or the friction member may be provided at the tip (top) of the cap or the rear end of the barrel (the part where the writing tip is not provided). In the case of retractable writing instruments, there are no particular limitations on where the friction element can be provided. For example, the barrel itself can be formed from the friction element, or if a clip is provided, the clip itself can be formed from the friction element, or the friction element can be provided near the barrel opening, at the rear end of the barrel (the part without the writing tip), or at the knock mechanism.

[0116] Cooling devices include Peltier elements for thermal color changers, thermal color changers filled with refrigerants such as cold water or ice chips, and the use of refrigerators and freezers.

[0117] A ballpoint pen filled with the ink composition according to the present invention can write on synthetic paper and water-resistant paper in addition to conventionally used paper. The writing produced on synthetic paper and water-resistant paper using the ballpoint pen is highly dense and free from writing defects such as skipped lines.

[0118] Synthetic paper and water-resistant paper are different from conventional paper made primarily from wood pulp, yet they possess similar appearance and physical properties to conventional paper. Compared to conventional paper, synthetic paper and water-resistant paper have superior durability, tear resistance, water resistance, chemical resistance, heat resistance, and oil resistance. The synthetic paper may have a structure comprising a base layer and a surface layer placed on the base layer. Here, the base layer is formed from, for example, polyethylene, polypropylene, high-density polyethylene, polyester, etc. The surface layer is formed from, for example, calcium carbonate, which has the effect of giving the synthetic paper a bright finish, high opacity, and a smooth texture. The aforementioned water-resistant paper is obtained by internally adding an appropriate amount of a water-resistant agent, such as a modified rosin emulsion, to a water-resistant base paper, and then surface-coating it with a water-resistant resin, such as synthetic rubber or acrylic resin.

[0119] Examples of synthetic papers include Polyart®, Appvion Appleton Digital®, Parax® Stone Paper, RockStock® Stone Paper, Nekoosa® XM, Nekoosa® OM, HopSynDLgrade®, and Yupo® FPG80.

[0120] The writing formed on synthetic paper or waterproof paper using the ballpoint pen according to the present invention can be erased by heat from a heating device such as the friction member, and can also be removed from the synthetic paper or waterproof paper by wiping it with a medium impregnated with a liquid such as water or alcohol. This allows the synthetic paper or waterproof paper to be returned to a blank state (initial state), making it possible to write on it again with the ballpoint pen. In other words, the process of removing the writing using the liquid-impregnated medium after writing on the synthetic paper or waterproof paper can be repeated, making it possible to reuse the synthetic paper or waterproof paper.

[0121] Examples of the aforementioned medium include cloth, sponge, paper towel, tissue paper, and the like.

[0122] The contents written on synthetic paper or waterproof paper with the 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 the liquid, and may be saved in a predetermined format so that OCR (optical character recognition) can be performed on the saved contents. Examples of scanning methods include using a digital scanner or taking a digital photograph and performing digital signal processing on the digital photograph. After scanning the contents and saving them in a suitable location, the synthetic paper or waterproof paper can be returned to its initial state and reused by erasing by heat or removal with a medium impregnated with the liquid.

[0123] Synthetic paper or water-resistant paper may be part of a bound notebook, or it may be separate and not bound. An example of a notebook with synthetic paper pages is the ROCKET BOOK® manufactured by ROCKET INNOVATIONS, INK.

[0124] A writing instrument set (package kit) can also be obtained by combining a notebook having pages made of synthetic paper or water-resistant paper with the ballpoint pen according to the present invention. The writing instrument set may also include a medium such as cloth. [Examples]

[0125] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" are based on mass. In this embodiment, the average particle size of the microcapsule pigment was measured using the volume-based average particle size (median diameter) of the laser diffraction / scattering particle size distribution analyzer (device name: LA-300, manufactured by Horiba, Ltd.) which was calibrated by the Coulter method (electrical detection band method).

[0126] Preparation of microcapsule pigment (1) Microcapsule pigment 1 was prepared by encapsulating a reversible thermochromic composition a, which has color memory properties, in microcapsules. The composition a consists of 1.0 part of spiro[5H-(1)benzopyrano[2,3-d]pyrimidine-5,1'(3'H)isobenzofuran]-3'-one,2-(diethylamino)-8-(diethylamino)-4-methyl as an electron-donating color-developing organic compound, 3.0 parts of 1,1-bis(4-hydroxyphenyl)-2-ethylhexane and 5.0 parts of 2,2-bis(4'-hydroxyphenyl)-hexafluoropropane as electron-accepting compounds, and 50.0 parts of 4-benzyloxyphenylethyl caprate as a reaction medium. The average particle size of microcapsule pigment 1 was 2.0 μm, the complete decolorization temperature (t4) was 53°C, and the complete color development temperature (t1) was -20°C. The pigment changed color from pink to colorless with temperature changes.

[0127] Preparation of microcapsule pigments (2) Microcapsule pigment 2 was prepared by encapsulating a reversible thermochromic composition b, which has color memory properties, in microcapsules. Composition b consists of an electron-donating chromogenic organic compound, 1.0 part of 3,6-bis(diphenylamino)fluorane as a component, 3.0 parts of 1,1-bis(4-hydroxyphenyl)-2-ethylhexane and 5.0 parts of 2,2-bis(4'-hydroxyphenyl)-hexafluoropropane as electron-accepting compounds, and 50.0 parts of 4-benzyloxyphenylethyl caprate as a reaction medium. The average particle size of microcapsule pigment 2 was 1.8 μm, the complete decolorization temperature (t4) was 55°C, and the complete color development temperature (t1) was -20°C. The pigment changed color from blue to colorless with temperature changes.

[0128] Preparation of ink composition Ink compositions No. 1 to No. 15 having the compositions shown in Table 1 below were prepared. The numerical values ​​of the compositions in the table represent mass %, and "-" indicates that no additive was added. Compositions No. 1 to No. 8 and No. 12 to No. 15 are examples, and No. 9 to No. 11 are comparative examples.

[0129] The viscosity of the ink composition was measured at 20°C using a rheometer "DHR-2" manufactured by TA Instruments.

[0130] The surface tension of the ink composition was measured using a surface tensimeter (product name: DY-300) manufactured by Kyowa Interface Science Co., Ltd., at 20°C, using the vertical plate method with a platinum plate.

[0131] [Table 1]

[0132] The details of each component in the table are explained below. (1) Xanthan gum (product name: Kelzan, manufactured by Sankyo Co., Ltd.) (2) Succinoglycan (product name: Leozan, manufactured by Sansho Co., Ltd.) (3) Product name: Sandec 70 (contains 70% by mass or more of starch syrups of 8 sugars or more and / or their reduced products), manufactured by Sanwa Starch Industry Co., Ltd. (4) Polyoxyethylene styrylphenyl phosphate (product name: Prysurf AL, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) (5) General formula (1): A1: methyl group, A2: methyl group, A3: lauryl group (product name: NIKKOL AM-301, active ingredient: 35% by mass, manufactured by Nikko Chemicals Co., Ltd.) (6) General formula (1): A1: methyl group, A2: methyl group, A3: stearyl group (product name: Anchitol 86B, active ingredient: 26% by mass, manufactured by Kao Corporation) (7) General formula (1): A1: methyl group, A2: methyl group, A3: myristyl group (product name: Rikabion A-200, active ingredient: 29-32% by mass, manufactured by Shin Nippon Rika Co., Ltd.) (8) General formula (1): A1: methyl group, A2: methyl group, A3: general formula (2) [A4: propyl group, A5: undecyl group] (Product 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 Co., Ltd.)

[0133] Making ballpoint pen refills Each of the obtained ink compositions was filled into an ink reservoir tube made of polypropylene resin, which had a ballpoint pen tip at its end that rotatably held a cemented carbide ball with an outer diameter of 0.5 mm. The rear end was filled with an ink backflow prevention body made of a viscous liquid. Then, a tail plug was fitted to the rear of the pipe to obtain each ballpoint pen refill. Furthermore, each of the ink compositions No. 1 to No. 15 was filled into a stainless steel ink reservoir tube equipped with the ballpoint pen tip at its end, and an ink backflow prevention body was filled into the rear end. Then, a tail plug was fitted to the rear of the pipe to obtain a ballpoint pen refill equipped with a metal ink reservoir tube.

[0134] Making a ballpoint pen The obtained ballpoint pen refill was installed into the casing of a ballpoint pen (product name: Frixion Ball 05, manufactured by Pilot Corporation). The following tests were conducted using the resulting ballpoint pen. The results are shown in the table below. Furthermore, the test paper used for writing was writing paper A, which conforms to the old JIS P3201 standard.

[0135] (Evaluation of overwriting capability) A 1cm square was colored onto the test paper using the aforementioned ballpoint pen. The square was then rubbed with the abrasive attached to the end of the ballpoint pen to remove the color. After removing the color, writing was done on the square using the same ballpoint pen used to color it (writing character: #), and the handwriting was observed visually. ○: No blurring or breaks are observed in the characters. Or, slight blurring or breaks are observed in the characters, but it does not pose a practical problem. ×: The characters show clear blurring and breaks. This presents a practical problem.

[0136] (Evaluation of resistance to drying up) A ballpoint pen was placed horizontally with the tip exposed and stored in a 50°C, 30% RH environment for 30 days. After that, at room temperature, 12 spiral circles were continuously written on a test paper in a single line, and the handwriting was observed visually. ○...It can produce smooth, uninterrupted handwriting from the start to the end of writing. Alternatively, slight smudging or breaks were observed in the handwriting immediately after the start of writing. However, these were not visible in the handwriting at the end of the writing session. ×...Unable to write.

[0137] (Evaluation of continuous writing ability) A ballpoint pen was attached to an automatic writing test machine, and spiral circles were continuously written on test paper until all the ink was consumed. The handwriting was then visually observed. ○...A clear handwriting is formed from the start to the end of writing. ×...The pen became unusable before the ink was completely consumed.

[0138] [Table 2] Equivalent evaluation results were obtained from ballpoint pen refills with polypropylene resin ink reservoirs and ballpoint pen refills with stainless steel ink reservoirs, both of which were filled with the same type of ink. Furthermore, in the evaluation of dry-up resistance, for No. 1 to No. 8 and No. 15, after 30 days of storage in a 50°C 30%RH environment, writing was possible without any smudging or interruption from the start to the end of writing. For No. 12 to 14, although some smudging or interruption was observed in the writing immediately after the start of writing, none was observed in the writing at the end of writing. [Explanation of Symbols]

[0139] t1 Full color temperature t2 Color development start temperature t3 Discoloration start temperature t4 Complete color erasure temperature T1 Complete color fading temperature T2 Decolorization start temperature T3 Color development start temperature T4 Full Color Temperature

Claims

1. A reversibly thermochromic aqueous ink composition for a writing instrument, comprising: a reversibly thermochromic microcapsule pigment encapsulating a reversibly thermochromic composition comprising (a) an electron-donating organic color-forming compound, (b) an electron-accepting compound, and (c) a reaction medium that determines the temperature at which the color-forming reactions of (a) and (b) occur; a betaine-type amphoteric surfactant represented by the following general formula (1); a shear-thinning agent; and water, wherein the shear-thinning agent is a polysaccharide. 【Chemistry 1】 In the formula, A １ , A ２ are independently an alkyl group having 1 to 3 carbon atoms; ３ is an alkyl group having 5 to 24 carbon atoms or a functional group represented by the following general formula (2). 【Chemistry 2】 In the formula, A ４ is an alkyl group having 1 to 5 carbon atoms. ５ is an alkyl group having 1 to 16 carbon atoms.

2. The ink composition according to claim 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. 2. The ink composition according to claim 1, wherein the content of the betaine-type amphoteric surfactant is 0.20 to 3.0% based on the total mass of the ink composition relative to the content of the reversible thermochromic microencapsulated pigment.

4. 2. The ink composition of claim 1, wherein the polysaccharide is xanthan gum and / or succinoglycan.

5. A writing instrument containing the ink composition according to any one of claims 1 to 4.

6. 6. The writing instrument of claim 5 which is a ballpoint pen.

7. 7. The ballpoint pen according to claim 6, further comprising a friction member.

8. A ballpoint pen refill containing the ink composition according to any one of claims 1 to 4.

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