Aqueous ink composition for reversible thermochromic inkjet printer, and ink jet printer and ink cartridge using the same

Abstract

To provide a reversible thermochromic aqueous ink composition for an inkjet printer which enables of formation of a printed image having high resolution and rich color development property, and an inkjet printer and an ink cartridge including the same.SOLUTION: An aqueous ink composition for a reversible thermochromic inkjet printer contains a reversible thermochromic microcapsule pigment containing a micro capsule made by including a reversible thermochromic composition with a film, water, and a polyhydric alcohol-based organic solvent. A volume-based average particle diameter (X) of the microcapsule is 0.1 to 2.0 μm, a cross section of the frozen microcapsule pigment is observed by a transmission electron microscope, and as for all the capsules in an observation visual field, and average cut cross section film thickness (Y) determined by expression: cut cross section film thickness=(cross section outer peripheral diameter-cross section inner peripheral diameter) / 2 is 0.02 to 0.4 μm.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a reversible thermochromic aqueous ink composition for inkjet printers, and also to an inkjet printer and an ink cartridge using the ink composition. [Background technology]

[0002] Ink compositions for inkjet printers that use thermochromic microcapsule pigments encapsulating transition element compounds or thermochromic compositions have been proposed (see, for example, Patent Documents 1 to 3). However, it has not been easy to obtain high-resolution, highly color-developable printed images, as well as to reduce nozzle clogging and enable stable image formation over a long period of time.

[0003] For example, when an ink composition containing microcapsules with a small particle size is used, clogging of the microcapsules in the printer's ejection section (nozzle) is suppressed, and good ink ejection is maintained, but the color development of the microcapsule pigment and the printed image is likely to decrease. Conversely, when a microcapsule pigment with a large particle size is used, the color development of the microcapsule pigment is improved, but the microcapsule pigment is likely to clog the nozzle, and the ink ejection properties and the definition of the printed image tend to decrease.

[0004] In addition, the use of humectants in inks to prevent nozzle clogging due to ink drying has also been considered. However, when humectants are used in ink compositions, the thermochromic composition in the microcapsules can leach into the ink solvent during storage, causing discoloration of the microcapsule pigment. Discoloration of microcapsule pigments can be prevented by thickening the microcapsule coating. However, simply increasing the coating thickness can lead to other problems. That is, if the coating is increased while maintaining the particle size, the amount of thermochromic composition encapsulated in the microcapsules decreases, resulting in a decrease in the color development of the microcapsule pigment. Conversely, if the coating is increased while maintaining the amount of thermochromic composition encapsulated, the particle size increases, resulting in a decrease in ink jetting performance and the resolution of printed images. For this reason, it has been difficult to simultaneously achieve shelf life, color development and resolution of printed images, and stable ink jetting performance in inkjet inks using microcapsule pigments encapsulating thermochromic compositions. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2009-227956 [Patent Document 2] International Publication No. 2018 / 190229 [Patent Document 3] International Publication No. 2018 / 190230 Summary of the Invention [Problem to be solved by the invention]

[0006] In view of the above problems, the present invention provides a reversible thermochromic aqueous ink composition for inkjet printers that has long-term storage stability, color development and fineness of printed images, and stable ink ejection properties. [Means for solving the problem]

[0007] The reversible thermochromic aqueous ink composition for inkjet printers according to the present invention comprises: (a) electron-donating color-forming organic compound; (b) an electron-accepting compound, and (c) a reaction medium that causes a reversible electron transfer reaction between the components (a) and (b) in a specific temperature range; a reversible thermochromic microcapsule pigment comprising microcapsules in which a reversible thermochromic composition comprising the compound is encapsulated in a coating; Water and Polyhydric alcohol organic solvents comprising The volume-based average particle diameter (X) of the microcapsules is 0.1 to 2 μm, and The cross section of the frozen microcapsule pigment was observed under a transmission electron microscope, and all capsules within the observation field were found to have the following formula: Cut cross-section film thickness = (cross-section outer diameter - cross-section inner diameter) / 2 (In the formula, the outer diameter and inner diameter of the cross section are calculated from the equivalent circle diameters of the area of ​​the region surrounded by the outer periphery of the cross section of the coating and the area of ​​the region surrounded by the inner periphery of the cross section of one microcapsule.) and the average value is taken as the average cross-sectional thickness, the average cross-sectional thickness (Y) of the microcapsules is 0.02 to 0.4 μm. It is characterized by the following.

[0008] The ink jet printer according to the present invention is characterized by containing the ink composition.

[0009] The ink cartridge according to the present invention is characterized by containing the ink composition. [Effects of the Invention]

[0010] The present invention provides a reversible thermochromic aqueous ink composition for inkjet printers that can form high-resolution, highly color-developable printed images. This ink composition has excellent stability over time and can maintain stable ejection properties over a long period of time. The present invention also provides an inkjet printer and ink cartridge that have such properties. [Brief explanation of the drawings]

[0011] [Figure 1] 1 is a graph illustrating the hysteresis characteristics in the color density-temperature curve of a reversibly thermochromic composition that is heat-discolorable. [Figure 2] 1 is a graph illustrating the hysteresis characteristics in the color density-temperature curve of a heat-discolorable, reversible thermochromic composition having color memory properties. [Figure 3] 1 is a graph illustrating the hysteresis characteristics in the color density-temperature curve of a reversibly thermochromic composition that develops color over time. [Figure 4] FIG. 1 is a schematic diagram illustrating an example of the configuration of an inkjet printer. DETAILED DESCRIPTION OF THE INVENTION

[0012] The reversible thermochromic aqueous ink composition for inkjet printers according to the present invention (hereinafter sometimes referred to as the "ink composition") contains at least a reversible thermochromic microencapsulated pigment, water, and a polyhydric alcohol-based organic solvent. Each component constituting the ink composition according to the present invention will be described below.

[0013] The ink composition according to the present invention contains a reversible thermochromic microencapsulated pigment (hereinafter sometimes referred to as "microencapsulated pigment") as a colorant.

[0014] The microcapsule pigment used in the ink composition of the present invention comprises microcapsules encapsulating a reversible thermochromic composition, and is typically an aggregate of microcapsules. This reversible thermochromic composition can be a thermally decolorizable (decolorizes upon heating and develops color upon cooling) reversible thermochromic composition containing at least three essential components: (i) an electron-donating color-forming organic compound, (ii) an electron-accepting compound, and (iii) a reaction medium that determines the temperature at which the color-forming reaction between components (i) and (ii) occurs.

[0015] An example of a reversible thermochromic composition to which such a microcapsule pigment can be applied is a composition described in Japanese Patent Publication Nos. 51-44706, 51-44707, and 1-29398, which changes color around a predetermined temperature (color change point), exhibiting a decolorized state in a temperature range above the high-temperature color change point and a colored state in a temperature range below the low-temperature color change point, with only one specific state existing at room temperature, and the other state being maintained while the heat or cold required to manifest that state is applied, but returning to the state it exhibits at room temperature when the heat or cold is removed; this composition has a relatively small hysteresis width (ΔH) (ΔH=1 to 7°C) (see Figure 1).

[0016] Other examples of reversible thermochromic compositions to which such microcapsule pigments can be applied include those described in JP-B-4-17154, JP-A-7-179777, JP-A-7-33997, JP-A-8-39936, and JP-A-2005-1369, which exhibit a large hysteresis width (ΔH=8-70°C), and in which the shape of the curve plotting the change in color density with temperature follows a significantly different path when the temperature is increased from below the color-change temperature range than when the temperature is decreased from above the color-change temperature range, and which exhibit color memory in a specific temperature range (the temperature range between the color-development onset temperature t2 and the color-discoloration onset temperature t3 (a temperature range in which two phases are essentially maintained)) that exhibits a colored state at temperatures below the complete color-development temperature t1 or a color-discolored state at temperatures above the complete color-discoloration temperature t4 (see Figure 2).

[0017] [Microcapsule pigment] Components (a), (b) and (c) will be specifically explained below. Component (A), that is, the electron-donating color-forming organic compound, is the component that determines the color, and is a compound that donates electrons to component (B), which is the color developer, to develop color.

[0018] Examples of the electron-donating color-forming organic compound include phthalide compounds, fluoran compounds, styrinoquinoline compounds, diazarhodamine lactone compounds, pyridine compounds, quinazoline compounds, and bisquinazoline compounds, and among these, phthalide compounds and fluoran compounds are preferred. Examples of the phthalide compound include a diphenylmethane phthalide compound, a phenylindolyl phthalide compound, an indolyl phthalide compound, a diphenylmethane azaphthalide compound, a phenylindolyl azaphthalide compound, and derivatives thereof. Among these, the phenylindolyl azaphthalide compound and derivatives thereof are preferred. Examples of the fluoran compound include aminofluoran compounds, alkoxyfluoran compounds, and derivatives thereof.

[0019] Examples of compounds that can be used as component (a) are listed below. 3,3-bis(4-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(1-n-butyl-2-methylindol-3-yl)phthalide, 3,3-bis(2-ethoxy-4-diethylaminophenyl)-4-azaphthalide, 3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3-(2-n-hexyloxy-4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3-[2-ethoxy-4-(N-ethylanilino)phenyl]-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3-(2-acetamido-4-diethylaminophenyl)-3-(1-propyl-2-methylindol-3-yl)-4-azaphthalide, 3,6-bis(diphenylamino)fluoran, 3,6-bis(N-phenyl-Np-tolylamino)fluoran, 3,6-dimethoxyfluoran, 3,6-di-n-butoxyfluorane, 2-methyl-6-(N-ethyl-Np-tolylamino)fluoran, 3-chloro-6-cyclohexylaminofluoran, 2-methyl-6-cyclohexylaminofluoran, 2-chloroamino-6-di-n-butylaminofluoran, 2-(2-chloroanilino)-6-di-n-butylaminofluoran, 2-(3-trifluoromethylanilino)-6-diethylaminofluoran, 2-(3-trifluoromethylanilino)-6-di-n-pentylaminofluoran, 2-dibenzylamino-6-diethylaminofluoran, 2-(N-methylanilino)-6-(N-ethyl-Np-tolylamino)fluoran, 1,3-dimethyl-6-diethylaminofluoran, 2-chloro-3-methyl-6-diethylaminofluoran, 2-anilino-3-methyl-6-diethylaminofluoran, 2-anilino-3-methoxy-6-diethylaminofluoran, 2-anilino-3-methyl-6-di-n-butylaminofluoran, 2-anilino-3-methoxy-6-di-n-butylaminofluoran, 2-xylidino-3-methyl-6-diethylaminofluoran, 2-anilino-3-methyl-6-(N-ethyl-Np-tolylamino)fluoran, 6-diethylamino-1,2-benzofluoran, 6-(N-ethyl-N-isobutylamino)-1,2-benzofluoran, 6-(N-ethyl-N-isopentylamino)-1,2-benzofluoran, 2-(3-methoxy-4-dodecoxystyryl)quinoline, 2-diethylamino-8-diethylamino-4-methylspiro[5H-[1]benzopyrano[2,3-d]pyrimidin-5,1′(3′H)-isobenzofuran]-3′-one, 2-di-n-butylamino-8-di-n-butylamino-4-methylspiro[5H-[1]benzopyrano[2,3-d]pyrimidin-5,1′(3′H)-isobenzofuran]-3′-one, 2-di-n-butylamino-8-diethylamino-4-methylspiro[5H-[1]benzopyrano[2,3-d]pyrimidin-5,1′(3′H)-isobenzofuran]-3′-one, 2-di-n-butylamino-8-(N-ethyl-N-isoamylamino)-4-methylspiro[5H-[1]benzopyrano[2,3-d]pyrimidin-5,1′(3′H)-isobenzofuran]-3′-one, 2-di-n-butylamino-8-di-n-pentylamino-4-methylspiro[5H-[1]benzopyrano[2,3-d]pyrimidin-5,1′(3′H)-isobenzofuran]-3′-one, 4,5,6,7-tetrachloro-3-(4-dimethylamino-2-methoxyphenyl)-3-(1-n-butyl-2-methylindol-3-yl)-1(3H)-isobenzofuranone, 4,5,6,7-tetrachloro-3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-1(3H)-isobenzofuranone, 4,5,6,7-tetrachloro-3-(4-diethylamino-2-ethoxyphenyl)-3-(1-n-pentyl-2-methylindol-3-yl)-1(3H)-isobenzofuranone, 4,5,6,7-tetrachloro-3-(4-diethylamino-2-methylphenyl)-3-(1-ethyl-2-methylindol-3-yl)-1(3H)-isobenzofuranone, 3',6'-bis[phenyl(2-methylphenyl)amino]spiro[isobenzofuran-1(3H),9'-[9H]xanthen]-3-one, 3',6'-bis[phenyl(3-methylphenyl)amino]spiro[isobenzofuran-1(3H),9'-[9H]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]

[0020] In addition, fluorans may be compounds having a substituent on the phenyl group forming the xanthene ring, or may be compounds that have a substituent on the phenyl group forming the xanthene ring and also have a substituent (for example, an alkyl group such as a methyl group, or a halogen atom such as a chlorine atom) on the phenyl group forming the lactone ring, and that exhibit a blue or black color.

[0021] Component (b), ie, the electron accepting compound, is a compound that accepts electrons from component (a) and functions as a developer for component (a). Examples of the electron-accepting compound include compounds selected from the group of compounds having an active proton, the group of pseudo-acidic compounds (compounds that are not acids but act as acids in the reversible thermochromic composition to cause component (A) to develop color), and the group of compounds having an electron vacancy. Among the above-mentioned component (B), compounds selected from the group of compounds having an active proton are preferred.

[0022] Examples of compounds having an active proton include compounds having a phenolic hydroxyl group and derivatives thereof, carboxylic acids and derivatives thereof, acidic phosphate esters and derivatives thereof, azole compounds and derivatives thereof, 1,2,3-triazole and derivatives thereof, cyclic carbosulfimides, halohydrins having 2 to 5 carbon atoms, sulfonic acids and derivatives thereof, and inorganic acids. Preferred examples of carboxylic acids and derivatives thereof include aromatic carboxylic acids and derivatives thereof, and aliphatic carboxylic acids having 2 to 5 carbon atoms and derivatives thereof. Examples of the pseudo-acidic compounds include metal salts of compounds having a phenolic hydroxyl group, 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. Compounds having electron vacancies include borates, borate esters, and inorganic salts.

[0023] Among the above-mentioned components (ii), compounds having a phenolic hydroxyl group are preferred because they can more effectively exhibit thermochromic properties. Compounds having a phenolic hydroxyl group include a wide range of compounds, from monophenol compounds to polyphenol compounds, and further include bisphenol compounds, trisphenol compounds, phenol-aldehyde condensation resins, etc. Compounds having a phenolic hydroxyl group preferably have at least two benzene rings. In addition, compounds having a phenolic hydroxyl group may have a substituent such as an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, a carboxyl group and its ester or amide group, or a halogen atom.

[0024] Examples of metals contained in metal salts of compounds having a phenolic hydroxyl group include sodium, potassium, calcium, zinc, zirconium, aluminum, magnesium, nickel, cobalt, tin, copper, iron, vanadium, titanium, lead, and molybdenum.

[0025] 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, thymol, 3-methyl-4-methylthiophenol, 2-tert-butyl-5-methylphenol, 2,6-bis(hydroxymethyl)-4-methylphenol, 2,3,5-trimethylphenol, 2,6-bis(hydroxymethyl)-4-tert-octylphenol, 6-hydroxy-1,3-benzoxathiol-2-one, 2,4-bis(phenylsulfonyl)phenol, 2,4-bis(phenylsulfonyl)-5-methylphenol, 2,4-bis(4-methylphenylsulfonyl)phenol, 2-phenylphenol, 4-phenylphenol, 2,6-diphenylphenol, 3-benzylbiphenyl-2-ol, 3,5-dibenzylbiphenyl-4-ol, 4-cyano-4′-hydroxybiphenyl, 1-hydroxybenzotriazole, 1-hydroxy-5-methylbenzotriazole, 1-hydroxy-5-chlorobenzotriazole, 1-hydroxy-5-methoxybenzotriazole, 1-hydroxy-4-benzoylaminobenzotriazole, 1-hydroxy-4,5,6,7-tetrachlorobenzotriazole, 1,4-hydroxybenzotriazole, 1-hydroxy-5-nitrobenzotriazole, 1-hydroxy-5-phenylbenzotriazole, 1-hydroxy-5-benzylbenzotriazole, 1-hydroxy-5-ethylbenzotriazole, 1-hydroxy-5-n-octylbenzotriazole, 1-hydroxy-5-n-butylbenzotriazole, n-Butyl 4-hydroxybenzoate, n-Octyl 4-hydroxybenzoate, 4-Hydroxybenzoic acid 2-heptadecafluorooctylethane, benzyl 4-hydroxybenzoate, 4-hydroxybenzoic acid benzyl ester, o-methylbenzyl 4-hydroxybenzoate, m-methylbenzyl 4-hydroxybenzoate, p-methylbenzyl 4-hydroxybenzoate, p-ethylbenzyl 4-hydroxybenzoate, p-propylbenzyl 4-hydroxybenzoate, p-tert-butylbenzyl 4-hydroxybenzoate, phenylethyl 4-hydroxybenzoate, 4-hydroxybenzoic acid-o-methylphenylethyl ester, m-Methylphenylethyl 4-hydroxybenzoate, p-methylphenylethyl 4-hydroxybenzoate, p-Ethylphenylethyl 4-hydroxybenzoate, p-propylphenylethyl 4-hydroxybenzoate, p-tert-butylphenylethyl 4-hydroxybenzoate Examples include:

[0026] 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, β-methyl resorcylate, β-benzyl resorcylate, 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:

[0027] Further, 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)ethyl propionate, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 2,2-bis(4-hydroxyphenyl)-4-methylhexane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 2,2-bis(3,5-dihydroxymethyl-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)butane, 2,2-bis(4-hydroxy-3-isopropylphenyl)propane, 2,2-bis(3-sec-butylphenyl-4-hydroxy)propane, 2,2-bis(4-hydroxy-3-phenylphenyl)propane, 2,2-bis(3-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(3-fluoro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dihydroxymethyl-4-hydroxyphenyl)propane, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, 1,4-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, 3,3-bis(4-hydroxyphenyl)oxindole, 3,3-bis(4-hydroxy-3-methylphenyl)oxindole, bis(2-hydroxyphenyl)methane, bis(2-hydroxy-5-methylphenyl)methane, bis(2-hydroxy-3-hydroxymethyl-5-methyl)methane, 4,4'-[1,4-phenylenebis(1-methylethylidene)]bis(2-methylphenol), 1,1-bis(4-hydroxy-3-phenylphenyl)cyclohexane, 3,3-ethyleneoxydiphenol, 1,4-bis(4-hydroxybenzoate)-3-methylbenzene, 4,4"-dihydroxy-3"-methyl-p-terphenyl, 4,4″-dihydroxy-3″-isopropyl-p-terphenyl, 2,2-dimethyl-1,3-bis(4-hydroxybenzoyloxy)propane, 2,2′-biphenol, 4,4′″-dihydroxy-p-quaterphenyl, 4,4-dihydroxydiphenyl ether, Bis(4-hydroxyphenylthioethyl) ether bis(4-hydroxyphenyl) sulfone, 4-benzyloxy-4′-hydroxydiphenyl sulfone, 4-(4-methylbenzyloxy)-4′-hydroxydiphenyl sulfone, 4-(4-ethylbenzyloxy)-4′-hydroxydiphenyl sulfone, 4-(4-n-propylbenzyloxy)-4′-hydroxydiphenyl sulfone, 4-(4-isopropylbenzyloxy)-4′-hydroxydiphenyl sulfone, 4-(4-n-butylbenzyloxy)-4′-hydroxydiphenyl sulfone, 4-(4-isobutylbenzyloxy)-4′-hydroxydiphenyl sulfone, 4-(4-sec-butylbenzyloxy)-4′-hydroxydiphenyl sulfone, 4-(4-tert-butylbenzyloxy)-4′-hydroxydiphenyl sulfone, 4-(3-methylbenzyloxy)-4′-hydroxydiphenyl sulfone, 4-(3-ethylbenzyloxy)-4′-hydroxydiphenyl sulfone, 4-(3-n-propylbenzyloxy)-4′-hydroxydiphenyl sulfone, 4-(3-isopropylbenzyloxy)-4′-dihydroxyphenyl sulfone, 4-(3-n-butylbenzyloxy)-4′-hydroxydiphenyl sulfone, 4-(3-isobutylbenzyloxy)-4′-hydroxydiphenyl sulfone, 4-(3-sec-butylbenzyloxy)-4'-hydroxydiphenyl sulfone, 4-(3-tert-butylbenzyloxy)-4'-hydroxydiphenyl sulfone, 4-(2-methylbenzyloxy)-4′-hydroxydiphenyl sulfone, 4-(2-ethylbenzyloxy)-4′-hydroxydiphenyl sulfone, 4-(2-n-propylbenzyloxy)-4′-hydroxydiphenyl sulfone, 4-(2-isopropylbenzyloxy)-4′-hydroxydiphenyl sulfone, 4-(2-n-butylbenzyloxy)-4′-hydroxydiphenyl sulfone, 4-(2-isobutylbenzyloxy)-4′-hydroxydiphenyl sulfone, 4-(2-sec-butylbenzyloxy)-4'-hydroxydiphenyl sulfone, 4-(2-tert-butylbenzyloxy)-4'-hydroxydiphenyl sulfone, 2,4′-dihydroxydiphenyl sulfone, 3,4′-dihydroxydiphenyl sulfone, 4-hydroxydiphenyl sulfone, 4-methyl-4'-hydroxyphenyl sulfone, 4-ethyl-4′-hydroxydiphenyl sulfone, 4-n-propyl-4′-hydroxydiphenyl sulfone, 4-isopropyl-4′-hydroxydiphenyl sulfone, 4-chloro-4′-hydroxydiphenyl sulfone, 4-fluoro-4′-hydroxydiphenyl sulfone, 4-chloro-2-methyl-4′-hydroxydiphenyl sulfone, 4-methoxy-4′-hydroxydiphenyl sulfone, 4-ethoxy-4′-hydroxydiphenyl sulfone, 4-n-propoxy-4′-hydroxydiphenyl sulfone, 4-isopropoxy-4′-hydroxydiphenyl sulfone, 4-n-butoxy-4′-hydroxydiphenyl sulfone, 4-isobutoxy-4′-hydroxydiphenyl sulfone, 4-sec-butoxy-4′-hydroxydiphenyl sulfone, 4-tert-butoxy-4′-hydroxydiphenyl sulfone, 4-n-pentyloxy-4′-hydroxydiphenyl sulfone, 4-isopentyloxy-4′-hydroxydiphenyl sulfone, 4-(1-propenyloxy)-4′-hydroxydiphenyl sulfone, 4-(2-propenyloxy)-4′-hydroxydiphenyl sulfone, 4-benzyloxy-4′-hydroxydiphenyl sulfone, 4-(β-phenoxyethoxy)-4′-hydroxydiphenyl sulfone, 4-(β-phenoxypropoxyl)-4′-hydroxydiphenyl sulfone, bis(2-allyl-4-hydroxydiphenyl) sulfone, bis[4-hydroxy-3-(2-propenyl)phenyl]sulfone, bis(3,5-dibromo-4-hydroxyphenyl) sulfone, bis(3,5-dichloro-4-hydroxyphenyl) sulfone, bis(3-phenyl-4-hydroxyphenyl) sulfone, bis(4-hydroxy-3-n-propylphenyl) sulfone, bis(4-hydroxy-3-methylphenyl) sulfone, 3,4-dihydroxydiphenyl sulfone, 3',4'-dihydroxy-4-methyldiphenyl sulfone, 3,4,4′-trihydroxydiphenyl sulfone, bis(3,4-dihydroxyphenyl) sulfone, 2,3,4-trihydroxydiphenyl sulfone, 4-isopropoxy-4′-hydroxydiphenyl sulfone, 4-n-propoxy-4′-hydroxydiphenyl sulfone, 4-allyloxy-4′-hydroxydiphenyl sulfone, 4-benzyloxy-4′-hydroxydiphenyl sulfone, 4-(2-propenyloxy)-4′-hydroxydiphenyl sulfone, 3-benzyl-4-benzyloxy-4′-hydroxydiphenyl sulfone, 3-phenethyl-4-phenethyloxy-4′-hydroxydiphenyl sulfone, 3-methylbenzyl-4-methylbenzyloxy-4′-hydroxydiphenyl sulfone, 4-benzyloxy-3′-benzyl-4′-hydroxydiphenyl sulfone, 4-phenethyloxy-3′-phenethyl-4′-hydroxydiphenyl sulfone, 4-methylbenzyloxy-3′-methylbenzyl-4′-hydroxydiphenyl sulfone, α,α′-bis{4-(p-hydroxyphenylsulfone)phenoxy}-p-xylene, 4,4′-{oxybis(ethylene oxide-p-phenylene sulfonyl)}diphenol, Bis(4-hydroxyphenyl) sulfide, bis(4-hydroxy-3-methylphenyl) sulfide, bis(3,5-dimethyl-4-hydroxyphenyl) sulfide, bis(3-ethyl-4-hydroxyphenyl) sulfide, bis(3,5-diethyl-4-hydroxyphenyl) sulfide, bis(4-hydroxy-3-n-propylphenyl) sulfide, bis(3,5-di-n-propyl-4-hydroxyphenyl) sulfide, bis(3-tert-butyl-4-hydroxyphenyl) sulfide, bis(3,5-di-tert-butyl-4-hydroxyphenyl) sulfide, bis(4-hydroxy-3-n-pentylphenyl) sulfide, bis(3-n-hexyl-4-hydroxyphenyl) sulfide, bis(3-n-heptyl-4-hydroxyphenyl) sulfide, bis(5-tert-octyl-2-hydroxyphenyl) sulfide, bis(2-hydroxy-3-tert-octylphenyl) sulfide, bis(2-hydroxy-5-n-octyl-phenyl) sulfide, bis(5-chloro-2-hydroxyphenyl) sulfide, bis(3-cyclohexyl-4-hydroxyphenyl) sulfide, bis(4-hydroxyphenylthioethoxy)methane, 1,5-(4-hydroxyphenylthio)-3-oxypentane, 1,8-bis(4-hydroxyphenylthio)-3,6-dioxaoctane Examples include:

[0028] Examples of compounds having three phenolic hydroxyl groups include pyrogallol, phloroglucinol, phloroglucinolcarboxylic acid, gallic acid, octyl gallate, and dodecyl gallate.

[0029] Further examples of trisphenol compounds include: 4,4′,4″-methylidynetrisphenol, 4,4′,4″-methylidynetris(2-methylphenol), 4,4'-[(2-hydroxyphenyl)methylene]bis(2,3,5-trimethylphenol), 4,4'-[(4-hydroxyphenyl)methylene]bis(2-methylphenol), 4,4'-[(4-hydroxyphenyl)methylene]bis(2,6-dimethylphenol), 4,4'-[(4-hydroxy-3-methoxyphenyl)methylene]bisphenol, 4,4'-[(4-hydroxyphenyl)methylene]bis(2-cyclohexyl-5-methylphenol), 4,4′,4″-ethylidynetrisphenol, 4,4′,4″-ethylidinetris(2-methylphenol), 4,4'-[(2-hydroxyphenyl)methylene]bis(2-cyclohexyl-5-methylphenol), 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol, 2,4-bis[(2-hydroxy-5-methylphenyl)methyl]-6-cyclohexylphenol, 4,4'-[1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}methylidene]bisphenol, 4,4'-[1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bisphenol, 4,4'-[1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}propylidene]bisphenol, 4,4'-[1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}butylidene]bisphenol, 4,4'-[1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}pentylidene]bisphenol, 4,4'-[1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}hexylidene]bisphenol, 4,4'-[1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}heptylidene]bisphenol, 4,4'-[1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}isobutylidene]bisphenol, 4,4'-[1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}neopentylidene]bisphenol, 2,2'-[1-{4-[1-(2-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bisphenol, 3,3′-[1-{4-[1-(3-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bisphenol, 4,4'-[1-{4-[1-(3-fluoro-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis(2-fluorophenol), 4,4'-[1-{4-[1-(3-chloro-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis(2-chlorophenol), 4,4'-[1-{4-[1-(3-bromo-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis(2-bromophenol), 4,4'-[1-{4-[1-(4-hydroxy-3-methylphenyl)-1-methylethyl]phenyl}ethylidene]bis(2-methylphenol), 4,4'-[1-{4-[1-(3-ethyl-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis(2-ethylphenol), 4,4'-[1-{4-[1-(3-tert-butyl-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis(2-tert-butylphenol), 4,4'-[1-{4-[1-(4-hydroxy-3-trifluoromethylphenyl)-1-methylethyl]phenyl}ethylidene]bis(2-trifluoromethylphenol), 1,1-bis(4-hydroxyphenyl)-4-(4-hydroxy-α-ethyl)benzylcyclohexane, 4,4'-[(3-ethoxy-4-hydroxyphenyl)methylene]bisphenol, 4,4'-[(3-hydroxyphenyl)methylene]bis(2,6-dimethylphenol), 2,2'-[(4-hydroxyphenyl)methylene]bis(3,5-dimethylphenol), 4,4'-[(4-hydroxy-3-methoxyphenyl)methylene]bis(2,6-dimethylphenol), 2,2'-[(2-hydroxyphenyl)methylene]bis(3,5,6-trimethylphenol), 4,4'-[(3-hydroxyphenyl)methylene]bis(2,3,6-trimethylphenol), 4,4'-[(4-hydroxyphenyl)methylene]bis(2,3,6-trimethylphenol), 4,4'-[(3-hydroxyphenyl)methylene]bis(2-cyclohexyl-5-methylphenol), 4,4'-[(4-hydroxyphenyl-3-methoxy)methylene]bis(2-cyclohexyl-5-methylphenol), 1,1-bis(4-hydroxyphenyl)-4-hydroxyphenylcyclohexane, 4,4'-[3-(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3-phenyl)propylidene]bis(2-cyclohexyl-5-methylphenol), 4,4'-[(2-hydroxyphenyl)methylene]bis(2-methylphenol), 2,4',4"-methylidynetrisphenol, 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-hydroxyphenyl)-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″-methylidynetris(2,6-dimethylphenol), α-(4-hydroxy-3-methylphenyl)-α,α′-bis(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene, α′-(4-hydroxy-3-methylphenyl)-α,α-bis(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene, α,α-bis(4-hydroxy-3-methylphenyl)-α′-(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene, α,α′-bis(4-hydroxy-3-methylphenyl)-α-(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene, 1,1-bis(4-hydroxyphenyl)-4-[1-(4-hydroxyphenyl)-1-methylpropyl]cyclohexane, 2,6-bis[(3,5-dimethyl-4-hydroxyphenyl)methyl]-4-ethylphenol, 1,1′-bis(4-hydroxyphenyl)-4-[1-(4-hydroxyphenyl)propyl]cyclohexane, 1,1′-bis(4-hydroxy-3-methylphenyl)-4-[1-(4-hydroxyphenyl)propyl]cyclohexane, 1,1′-bis(3,5-dimethyl-4-hydroxyphenyl)-4-[1-(4-hydroxyphenyl)propyl]cyclohexane, 1-(4-hydroxyphenyl)-1-[4,4-bis(4-hydroxyphenyl)cyclohexyl]-4-isopropylcyclohexane, 4,4'-[3-(2,5-dimethyl-4-hydroxyphenyl)butylene]bis(2,5-dimethylphenol), 1,3,5-tri(4-hydroxy-3-phenylphenyl)adamantane, 1,3,5-tri(3-cyclohexyl-4-hydroxyphenyl)adamantane, 2,4-bis[(3,5-dimethyl-4-hydroxyphenyl)methyl]-6-cyclohexylphenol, 2,6-bis[(2,5-dimethyl-4-hydroxyphenyl)methyl]-4-cyclohexylphenol, 2,4-bis[(3-cyclohexyl-4-hydroxyphenyl)methyl]-6-methylphenol, 2,4-bis[(4-hydroxy-2,3,5-trimethylphenyl)methyl]-6-cyclohexylphenol, 2,6-bis[(5-fluoro-2-hydroxyphenyl)methyl]-4-fluorophenol, 2,6-bis[(3-fluoro-4-hydroxyphenyl)methyl]-4-fluorophenol, 2,4-bis[(3-fluoro-4-hydroxyphenyl)methyl]-6-methylphenol, 4,4'-[3-(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3-biphenylpropylidene]bis(5-cyclohexyl-2-methylphenol), 4,4'-[3-(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropylidene]bis(2,5-dimethylphenol), 2,4-bis[(2,5-dimethyl-4-hydroxyphenyl)methyl]-6-methylphenol, 1,1,2-tris(4-hydroxyphenyl)ethane, 1,1,3-tris(4-hydroxyphenyl)propane, 1,1,4-tris(4-hydroxyphenyl)butane, 1,2,2-tris(4-hydroxyphenyl)propane, 1,2,2-tris(4-hydroxyphenyl)butane, 1,2,2-tris(4-hydroxyphenyl)pentane, 1,2,2-tris(4-hydroxyphenyl)hexane, 1,2,2-tris(4-hydroxyphenyl)heptane, 1,2,2-tris(4-hydroxyphenyl)octane, 1,2,2-tris(4-hydroxyphenyl)-3-methylbutane 1,2,2-tris(4-hydroxyphenyl)-3,3-dimethylbutane, 1,2,2-tris(4-hydroxyphenyl)-4,4-dimethylpentane, 1,3,3-tris(4-hydroxyphenyl)butane, 1,3,3-tris(4-hydroxyphenyl)pentane, 1,3,3-tris(4-hydroxyphenyl)hexane, 1,3,3-tris(4-hydroxyphenyl)heptane, 1,3,3-tris(4-hydroxyphenyl)octane, 1,3,3-tris(4-hydroxyphenyl)nonane, 1,4,4-tris(4-hydroxyphenyl)pentane, 1,4,4-tris(4-hydroxyphenyl)hexane, 1,4,4-tris(4-hydroxyphenyl)heptane, 1,4,4-tris(4-hydroxyphenyl)octane, 1,4,4-tris(4-hydroxyphenyl)nonane, 1,4,4-tris(4-hydroxyphenyl)decane, 1,2,2-tris(2-hydroxyphenyl)propane, 1,1,2-tris(3-hydroxyphenyl)propane, 1-(4-hydroxyphenyl)-2,2-bis(2-hydroxyphenyl)propane, 1,2,2-tris(3-fluoro-4-hydroxyphenyl)propane, 1,2,2-tris(3-chloro-4-hydroxyphenyl)propane, 1,2,2-tris(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3-ethyl-4-hydroxyphenyl)-1-(4-hydroxyphenyl)propane, 2,2-bis(3-tert-butyl-4-hydroxyphenyl)-1-(4-hydroxyphenyl)propane, 2,2-bis(2-hydroxy-3-biphenylyl)-1-(4-hydroxyphenyl)propane, 2,2-bis(3-trifluoromethyl-4-hydroxyphenyl)-1-(4-hydroxyphenyl)propane, 2-(3-methyl-4-hydroxyphenyl)-1,2-bis(4-hydroxyphenyl)propane, 1-(3-methyl-4-hydroxyphenyl)-2,2-bis(4-hydroxyphenyl)propane, 3-(3-methyl-4-hydroxyphenyl)-1,3-bis(4-hydroxyphenyl)butane, 1-(3-methyl-4-hydroxyphenyl)-3,3-bis(4-hydroxyphenyl)butane, 4-(3-methyl-4-hydroxyphenyl)-1,4-bis(4-hydroxyphenyl)pentane, 1-(3-methyl-4-hydroxyphenyl)-4,4-bis(4-hydroxyphenyl)pentane, 1,2-bis(3-methyl-4-hydroxyphenyl)-2-(4-hydroxyphenyl)propane, 3,3-bis(3-methyl-4-hydroxyphenyl)-1-(4-hydroxyphenyl)butane, 1,3-bis(3-methyl-4-hydroxyphenyl)-3-(4-hydroxyphenyl)butane, 4,4-bis(3-methyl-4-hydroxyphenyl)-1-(4-hydroxyphenyl)pentane, 1,4-bis(3-methyl-4-hydroxyphenyl)-4-(4-hydroxyphenyl)pentane, 1,1,2-tris(3-methyl-4-hydroxyphenyl)ethane, 1,2,2-tris(3-methyl-4-hydroxyphenyl)propane, 1,1,3-tris(3-methyl-4-hydroxyphenyl)propane, 1,3,3-tris(3-methyl-4-hydroxyphenyl)butane, 1,1,4-tris(3-methyl-4-hydroxyphenyl)butane, 1,4,4-tris(3-methyl-4-hydroxyphenyl)pentane, 4,4'-[4-(4-hydroxyphenyl)-sec-butylidene]bis(2-methylphenol) Examples include:

[0030] 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(methylidyne)tetrakis(2,6-dimethylphenol), 2,2-bis[4,4-bis(4-hydroxy-3-methylphenyl)cyclohexyl]propane, 2,2'-[(3,4-dihydroxyphenyl)methylene]bis(3,5-dimethylphenol), 4,6-bis[(3,5-dimethyl-4-hydroxyphenyl)methyl]-1,3-benzenediol, 2,2'-[(3,4-dihydroxyphenyl)methylene]bis(3,5,6-trimethylphenol), 4,4'-[(3,4-dihydroxyphenyl)methylene]bis(2-cyclohexylphenol), Bis[4-hydroxy-3-(2-hydroxybenzyl)-5-methylphenyl]methane, Bis[4-hydroxy-3-(3-hydroxybenzyl)-5-methylphenyl]methane, bis[4-hydroxy-3-(4-hydroxybenzyl)-5-methylphenyl]methane, Bis[2-hydroxy-3-(2-hydroxybenzyl)-5-methylphenyl]methane, Bis[2-hydroxy-3-(3-hydroxybenzyl)-5-methylphenyl]methane, Bis[2-hydroxy-3-(4-hydroxybenzyl)-5-methylphenyl]methane, Bis[2-hydroxy-3-(3-hydroxy-4-methylbenzyl)-5-methylphenyl]methane, Bis[2-hydroxy-3-(4-hydroxy-3-methylbenzyl)-5-methylphenyl]methane, Bis[2-hydroxy-3-(3-hydroxy-2-methylbenzyl)-5-methylphenyl]methane, Bis[2-hydroxy-3-(2-hydroxy-3-methylbenzyl)-5-methylphenyl]methane, α,α′,α″,α′″-tetrakis(4-hydroxyphenyl)-p-xylene, Bis[2-hydroxy-3-(4-hydroxy-2,3,5-trimethylbenzyl)-5-methylphenyl]methane, Bis[2-hydroxy-3-(2,5-dimethyl-3-hydroxybenzyl)-5-methylphenyl]methane, Bis[2-hydroxy-3-(2,5-dimethyl-4-hydroxybenzyl)-5-methylphenyl]methane, Bis[2-hydroxy-3-(2,5-dimethyl-5-hydroxybenzyl)-5-methylphenyl]methane, Bis[2-hydroxy-3-(3,5-dimethyl-4-hydroxybenzyl)-5-methylphenyl]methane, Bis[2-hydroxy-3-(2-hydroxy-3,4,6-trimethylbenzyl)-5-methylphenyl]methane, Bis[2-hydroxy-3-(4-hydroxy-2,3,6-trimethylbenzyl)-5-methylphenyl]methane, 4,4,4′,4′-tetrakis(4-hydroxyphenyl)bicyclohexyl, Bis[4-hydroxy-3-(5-cyclohexyl-4-hydroxy-2-methylbenzyl)-5-methylphenyl]methane, 4,4,4′,4′-tetrakis(4-hydroxy-3-methylphenyl)bicyclohexyl, 4,6-bis(3,5-dimethyl-4-hydroxyphenyl)-1,2-benzenediol, 4,4,4′,4′-tetrakis(3,5-dimethyl-4-hydroxyphenyl)bicyclohexyl, 1,1-bis[5-cyclohexyl-4-hydroxy-3-(2-hydroxy-5-methylbenzyl)phenyl]cyclohexane, 1,1-bis[5-cyclohexyl-4-hydroxy-3-(3,5-dimethyl-4-hydroxybenzyl)phenyl]cyclohexane, 1,1-bis[5-cyclohexyl-4-hydroxy-3-(5-cyclohexyl-4-hydroxy-2-methylbenzyl)phenyl]cyclohexane, 4,6-bis[1-(4-hydroxyphenyl)ethyl]-1,3-benzenediol, 2,2-bis[4-hydroxy-3-(4-hydroxy-3-methylbenzyl)-5-methylphenyl]propane, 2,6-bis[(3,5-dimethyl-4-hydroxyphenyl)benzyl]-4-[α-methyl-(3,5-dimethyl-4-hydroxyphenyl)benzyl]phenol, 4,4,4',4'-tetrakis(3-isopropyl-4-hydroxyphenyl)bicyclohexyl, 4,4'-bis[(3,4-dihydroxyphenyl)methylene]bis(2-isopropylphenol), 2,2'-bis[4,4-bis(4-hydroxyphenyl)cyclohexyl]propane, 2,4,6-tris(4-hydroxybenzyl)-1,3-benzenediol, 4,6-bis(3,5-dimethyl-4-hydroxybenzyl)-1,2,3-benzenetriol, 3,3'-[(2-hydroxyphenyl)methylene]bis(5-methyl-1,2-benzenediol), 2,6-bis(2,4-dihydroxybenzyl)-4-ethylphenol, 2,4-bis(2,4-dihydroxybenzyl)-6-cyclohexylphenol, 2,6-bis(5-tert-butyl-2,3-dihydroxybenzyl)-4-methylphenol, 2,4,6-tris(3,5-dimethyl-4-hydroxybenzyl)-1,2-benzenediol, 2,4,6-tris(3,5-dimethyl-2-hydroxybenzyl)-1,2-benzenediol, 2,6-bis(2,4-dihydroxybenzyl)-3,4-dimethylphenol, 2,6-bis[3-(2-hydroxy-5-methylbenzyl)-2,5-dimethyl-4-hydroxybenzyl]-3,4-dimethylphenol, 4,6-bis(α-methyl-4-hydroxybenzyl)-1,2,3-benzenetriol, 4,4'-[1-{4-[1-(3,5-bis(4-hydroxybenzyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[2,6-bis(4-hydroxybenzyl)phenol], 4,4'-[1-{4-[1-(3,5-bis(4-hydroxy-3-methylbenzyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[2,6-bis(4-hydroxy-3-methylbenzyl)phenol], 4,4'-[1-{4-[1-(3,5-bis(3,5-dimethyl-4-hydroxybenzyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[2,6-bis(3,5-dimethyl-4-hydroxybenzyl)phenol], 4,4'-[1-{4-[1-(3,5-bis(4-hydroxy-2,3,6-trimethylbenzyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[2,6-bis(4-hydroxy-2,3,6-trimethylbenzyl)phenol], Bis[5-(2,4-dihydroxybenzyl)-4-hydroxy-3-methylphenyl]methane, Bis[3-(2,4-dihydroxybenzyl)-2,5-dimethyl-4-hydroxyphenyl]methane, Bis[3-(2,4-dihydroxy-3-methylbenzyl)-2,5-dimethyl-4-hydroxyphenyl]methane, Bis[5-(4-hydroxybenzyl)-2,3,4-trihydroxyphenyl]methane, 1,1-bis[5-(4-hydroxybenzoyl)-2,3,4-trihydroxyphenyl]ethane, 3,3′,5,5′-tetrakis(4-hydroxybenzyl)-4,4′-dihydroxybiphenyl, 3,3′,5,5′-tetrakis(4-hydroxy-3-methylbenzyl)-4,4′-dihydroxybiphenyl, 3,3′,5,5′-tetrakis(2-hydroxy-5-methylbenzyl)-4,4′-dihydroxybiphenyl, 3,3′,5,5′-tetrakis(3,5-dimethyl-4-hydroxybenzyl)-4,4′-dihydroxybiphenyl, Bis[3-(α,α-bis(4-hydroxy-3-methylphenyl)methyl-4-hydroxyphenyl]methane, Bis[3,5-bis(2-hydroxy-5-methylbenzyl)-4-hydroxyphenyl]methane, 4,4',4"-ethylidinetris{[2-(2-hydroxy-5-methyl)benzyl]-6-methylphenol}, 2,2-bis[3,5-bis(2-hydroxy-5-methylphenylmethyl)phenyl]propane, Bis[3-(α,α-bis(2,5-dimethyl-4-hydroxyphenyl)methyl-4-hydroxyphenyl]methane, Bis[5-(3,5-dimethyl-4-hydroxybenzyl)-2,3,4-trihydroxyphenyl]methane, Bis[3-(2,3,4-trihydroxybenzyl)-2,5-dimethyl-4-hydroxyphenyl]methane, 1,1-bis[3-(2,3,4-trihydroxybenzyl)-5-cyclohexyl-4-hydroxyphenyl]cyclohexane, 1,8,15,22-tetranonyl-3,5,10,12,17,19,24,26-octahydroxy[1,1,1,1]-metacyclophane, 4,4'-[1-{4-[1-(3,5-bis(4-hydroxy-2-methylbenzyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[2,6-bis(4-hydroxy-2-methylbenzyl)phenol], 4,4'-[1-{4-[1-(3,5-bis(2-hydroxy-5-methylbenzyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[2,6-bis(2-hydroxy-5-methylbenzyl)phenol], 4,4'-[1-{4-[1-(3,5-bis(3-ethyl-4-hydroxybenzyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[2,6-bis(3-ethyl-4-hydroxybenzyl)phenol], 4,4'-[1-{4-[1-(3,5-bis(3,5-dimethyl-2-hydroxyphenyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[2,6-bis(3,5-dimethyl-2-hydroxyphenyl)phenol], 4,4'-[1-{4-[1-(3,5-bis(4-hydroxy-3-isopropylphenyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[2,6-bis(4-hydroxy-3-isopropylphenyl)phenol], Bis[3-(α,α-bis(3,5-dimethyl-4-hydroxyphenyl)methyl-4-hydroxyphenyl]methane, Bis[3-(α,α-bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)methyl-4-hydroxyphenyl]methane, 4,4'-[4-hydroxy-3,5-bis(2-hydroxybenzyl)methylene]bis[2,6-bis(2-hydroxybenzyl)]phenol, 4,4'-[4-hydroxy-3,5-bis(4-hydroxybenzyl)methylene]bis[2,6-bis(4-hydroxybenzyl)]phenol, 4,4',4"-Ethylidinetris[2,6-bis(2-hydroxybenzyl)phenol], 4,4',4"-Ethylidinetris[2,6-bis(4-hydroxybenzyl)phenol], 2,2-bis[3,5-bis(4-hydroxy-3-methylbenzyl)-4-hydroxyphenyl]propane, 1,8,15,22-tetraethyl-3,5,10,12,17,19,24,26-octahydroxy[1,1,1,1]-metacyclophane, α,α′,α″,α′″-tetrakis(3,5-dimethyl-4-hydroxyphenyl)-1,4-dimethylbenzene, 4,4'-[1-{4-[1-(3,5-bis(2-hydroxy-5-isopropylphenyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[2,6-bis(2-hydroxy-5-isopropylphenyl)phenol], 4,4'-[1-{4-[1-(3,5-bis(4-hydroxy-2,3,5-trimethylphenyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[2,6-bis(4-hydroxy-2,3,5-trimethylphenyl)phenol], 4,4'-[1-{4-[1-(3,5-bis(3-sec-butyl-4-hydroxyphenyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[2,6-bis(3-sec-butyl-4-hydroxyphenyl)phenol], 4,4'-[1-{4-[1-(3,5-bis(3-tert-butyl-4-hydroxyphenyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[2,6-bis(3-tert-butyl-4-hydroxyphenyl)phenol], 2,6-bis{[3-(2,4-dihydroxybenzyl)-2,5-dimethyl-4-hydroxy]benzyl}-4-methylphenol, 1,1-bis[5-(2,4-dihydroxybenzyl)-3-cyclohexyl-4-hydroxyphenyl]cyclohexane, 1,1-bis[5-(2,3,4-trihydroxybenzyl)-3-cyclohexyl-4-hydroxyphenyl]cyclohexane, 2,2-bis[4,4',4'',4'''-tetrakis(3,5-dihydroxymethyl-4-hydroxyphenyl)cyclohexyl]propane Examples include:

[0031] 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-distyrenated salicylic acid, N-(p-toluenesulfonyl)-glycine, N-(p-toluenesulfonyl)-alanine, N-(p-toluenesulfonyl)-β-alanine, N-phenylaminocarbonyl-glycine, N-phenylaminocarbonyl-valine, N-(m-tolylaminocarbonyl)-phenylalanine, N-(m-tolylaminocarbonyl)-cysteine-S-benzyl, N-(m-tolylaminocarbonyl)-methionine, N-(m-tolylaminocarbonyl)-tyrosine, N-(p-tolylaminocarbonyl)-phenylalanine, N-(p-tolylaminocarbonyl)-cysteine-S-benzyl, N-(p-tolylaminocarbonyl)-methionine, N-(phenylaminocarbonyl)-methionine, N-(p-tolylaminocarbonyl)-tyrosine, 2-O-(phenylaminocarbonyl)-mandelic acid, 2-O-(p-tolylaminocarbonyl)-mandelic acid, 2-O-(m-tolylaminocarbonyl)-mandelic acid, 2-O-(o-tolylaminocarbonyl)-mandelic acid, 2-O-(1-naphthylaminocarbonyl)-mandelic acid, 2-O-(3-isopropenyl-α,α-dimethylbenzylaminocarbonyl)-mandelic acid, 2-O-(benzylaminocarbonyl)-mandelic acid, 2-O-(phenethylaminocarbonyl)-mandelic acid, 2-O-(phenylaminocarbonyl)-lactic acid, 2-O-(p-tolylaminocarbonyl)-lactic acid, 2-O-(m-tolylaminocarbonyl)-lactic acid, 2-O-(o-tolylaminocarbonyl)-lactic acid, 2-O-(1-naphthylaminocarbonyl)-lactic acid, 2-O-(3-isopropenyl-α,α-dimethylbenzylaminocarbonyl)-lactic acid, 2-O-(benzylaminocarbonyl)-lactic acid, 2-O-(phenethylaminocarbonyl)-lactic acid Examples include:

[0032] Examples of acidic phosphate ester compounds include methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, isodecyl acid phosphate, isotridecyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, monobutyl phosphate, dibutyl phosphate, monoisodecyl phosphate, and bis(2-ethylhexyl) phosphate.

[0033] As component (b), a compound having a phenolic hydroxyl group is preferred because it can more effectively exhibit thermochromic properties, but compounds selected from aromatic carboxylic acids, aliphatic carboxylic acids having 2 to 5 carbon atoms, carboxylic acid metal salts, acidic phosphate esters and metal salts thereof, and 1,2,3-triazole and derivatives thereof may also be used.

[0034] The component (c) of the reaction medium that reversibly induces an electron donor-acceptor reaction between the components (a) and (b) in a specific temperature range will now be described. Examples of the component (c) include alcohols, esters, ketones, ethers, and acid amides.

[0035] When a reversible thermochromic composition is encapsulated in microcapsules and used for secondary processing, low molecular weight compounds will evaporate out of the capsules when subjected to high heat treatment, so compounds with 10 or more carbon atoms are preferably used to stably retain the composition within the capsules.

[0036] As the alcohols, aliphatic monohydric saturated alcohols having 10 or more carbon atoms are effective, and examples thereof include decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, heptadecyl alcohol, octadecyl alcohol, eicosyl alcohol, and docosyl alcohol.

[0037] As the esters, esters having 10 or more carbon atoms are effective, and examples thereof include esters obtained from any combination of a monocarboxylic acid having an aliphatic, alicyclic or aromatic ring and a monohydric alcohol having an aliphatic, alicyclic or aromatic ring, esters obtained from any combination of a polycarboxylic acid having an aliphatic, alicyclic or aromatic ring and a monohydric alcohol having an aliphatic, alicyclic or aromatic ring, esters obtained from any combination of a monocarboxylic acid having an aliphatic, alicyclic or aromatic ring and a polyhydric alcohol having an aliphatic, alicyclic or aromatic ring, and Examples of esters include esters obtained from any combination thereof, such as 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 stearate. n-Undecyl tearic acid, pentadecyl stearate, stearyl stearate, cyclohexylmethyl stearate, isopropyl behenate, hexyl behenate, lauryl behenate, behenyl behenate, cetyl benzoate, stearyl 4-tert-butylbenzoate, dimyristyl phthalate, distearyl phthalate, dimyristyl oxalate, dicetyl oxalate, dicetyl malonate, dilauryl succinate, dilauryl glutarate, diundecyl adipate, dilauryl azelate, di-(n-nonyl) sebacate ), dineopentyl 1,18-octadecylmethylenedicarboxylate, ethylene glycol dimyristate, propylene glycol dilaurate, propylene glycol distearate, hexylene glycol dipalmitate, 1,5-pentanediol distearate, 1,2,6-hexanetriol trimyristate, 1,4-cyclohexanediol didecyl, 1,4-cyclohexanedimethanol dimyristate, xylene glycol dicaprinate, xylene glycol distearate, and the like can be mentioned as examples.

[0038] Also effective are esters of saturated fatty acids and branched fatty alcohols, and ester compounds of unsaturated fatty acids or branched or substituted saturated fatty acids and branched aliphatic alcohols or aliphatic alcohols having 16 or more carbon atoms.

[0039] Examples of the 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 lauric 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 3,7-dimethyloctyl erucate, 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, and behenyl butyrate.

[0040] Furthermore, in order to cause a color change that exhibits large hysteresis characteristics in the color density-temperature curve and to impart color memory properties that depend on temperature changes, exemplified are 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 a substituted aromatic ring in the molecule, esters of carboxylic acids containing an unsubstituted aromatic ring and aliphatic alcohols having 10 or more carbon atoms, carboxylic acid esters containing a cyclohexyl group in the molecule, esters of fatty acids having 6 or more carbon atoms and unsubstituted aromatic alcohols or phenols, esters of fatty acids having 8 or more carbon atoms and branched aliphatic alcohols, esters of dicarboxylic acids and aromatic alcohols or branched aliphatic alcohols, dibenzyl cinnamate, heptyl stearate, didecyl adipate, dilauryl adipate, dimyristyl adipate, dicetyl adipate, distearyl adipate, trilaurin, trimyristin, tristearin, dimyristin, and distearin.

[0041] Also effective are fatty acid ester compounds obtained from an odd-numbered aliphatic monohydric alcohol having 9 or more carbon atoms and an even-numbered aliphatic carboxylic acid, and fatty acid ester compounds having a total of 17 to 23 carbon atoms obtained from n-pentyl alcohol or n-heptyl alcohol and an even-numbered aliphatic carboxylic acid having 10 to 16 carbon atoms.

[0042] 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. , 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-undelci eicosanoate, n-tridecyl eicosanoate, n-pentadecyl eicosanoate, n-nonyl behenate, n-undecyl behenate, n-tridecyl behenate, n-pentadecyl behenate, and the like.

[0043] As the ketones, aliphatic ketones having a total carbon number of 10 or more are effective, and examples thereof 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, and the like.

[0044] Further, aryl alkyl ketones having a total carbon number of 12 to 24, for example, n-octadecanophenone, n-heptadecanophenone, n-hexadecanophenone, n-pentadecanophenone, n-tetradecanophenone, 4-n-dodecaacetophenone, n-tridecanophenone, 4-n-undecanoacetophenone, n-laurophenone, 4-n-decanoacetophenone, n-undecanophenone, 4-n-nonylacetophenone, n-decanophenone, 4-n-octylacetophenone, n ... Examples of acetophenone include 4-n-heptylacetophenone, n-octanophenone, 4-n-hexylacetophenone, 4-n-cyclohexylacetophenone, 4-tert-butylpropiophenone, n-heptaphenone, 4-n-pentylacetophenone, cyclohexyl phenyl ketone, benzyl-n-butyl ketone, 4-n-butylacetophenone, n-hexanophenone, 4-isobutylacetophenone, 1-acetonaphthone, 2-acetonaphthone, and cyclopentyl phenyl ketone.

[0045] As the ethers, aliphatic ethers having a total of 10 or more carbon atoms are effective, and examples thereof 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, and undecanediol diethyl ether.

[0046] Examples of acid amides include acetamide, propionic acid amide, butyric acid amide, caproic acid amide, caprylic acid amide, capric acid amide, lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, 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 caproate. amide, caprylic acid N-methylamide, capric acid N-methylamide, lauric acid N-methylamide, myristic acid N-methylamide, palmitic acid N-methylamide, stearic acid N-methylamide, behenic acid N-methylamide, oleic acid N-methylamide, erucic acid N-methylamide, lauric acid N-ethylamide, myristic acid N-ethylamide, palmitic acid N-ethylamide, stearic acid N-ethylamide, oleic acid N-ethylamide, lauric acid N-butylamide, myristic acid N-butylamide, palmitic acid N-butylamide, stearate Stearic acid N-butylamide, oleic acid N-butylamide, lauric acid N-octylamide, myristic acid N-octylamide, palmitic acid N-octylamide, stearic acid N-octylamide, oleic acid N-octylamide, lauric acid N-dodecylamide, myristic acid N-dodecylamide, palmitic acid N-dodecylamide, stearic acid N-dodecylamide, oleic acid N-dodecylamide, dilauric acid amide, dimyristic acid amide, dipalmitic acid amide, distearic acid amide, dioleic acid amide, trilauric acid amide, trilauric acid amide Rimyristic acid amide, tripalmitic acid amide, tristearic acid amide, trioleic acid amide, succinic acid amide, adipic acid amide, glutaric acid amide, malonic acid amide, azelaic acid amide, maleic acid amide, succinic acid N-methylamide, adipic acid N-methylamide, glutaric acid N-methylamide, malonic acid N-methylamide, azelaic acid N-methylamide, succinic acid N-ethylamide, adipic acid N-ethylamide, glutaric acid N-ethylamide, malonic acid N-ethylamide, azelaic acid N-ethylamide, succinic acid N-butylamide,Examples include adipic acid N-butylamide, glutaric acid N-butylamide, malonic acid N-butylamide, adipic acid N-octylamide, and adipic acid N-dodecylamide.

[0047] Furthermore, the component (iii) may be a compound represented by the following formula (1). [ka] [wherein R1 represents a hydrogen atom or a methyl group, m represents an integer of 0 to 2, and either X1 or X2 represents -(CH2) n OCOR2 or (CH2) n COOR2, and the other represents a hydrogen atom; n represents an integer of 0 to 2; R2 represents an alkyl or alkenyl group having 4 or more carbon atoms; Y1 and Y2 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, or a halogen atom; and r and p each independently represent an integer of 1 to 3.

[0048] Of the compounds represented by formula (3), it is preferable that R1 is a hydrogen atom, since this results in a reversible thermochromic composition with a wider hysteresis width, and it is even more preferable that R1 is a hydrogen atom and m is 0.

[0049] Among the compounds represented by formula (1), the compound represented by the following formula (2) is more preferred. [ka] (In the formula, R represents an alkyl group or alkenyl group having 8 or more carbon atoms, preferably an alkyl group having 10 to 24 carbon atoms, and more preferably an alkyl group having 12 to 22 carbon atoms.)

[0050] Examples of the compound represented by formula (2) include 4-benzyloxyphenylethyl octanoate, 4-benzyloxyphenylethyl nonanoate, 4-benzyloxyphenylethyl decanoate, 4-benzyloxyphenylethyl undecanoate, 4-benzyloxyphenylethyl dodecanoate, 4-benzyloxyphenylethyl tridecanoate, 4-benzyloxyphenylethyl tetradecanoate, 4-benzyloxyphenylethyl pentadecanoate, 4-benzyloxyphenylethyl hexadecanoate, 4-benzyloxyphenylethyl heptadecanoate, and 4-benzyloxyphenylethyl octadecanoate.

[0051] Furthermore, the component (iii) may be a compound represented by the following formula (3). [ka] (In the formula, R represents an alkyl or alkenyl group having 8 or more carbon atoms, m and n each independently represent an integer of 1 to 3, and X and Y each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom.)

[0052] Examples of the compound represented by formula (3) 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, and 1,1-diphenylmethyl octadecanoate.

[0053] Furthermore, the component (iii) may be a compound represented by the following formula (4). [ka] (In the formula, X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, or a halogen atom; m represents an integer of 1 to 3; and n represents an integer of 1 to 20.)

[0054] Examples of the compound represented by formula (4) include a diester of malonic acid and 2-[4-(4-chlorobenzyloxy)phenyl]ethanol, a diester of succinic acid and 2-(4-benzyloxyphenyl)ethanol, a diester of succinic acid and 2-[4-(3-methylbenzyloxy)phenyl]ethanol, a diester of glutaric acid and 2-(4-benzyloxyphenyl)ethanol, a diester of glutaric acid and 2-[4-(4-chlorobenzyloxy)phenyl]ethanol, a diester of adipic acid and 2-(4-benzyloxyphenyl)ethanol, a diester of pimelic acid and 2-(4-benzyloxyphenyl)ethanol, a diester of suberic acid and 2-(4-benzyloxyphenyl)ethanol, a diester of suberic acid and 2-[4-(3-methylbenzyloxy)phenyl]ethanol, a diester of glutaric acid and 2-(4-benzyloxyphenyl)ethanol, a diester of adipic acid and 2-(4-benzyloxyphenyl)ethanol, a diester of pimelic acid and 2-(4-benzyloxyphenyl)ethanol, a diester of suberic acid and 2-[4-(3-methylbenzyloxy)phenyl]ethanol, a diester of adipic acid and 2-(4-benzyloxyphenyl) ... Examples include the diester of suberic acid and 2-[4-(4-chlorobenzyloxy)phenyl]ethanol, the diester of suberic acid and 2-[4-(2,4-dichlorobenzyloxy)phenyl]ethanol, the diester of suberic acid and 2-[4-(2,4-dichlorobenzyloxy)phenyl]ethanol, the diester of azelaic acid and 2-(4-benzyloxyphenyl)ethanol, the diester of sebacic acid and 2-(4-benzyloxyphenyl)ethanol, the diester of 1,10-decanedicarboxylic acid and 2-(4-benzyloxyphenyl)ethanol, the diester of 1,18-octadecanedicarboxylic acid and 2-(4-benzyloxyphenyl)ethanol, and the diester of 1,18-octadecanedicarboxylic acid and 2-[4-(2-methylbenzyloxy)phenyl]ethanol.

[0055] Furthermore, the component (iii) may be a compound represented by the following formula (5). [ka] (In the formula, R represents an alkyl group or alkenyl group having 1 to 21 carbon atoms, and n represents an integer of 1 to 3.)

[0056] Examples of the compound represented by formula (5) include a diester of 1,3-bis(2-hydroxyethoxy)benzene and capric acid, a diester of 1,3-bis(2-hydroxyethoxy)benzene and undecanoic acid, a diester of 1,3-bis(2-hydroxyethoxy)benzene and lauric acid, a diester of 1,3-bis(2-hydroxyethoxy)benzene and myristic acid, a diester of 1,4-bis(hydroxymethoxy)benzene and butyric acid, a diester of 1,4-bis(hydroxymethoxy)benzene and isovaleric acid, and a diester of 1,4-bis(2-hydroxyethoxy)benzene and acetic acid. Examples of such esters include esters of 1,4-bis(2-hydroxyethoxy)benzene and propionic acid, diesters of 1,4-bis(2-hydroxyethoxy)benzene and valeric acid, diesters of 1,4-bis(2-hydroxyethoxy)benzene and caproic acid, diesters of 1,4-bis(2-hydroxyethoxy)benzene and caprylic acid, diesters of 1,4-bis(2-hydroxyethoxy)benzene and capric acid, diesters of 1,4-bis(2-hydroxyethoxy)benzene and lauric acid, and diesters of 1,4-bis(2-hydroxyethoxy)benzene and myristic acid.

[0057] Furthermore, the component (iii) may be a compound represented by the following formula (6). [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 of 1 to 3; and n represents an integer of 1 to 20.)

[0058] Examples of the compound represented by formula (6) include a diester of succinic acid and 2-phenoxyethanol, a diester of suberic acid and 2-phenoxyethanol, a diester of sebacic acid and 2-phenoxyethanol, a diester of 1,10-decanedicarboxylic acid and 2-phenoxyethanol, and a diester of 1,18-octadecanedicarboxylic acid and 2-phenoxyethanol.

[0059] Furthermore, the component (iii) may be a compound represented by the following formula (7). [ka] (In the formula, R represents an alkyl group having 4 to 22 carbon atoms, a cycloalkylalkyl group, a cycloalkyl group, or an alkenyl group having 4 to 22 carbon atoms; 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; and n represents 0 or 1.)

[0060] Examples of the compound represented by formula (7) include decyl 4-phenylbenzoate, lauryl 4-phenylbenzoate, myristyl 4-phenylbenzoate, cyclohexylethyl 4-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.

[0061] Furthermore, the component (iii) may be a compound represented by the following formula (8). [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 the compound represented by formula (8) include phenoxyethyl 4-butoxybenzoate, phenoxyethyl 4-pentyloxybenzoate, phenoxyethyl 4-tetradecyloxybenzoate, esters of phenoxyethyl 4-hydroxybenzoate and dodecanoic acid, and dodecyl ether of phenoxyethyl vanillate.

[0062] Furthermore, the component (iii) may be a compound represented by the following formula (9). [ka] (In the formula, R represents any one of an alkyl group having 4 to 22 carbon atoms, an alkenyl group having 4 to 22 carbon atoms, a cycloalkylalkyl group, and a cycloalkyl group; X represents any one of a hydrogen atom, an alkyl group, an alkoxy group, and a halogen atom; Y represents any one of a hydrogen atom, an alkyl group, an alkoxy group, and a halogen atom; and n represents 0 or 1.)

[0063] Examples of the compound represented by formula (9) include the benzoate ester of octyl 4-hydroxybenzoate, the benzoate ester of decyl 4-hydroxybenzoate, the 4-methoxybenzoate ester of heptyl 4-hydroxybenzoate, the 2-methoxybenzoate ester of dodecyl 4-hydroxybenzoate, and the benzoate ester of cyclohexylmethyl 4-hydroxybenzoate.

[0064] Furthermore, the component (iii) may be a compound represented by the following formula (10). [ka] (In the formula, R represents any one of an alkyl group having 3 to 18 carbon atoms, a cycloalkylalkyl group having 6 to 11 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, and an alkenyl group having 3 to 18 carbon atoms; X represents any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a halogen atom; and Y represents any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, an ethoxy group, and a halogen atom.)

[0065] Examples of the compound represented by formula (10) 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.

[0066] Furthermore, the component (iii) may be a compound represented by the following formula (11). [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 of 1 to 3.)

[0067] Examples of the compound represented by formula (11) include a diester of 1,3-bis(2-hydroxyethoxy)benzene and cyclohexanecarboxylic acid, a diester of 1,4-bis(2-hydroxyethoxy)benzene and cyclohexanepropionic acid, and a diester of 1,3-bis(2-hydroxyethoxy)benzene and cyclohexanepropionic acid.

[0068] Furthermore, the component (iii) may be a compound represented by the following formula (12). [ka] (In the formula, R represents any one of an alkyl group having 3 to 17 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and a cycloalkylalkyl group having 5 to 8 carbon atoms; X represents any one of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a methoxy group, an ethoxy group, and a halogen atom; and n represents an integer of 1 to 3.)

[0069] Examples of the compound represented by formula (12) include a diester of 4-phenylphenol ethylene glycol ether and cyclohexanecarboxylic acid, a diester of 4-phenylphenol diethylene glycol ether and lauric acid, a diester of 4-phenylphenol triethylene glycol ether and cyclohexanecarboxylic acid, a diester of 4-phenylphenol ethylene glycol ether and octanoic acid, a diester of 4-phenylphenol ethylene glycol ether and nonanoic acid, a diester of 4-phenylphenol ethylene glycol ether and decanoic acid, and a diester of 4-phenylphenol ethylene glycol ether and myristic acid.

[0070] Furthermore, reversible thermochromic compositions of the heat-coloring type (which develops color upon heating and loses color upon cooling) can also be applied (see FIG. 3), using specific alkoxyphenol compounds having a linear or branched alkyl group with 3 to 18 carbon atoms as the electron-accepting compound (Japanese Patent Application Laid-Open Nos. 11-129623 and 11-5973), specific hydroxybenzoic acid esters (Japanese Patent Application Laid-Open No. 2001-105732), or gallic acid esters (Japanese Patent Application Laid-Open Nos. 51-44706 and 2003-253149).

[0071] The above-mentioned reversible thermochromic composition is a compatible solution containing the above-mentioned components (a), (b), and (c) as essential components, and the proportions of each component depend on the concentration, discoloration temperature, discoloration form, and type of each component. Generally, the component ratios that achieve the desired properties are in the range of 1 part of component (a) to 0.1 to 100, preferably 0.1 to 50, and more preferably 0.5 to 20, of component (b), and 5 to 200, preferably 5 to 100, and more preferably 10 to 100, of component (c) (all of the above proportions are in parts by mass).

[0072] Furthermore, the reversible thermochromic composition may contain various light stabilizers as required. The light stabilizer is included to prevent photodegradation of the reversible thermochromic composition consisting of components (A), (B), and (C), and is blended in a proportion 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 block ultraviolet rays contained in sunlight and the like, preventing photodegradation caused by the excited state resulting from the photoreaction of component (A). Furthermore, antioxidants, singlet oxygen quenchers, superoxide anion quenchers, ozone quenchers, etc., inhibit photooxidation reactions. The light stabilizers may be used alone or in combination of two or more.

[0073] In the present invention, the microcapsules have a specific structure, which is expressed by the average particle size (X) of the microcapsules contained in the microcapsule pigment or the microcapsules contained in the ink composition, and the average cross-sectional film thickness (Y) obtained by image analysis.

[0074] In the present invention, the average particle size is a volume-based average particle size (median size). The optimal method for measuring the average particle size is to use a laser diffraction / scattering particle size distribution analyzer calibrated by a direct measurement method, such as the laser diffraction particle size distribution analyzer LA-300 (trade name, manufactured by Horiba, Ltd.).

[0075] Direct measurement methods used for calibration include: (i) Image analysis method to measure the area (2D) of individual particles from images taken with a microscope to determine their equivalent diameter; (ii) The Coulter method (electrical sensing zone method) 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.Calibration of the laser measurement method is performed based on the values ​​obtained by these methods.

[0076] The average particle diameter can be measured by image analysis, for example, by determining the particle region using image analysis particle size distribution measurement software "MacView" (trade name, manufactured by Mountec Co., Ltd.), calculating the diameter equivalent to a circle with a projected area (Heywood diameter) from the area of ​​the particle region, and measuring the average particle diameter of particles equivalent to a sphere with an equal volume using this value. The Coulter method can be used to measure the average particle size when the particle size of all or most of the particles exceeds 0.2 μm. For example, the method can be used with a particle size distribution analyzer, such as the Beckman Coulter Multisizer 4e.

[0077] Furthermore, the microcapsule pigment contained in the ink composition according to the present invention is specified by the average cross-sectional thickness (Y) of the microcapsules. The cross-sectional thickness can be obtained by image analysis of a cross-sectional image of the frozen microcapsule pigment. Specifically, (i) freezing a dispersion of the microencapsulated pigment, for example, a water dispersion; (ii) A thin section sample of 50 μm thickness was prepared using a microtome. (iii) The obtained thin film sample is observed using a transmission electron microscope, such as HT7700 (trade name, manufactured by Hitachi High-Technologies Corporation), in a field of view where the number of microcapsules within the field of view is approximately 100 to 200, (iv) For each microcapsule in the field of view, the area of ​​the region surrounded by the outer periphery of the cross section of the coating and the area of ​​the region surrounded by the inner periphery of the cross section of the coating are measured; (v) From the two areas found, the outer diameter and inner diameter of the cross section are calculated, respectively. (vi) For all microcapsules within the field of view, Cut cross-section film thickness = (cross-section outer diameter - cross-section inner diameter) / 2 The cut cross-sectional thickness is calculated based on the above, and the average value is taken as the average cut cross-sectional thickness. The outer diameter and inner diameter of the cross section in (iv) and (v) can be determined using the image analysis software described above. The calculation of the average cross-sectional thickness in the present invention is for capsules whose cross-sectional thickness can be measured and calculated by the above (iv) and (v).

[0078] In this invention, the cross-sectional thickness does not simply correspond to the thickness of the microcapsule coating; it is a different parameter from the coating. Measuring the coating thickness of a microcapsule is generally very difficult. This is because, to directly observe the coating thickness, a cross-section passing through the center of the microcapsule must be observed. However, it is difficult to obtain such a cross-section for all microcapsules with a particle size distribution. Furthermore, although microcapsules often have a nearly spherical shape, they can become deformed due to the expansion and contraction of the inclusions, making it difficult to determine the center of the microcapsule. These combined factors make measuring the coating thickness difficult. In contrast, this invention focuses on the cross-sectional thickness instead of the coating thickness. This cross-sectional thickness does not coincide with the membrane thickness. This is because the cross-section formed when preparing a thin section sample often does not pass through the center of the microcapsule being cut. Furthermore, the fact that actual microcapsules have a particle size distribution further complicates measuring the particle size and coating thickness of microcapsules.

[0079] On the other hand, the present invention was completed based on the finding that when these parameters and the average particle size satisfy certain conditions, the ink composition exhibits excellent effects. First, the microcapsules contained in the ink composition of the present invention have a volume-based average particle diameter (X) of 0.1 to 2.0 μm, preferably 0.3 to 1.5 μm. If the volume-based average particle diameter (X) of the microcapsules is excessively small, the color density generally tends to decrease, while if it is excessively large, it may cause the microcapsules to settle or the ink jetting performance to decrease, so care must be taken. Therefore, by ensuring that the volume-based average particle diameter (X) is within the above range, the color density and the jetting performance of the composition containing the microcapsule pigment can be maintained at a good level.

[0080] In order to maintain the ejection properties and ejection stability of the ink composition, it is preferable that the content of coarse microcapsules is low. Specifically, the content of microcapsules with a particle size of 5 μm or more (hereinafter sometimes referred to as the large particle content) is preferably 1% by volume or less based on the total volume of microcapsules in the microcapsule pigment.

[0081] The average cross-sectional thickness (Y) is 0.02 to 0.4 μm, preferably 0.02 to 0.3 μm, and more preferably 0.03 to 0.3 μm. When the average cross-sectional thickness (Y) is within an appropriate range, a reversible thermochromic microcapsule pigment having an excellent balance between durability and color density can be obtained.

[0082] Furthermore, the ratio Y / X of the average particle diameter (X) to the average cross-sectional film thickness (Y) of the microcapsules contained in the ink composition according to the present invention preferably satisfies the following formula (1), more preferably (1a), and sometimes preferably (1b): Furthermore, the ratio Y / X preferably satisfies the following formula (2), more preferably (2a), and sometimes preferably (2b): By keeping the ratio Y / X within an appropriate range, a reversible thermochromic microcapsule pigment having an excellent balance between durability and color density can be obtained. Y / X<0.3 (1) Y / X<0.25 (1a) Y / X<0.2 (1b) 0.02 <Y / X (2) 0.03 <Y / X (2a) 0.04 <Y / X (2b)

[0083] [Method of manufacturing microcapsules] The microcapsule pigment used in the ink composition of the present invention comprises microcapsules having a coating that encapsulates a reversible thermochromic composition containing the above components (i), (ii), and (iii).

[0084] By encapsulating the reversible thermochromic composition in microcapsules, a chemically and physically stable pigment can be formed. Furthermore, the reversible thermochromic composition maintains the same composition under various conditions of use, allowing it to exhibit the same effects.

[0085] The microencapsulation method is appropriately selected depending on the application from conventionally known manufacturing methods such as an isocyanate-based interfacial polymerization method, an in situ polymerization method such as a melamine-formalin-based method, a liquid curing coating method, a phase separation method from an aqueous solution, a phase separation method from an organic solvent, a melt-dispersion cooling method, an air suspension coating method, a spray drying method, etc. Furthermore, a secondary resin coating can be further provided on the surface of the microcapsules depending on the purpose to impart durability or to modify the surface properties for practical use.

[0086] In the present invention, it is necessary that the average particle size (X) and average cross-sectional thickness (Y) of the microcapsules contained in the microcapsule pigment satisfy specific conditions. To satisfy the specific conditions, it is necessary to adjust the manufacturing conditions of the microcapsules. As mentioned above, there are various methods for producing microcapsules, and the appropriate conditions vary depending on each method. Furthermore, the appropriate conditions also vary depending on the components constituting the reversibly thermochromic composition used and the components forming the microcapsule coating. Therefore, in order to produce the microcapsules according to the present invention, it is common to create a calibration curve for different production conditions and search for the optimal conditions.

[0087] For example, when microcapsules are produced by interfacial polymerization, the average particle size (X) and average cross-sectional thickness (Y) of the microcapsules vary depending on factors such as the polymerization temperature, polymerization time, the blending ratio of the reversible thermochromic composition to the coating material, and the stirring speed of the reaction solution. Several types of microcapsules are produced by varying only one of these parameters, and the average particle size (X) and average cross-sectional thickness (Y) are measured to create a calibration curve. If the production conditions for the desired microcapsules cannot be determined using this calibration curve alone, another parameter is varied to create a calibration curve. In this way, microcapsules with the desired average particle size (X) and average cross-sectional thickness (Y) can be produced.

[0088] [Inkjet ink composition] The inkjet ink composition according to the present invention comprises a reversible thermochromic microcapsule pigment, water, and a polyhydric alcohol-based organic solvent. The content of the reversible thermochromic microencapsulated pigment is preferably 3 to 30% by mass, and more preferably 5 to 30% by mass, based on the total mass of the ink composition. When the content of the microencapsulated pigment is within the above range, both good ink dischargeability and excellent color development of the printed image can be achieved.

[0089] (Polyhydric alcohol organic solvent) The ink composition contains a polyhydric alcohol organic solvent, and the polyhydric alcohol primarily exerts a moisturizing effect.

[0090] Examples of polyhydric alcohol-based organic solvents that can be used in the ink composition include glycerin, alkanediols, glycol ethers, etc. Examples of alkanediols include 1,2-alkanediols such as 1,2-ethanediol, 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, and 1,2-octanediol; 1,3-propanediol, 1,3-butanediol, 1,3-pentanediol, 1,3-hexanediol, 1,3-heptanediol, and 1, 1,3-alkanediols such as 3-octanediol; and other diols such as 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-ethyl-2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 3-methyl-1,5-pentanediol, 2,5-hexanediol, and 2,3-dimethyl-1,4-butanediol. Examples of glycol ethers include ethylene glycol ethers such as ethylene glycol monomethyl ether, diethylene glycol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, triethylene glycol diethyl ether, ethylene glycol ethyl methyl ether, diethylene glycol ethyl methyl ether, and triethylene glycol ethyl methyl ether;Examples of propylene glycol ethers include propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, and tripropylene glycol monoethyl ether;

[0091] Considering the prevention of nozzle clogging due to drying of the ink composition and the prevention of elution of the microcapsule pigment encapsulated in the ink composition, preferred polyhydric alcohol organic solvents for the ink composition are glycerin and alkanediols, and more preferred are glycerin, 1,2-ethanediol, and 1,3-butanediol.

[0092] The blending ratio of the polyhydric alcohol-based organic solvent is preferably 5 to 60 mass %, more preferably 10 to 60 mass %, even more preferably 20 to 60 mass %, and particularly preferably 30 to 50 mass %, based on the total mass of the ink composition. Two or more types of polyhydric alcohol organic solvents may be used in combination.

[0093] (Polyether phosphate ester) The ink composition preferably further comprises a polyether phosphate ester. The polyether phosphate ester has the effect of suppressing aggregation of the microencapsulated pigment and improving the dispersibility of the microencapsulated pigment, thereby further improving the ink flowability and ink dischargeability. The polyether phosphate ester may be an alkali metal salt, an ammonium salt, or an alkanolamine salt.

[0094] Specific examples of commercially available polyether phosphate esters include Plysurf A212C, A215C, A208F, M208F, A208N, A208B, A219B, DB-01, A210D, and AL as part of the Plysurf series (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), and Phosphanol 2P and ML as part of the Phosphanol series (manufactured by Toho Chemical Industry Co., Ltd.). -200, GF-185, BH-650, ED-200, RA-600, ML-220, ML-240, RD-510Y, RS-410, RS-610, RS-710, RL-210, RL-310, RB-410, RD-710, RP-710, LF-200, RM-410, RM-510, SP-212, CP-120, 720, SC-6103, RD-720, LP-700, LP-500, LB-400, etc. In addition, the Anstex series (manufactured by Toho Chemical Industry Co., Ltd.) includes Anstex AK-25, AK-25B, SM-172, GF-339, GF-199, ML-200, and GF-185, as well as Disparlon AQ-320 and Disparlon AQ-330 (all manufactured by Kusumoto Chemical Co., Ltd.). Polyether phosphate esters applicable to the ink composition are not limited to these. Two or more types of polyether phosphate esters may be used in combination.

[0095] The content of the polyether phosphate ester is preferably 1 to 10 mass % based on the total mass of the ink composition, and more preferably 1 to 5 mass %. When the blending ratio is within the above range, the dispersibility of the microcapsule pigment can be improved, while the elution of the material contained in the microcapsule pigment into the ink can be suppressed.

[0096] (additives) The ink composition may further contain any additives as necessary. Specific examples of such additives include 2-pyrrolidone, polyvinylpyrrolidone, urethane resins, styrene-butadiene resins, alkyd resins, sulfamide resins, maleic acid resins, polyvinyl acetate resins, ethylene vinyl acetate resins, vinyl chloride-vinyl acetate resins, styrene and maleic acid ester copolymers, styrene-acrylonitrile resins, cyanate-modified polyalkylene glycols, ester gums, xylene resins, urea resins, urea aldehyde resins, phenolic resins, alkylphenolic resins, terpene phenolic resins, rosin resins and their hydrogenated compounds, rosin phenolic resins, polyvinyl alkyl ethers, polyamide resins, polyolefin resins, nylon resins, polyester resins, cyclohexanone resins, water-soluble inorganic salts, silicone surfactants, fluorine-containing surfactants, and sulfosuccinic acid surfactants.

[0097] The ink composition may also contain conventionally known substances such as preservatives, anti-rust agents, anti-fungal agents, antioxidants, wetting agents, ultraviolet absorbers, chelating agents, pH adjusters, anti-foaming agents, and viscosity adjusters.

[0098] Examples of preservatives or antifungal agents include 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-(methylsulfonyl)pyridine. Examples of rust inhibitors include benzotriazole and tolyltriazole. Examples of wetting agents include saponin, urea, sorbitol, mannitol, sucrose, glucose, reduced starch hydrolysates, and sodium pyrophosphate. Examples of pH adjusters include acidic substances such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid, boric acid, lactic acid, citric acid, tartaric acid, and malic acid, and basic substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, sodium hydrogen phosphate, and potassium hydrogen phosphate. Examples of basic substances that can be used include alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine. The basic substance can also be used as a neutralizing substance for the polyether phosphate ester.

[0099] The viscosity of the ink composition is preferably 2 to 30 mPa·s, and more preferably 2 to 20 mPa·s. When the viscosity is within the above range, the ink dischargeability is good, the color developability is excellent, and it becomes easy to form a high-resolution image. In the present invention, viscosity is measured using a BL type viscometer under conditions of 20°C and 30 rpm, and for example, a TVB-M type viscometer (product name: L-type rotor, manufactured by Toki Sangyo Co., Ltd.) can be used for the measurement.

[0100] The surface tension of the ink composition is preferably 20 to 50 mN / m, and more preferably 20 to 35 mN / m. By setting the surface tension within the above range, the penetration of the ink composition is improved, and the drying properties of the image are likely to be good. In the present invention, the surface tension is measured by the vertical plate method using a platinum plate at 20° C. A surface tension measuring instrument manufactured by Kyowa Interface Science Co., Ltd. can be used as the measuring instrument.

[0101] The pH value of the ink composition at 20° C. is preferably 4 to 8, more preferably 5 to 7. By adjusting the pH within the above range, the ink composition can have good stability over time.

[0102] The aqueous ink composition according to the present invention can be produced using various stirrers such as a propeller stirrer, a homodisper, or a homomixer, or various dispersers such as a bead mill. As an example of a specific manufacturing method, a reversible thermochromic microcapsule pigment is mixed with water and a polyhydric alcohol-based organic solvent to prepare a reversible thermochromic microcapsule pigment dispersion, and then an additive such as a polyether phosphate ester is mixed therewith.

[0103] The ink composition of the present invention is applied to an ink jet printer.

[0104] [Inkjet printer] One example of an inkjet printer is a device that includes an ink storage section that stores the ink composition, a printer head, an ink supply flow path that supplies the ink composition from the ink storage section to the printer head, and an ink recovery flow path that returns the ink composition that was not ejected from the nozzles (ink ejection section) of the printer head from the printer head to the ink supply flow path, and that includes a mechanism for circulating the ink composition through the ink supply flow path, the printer head, and the ink recovery flow path.

[0105] In the inkjet printer, the ink composition circulates in the ink flow path (the ink supply flow path and the ink recovery flow path) and in the printer head, preventing the ink composition from stagnating and causing the microcapsule pigment to aggregate, thereby improving the ink ejection properties from the nozzles of the printer head.

[0106] In order to further consider the prevention of aggregation of the microcapsule pigment, the printer head preferably has a flow path through which the ink composition circulates within the printer head. By providing the printer head with a flow path through which the ink composition described above circulates, the ink composition circulates within the printer head, making it easier to prevent the ink composition from stagnating in the printer head, and therefore easier to prevent the microcapsule pigment from agglomerating within the printer head. The ink jet printer may be equipped with a degassing mechanism, a heating mechanism, and the like in addition to the above-mentioned mechanisms.

[0107] The ink ejection method of the printer head can be any known method, such as a charge control method that uses electrostatic attraction to eject ink, a piezoelectric method that uses voltage-induced deformation of a piezoelectric element to eject an ink composition, an acoustic inkjet method that converts an electric signal into an acoustic beam and irradiates the ink with it to eject the ink using radiation pressure, or a thermal inkjet (Bubble Jet (registered trademark)) method that heats the ink to form bubbles and uses the resulting pressure. Since reversibly thermochromic ink compositions change color with temperature changes, it is preferable that the ink composition undergo little temperature change, and piezoelectric methods and acoustic inkjet methods, which experience relatively little temperature change, are preferred. However, a thermal inkjet method can also be employed by adjusting the color change temperature of the ink composition.

[0108] The nozzle of the printer head has an inner diameter that allows the ink composition to be ejected satisfactorily. In order to ensure good color development and fineness of the printed image, the inner diameter is preferably 10 μm to 100 μm, and more preferably 10 μm to 50 μm. The nozzle inner diameter is more preferably 10 μm to 30 μm.

[0109] When the ink composition contains a radically polymerizable compound and a radical polymerization initiator, the inkjet printer preferably includes a UV light irradiation unit. By irradiating a printed image formed with the ink composition with UV light, the radically polymerizable compound polymerizes, causing the ink composition to quickly adhere to the printed surface, thereby improving the fixability of the printed image. Furthermore, the ink storage section may be provided with a mechanism for mounting an ink cartridge, which contains the ink composition described above.

[0110] An example of an inkjet printer according to this embodiment will be described below with reference to the drawings.

[0111] Figure 4 is a schematic diagram showing an example of the configuration of an inkjet printer equipped with an ink circulation mechanism. The ink supply device 1 shown in Figure 4 includes an ink storage section 2, a printer head 3, an ink supply flow path 4a, a pump 5, a wiping means 6, and an ink recovery flow path 4b (the flow path to the left of the printer head 3 in the figure) that returns ink from the head to the ink supply flow path 4a and circulates the ink composition.

[0112] The printer head 3 has ink discharge portions 8 of a plurality of nozzles 7 formed on one surface, each of which discharges an ink composition 9. The ink composition 9 in the nozzles 7 is pushed out by a piezoelectric element and discharged from the ink discharge ports 8 of the nozzles 7. The printer head 3 also has an ink inlet 3b that takes in the ink composition from an ink supply flow path 4a, an ink outlet 3a that discharges the ink composition into an ink recovery flow path 4b, and an internal flow path 3c that connects the plurality of nozzles 7, the ink inlet 3b, and the ink outlet 3a. The density of the nozzles 7 in the printer head may be, for example, 600 npi (nozzles per inch) or 2400 npi.

[0113] The ink circulation path connects the ink inlet 3b and ink outlet 3a of the printer head 3 via an ink flow path, and is a path through which the ink composition 9 is circulated. In FIG. 4, the ink supply path 4a, the internal path 3c of the printer head 3, and the ink recovery path 4b form a circular path through which the ink composition 9 is circulated. While printing is stopped, it is preferable to circulate the ink composition 9 through the circular path to prevent the microencapsulated pigment in the ink composition 9 from settling or agglomerating within the printer head 3. The ink supply path 4a and the ink recovery path 4b can be, for example, pipes with a diameter of 1 to 10 mm, and can be made of silicone piping. The circumferential length of the circulation path can be 800 mm to 10 m, preferably 1 to 9 m, and particularly preferably 3 to 8 m.

[0114] Pump 5 is disposed upstream of printer head 3 within ink supply flow path 4a, and supplies ink composition 9 to printer head 3. By supplying ink composition 9 to printer head 3 and circulating ink composition 9 in the circular path, ink composition 9 flows within internal flow path 3c of printer head 3, and it is possible to prevent the microcapsule pigment in ink composition 9 from settling or agglomerating within printer head 3.

[0115] During inkjet printing, it is preferable to circulate the ink composition by a pump. Also, while inkjet printing is stopped, it is preferable to circulate the ink composition by placing a cap (not shown) on the nozzle discharge section.

[0116] The ink is sprayed onto any object such as paper, synthetic paper, coated paper, plastic sheet, plastic, wood, metal, glass, or other shaped body, fabric, or nonwoven fabric using the inkjet printer to form a suitable printed image, thereby obtaining a reversible thermochromic printed matter.

[0117] [Ink cartridges] The ink composition may be contained in an ink cartridge. The ink cartridge is not particularly limited as long as it can accommodate the ink composition, and can be constructed from a variety of materials and in a variety of shapes.

[0118] Examples of materials that can be used to make ink cartridges include plastics such as polyethylene terephthalate (PET), ABS resin, and polystyrene (PS), various metals (including alloys), and polyolefins such as polyethylene, ethylene vinyl acetate copolymer, and polypropylene. Furthermore, the materials are not limited to these, and may also include polymers and films obtained by blending or laminating the above polymers in appropriate ratios. Examples of ink cartridge forms include packs, bottles, tanks, jars, and cans.

[0119] The ink cartridge may have a container in which a plurality of ink chambers are provided so as to be independent from each other, and each chamber may contain ink compositions of a plurality of colors so that the inks in each chamber are of different colors.

[0120] In addition, a plurality of ink cartridges can be combined to form an ink cartridge set. The ink cartridge set may be made up of inks of the same color, or may be made up of inks of multiple colors.

[0121] Furthermore, the ink cartridge may have a structure that allows it to be mounted in an ink jet printer and supply the ink composition from the ink cartridge to an ink flow path.

[0122] [Example] Examples are described below, in which "parts" refers to parts by mass.

[0123] Example 1 (Preparation of reversible thermochromic microcapsule pigment) A reversible thermochromic composition was prepared by mixing 3.0 parts of 7-[2-(acetylamino)-4-(diethylamino)phenyl]-7-(2-methyl-1-propyl-1H-indol-3-yl)furo[3,4-b]pyridin-5(7H)-one as component (A), 15.0 parts of 1,1'-bis(4'-hydroxyphenyl)n-nonane as component (B), and 50.0 parts of 4-benzyloxyphenylethyl caprate as component (C). This composition was then added to a mixed solution consisting of 45 parts of aromatic polyisocyanate prepolymer and 40.0 parts of cosolvent as a coating material. This mixed solution was emulsified and dispersed in a 10% aqueous polyvinyl alcohol solution. The mixture was heated and stirred at 10,000 rpm using a homomixer. Then, 2.5 parts of a water-soluble aliphatic modified amine was added, and further stirring was continued to prepare a microcapsule pigment dispersion. The microcapsule dispersion was filtered using a filter press to obtain a microcapsule pigment.

[0124] The volume-average particle size (X) of the microcapsules contained in the reversible thermochromic microcapsule pigment was measured using a laser diffraction / scattering particle size distribution analyzer (instrument name: LA-300, manufactured by Horiba, Ltd.) calibrated by image analysis. The obtained measurements showed that the volume-based average particle size (X) was 0.75 μm and the maximum particle size was 1.8 μm.

[0125] The average cross-sectional thickness (Y) of the microcapsules contained in the reversible thermochromic microcapsule pigment was measured by freezing an aqueous dispersion of the pigment in a reversible thermochromic composition colored state, eliminating any variation in the pigment's shape, and preparing a 50 μm-thick thin section sample using a microtome. The observed image was analyzed using a transmission electron microscope (product name: HT7700, manufactured by Hitachi High-Tech Corporation). The number of microcapsules within the field of view of the observed image was 150. The cross-sectional thicknesses of all microcapsules were calculated by image analysis, and the average cross-sectional thickness (Y) obtained from the average was 0.08 μm.

[0126] The resulting microcapsule pigment has a complete decolorization temperature t4 of 60°C and a complete color development temperature t1 of -25°C, and changes color from cyan to colorless when heated.

[0127] (Preparation of reversible thermochromic water-based ink composition) 10 parts of the obtained microcapsule pigment (previously cooled to develop color), 10 parts of glycerin, 1.2 parts of polyether phosphate ester (trade name: Phosphanol RS-410, manufactured by Toho Chemical Industry Co., Ltd.), 0.2 parts of preservative (pyridine-2-thiol 1-oxide, sodium salt, product name: Sodium Omadine, manufactured by Lonza Japan Co., Ltd.), 0.2 parts of preservative (3-iodo-2-propynyl butylcarbamate, product name: Glykasil 2000, manufactured by Lonza Japan Co., Ltd.), 0.02 parts of antifoaming agent, 0.1 parts of pH adjuster (citric acid), and 78.28 parts of water were uniformly mixed to obtain a reversible thermochromic aqueous ink composition.

[0128] The viscosity of the resulting water-based ink composition was measured and found to be 5.46 mPa·s at 20° C. and a rotation speed of 30 rpm. The resulting water-based ink composition was contained in a polystyrene ink cartridge.

[0129] Example 2 (Preparation of reversible thermochromic microcapsule pigment) The reversible thermochromic microcapsule pigment obtained in Example 1 was used.

[0130] (Preparation of reversible thermochromic water-based ink composition) 10 parts of the obtained microcapsule pigment (previously cooled to develop color), 6.5 parts of glycerin, 2.5 parts of 1,2-ethanediol, 1 part of 1,3-butanediol, 1.2 parts of polyether phosphate ester (trade name: Phosphanol RS-710, manufactured by Toho Chemical Industry Co., Ltd.), 0.2 parts of preservative (pyridine-2-thiol 1-oxide, sodium salt, product name: Sodium Omadine, manufactured by Lonza Japan Co., Ltd.), 0.2 parts of preservative (3-iodo-2-propynyl butylcarbamate, product name: Glykasil 2000, manufactured by Lonza Japan Co., Ltd.), 0.02 parts of antifoaming agent, 0.1 parts of pH adjuster (citric acid), and 78.28 parts of water were uniformly mixed to obtain a reversible thermochromic aqueous ink composition.

[0131] The viscosity of this water-based ink composition was measured and found to be 4.96 mPa·s at 20° C. and a rotation speed of 30 rpm. The resulting water-based ink composition was contained in a polystyrene ink cartridge.

[0132] Examples 3 to 20 The amounts of coating materials added and stirring speed conditions of Example 1 were changed as shown in Table 1 to prepare reversible thermochromic microcapsule pigments and reversible thermochromic water-based ink compositions of Examples 3 to 20.

[0133] Example 21 A reversible thermochromic microcapsule pigment and a reversible thermochromic water-based ink composition were obtained under the same conditions as in Example 16, except that the polyvinyl alcohol aqueous solution in Example 16 was changed to an 8% polyvinyl alcohol aqueous solution. The obtained water-based ink compositions were each housed in a polystyrene ink cartridge.

[0134] Comparison Example 1 A reversible thermochromic microcapsule pigment and a reversible thermochromic water-based ink composition were obtained by adjusting the amounts of coating materials added and the stirring speed conditions of Example 2 as shown in Table 1. The obtained water-based ink composition was housed in a polystyrene ink cartridge.

[0135] Comparison Example 2 A reversible thermochromic microcapsule pigment was obtained by adjusting the amounts of coating materials added and the stirring speed conditions of Example 1 as shown in Table 1. The resulting water-based ink composition was contained in a polystyrene ink cartridge.

[0136] Table 1 shows the average particle size (X), average cross-sectional thickness (Y), Y / X, and maximum particle size of the microcapsules contained in the reversible thermochromic microcapsule pigments obtained in Examples 1 to 21 and Comparative Examples 1 and 2. The maximum particle size of the microcapsules contained in the microcapsule pigment obtained in Example 21 was 5 μm or more, and the content of microcapsule pigments having particle sizes of 5 μm or more (large particle content) was 1.2 vol% based on the total volume of the microcapsule pigment. The large particle content in all other examples was 0 vol%.

[0137] The ink cartridge thus prepared was installed in an inkjet printer, and printing and evaluation of the ink composition were carried out according to the following procedure: During printing, the ink ejection amount and printing resolution were set to 10 pL per pixel and 600 dpi vertically and 600 dpi horizontally, respectively.

[0138] (Print color development) A straight line 0.2 mm wide was printed using an inkjet printer equipped with a cartridge, and the color development of the printed line was visually observed. The printing paper used was Inkjet Plain Paper, manufactured by Seiko Epson Corporation. The evaluation criteria were as follows: A: Very dark and clear. B: Strong. C: The color is slightly pale. Visibility is sufficient. D: The color is slightly pale, but there is no problem in practical use. E: The color is light and visibility is poor. There is a problem in practical use.

[0139] (Print definition) The characters "Komoro naru" were printed and the characters were visually observed. The same type of paper as that used for the evaluation of print color development was used for printing. The evaluation criteria were as follows: A: There is no blurring and the outline of the letters is clear. B: There is some fading or the outlines of the characters are slightly unclear, but this does not pose a problem for practical use. C: There is significant fading or the outlines of the characters are unclear, which poses a problem for practical use.

[0140] (Ink stability over time) The ink cartridge used to evaluate the color development of the printed image was stored at 40°C for 30 days, and then the ink cartridge was attached to an inkjet printer and a straight line 0.2 mm wide was printed. The color development of the printed line was visually compared with that of the printed line formed with the ink cartridge before storage.

[0141] The evaluation criteria were as follows: A: There is no change in the density of the printed lines. B: The printed lines formed by the ink cartridge after storage are slightly thinner. C: The printed lines formed with the ink cartridge after storage are somewhat thinner, but this does not pose a problem in practical use. D: The printed lines formed with the ink cartridge after storage are significantly thinner. This is problematic for practical use.

[0142] The evaluation results are shown in Table 1.

[0143] Application Examples Except for changing the components of the reversible thermochromic color-memory composition in Example 1 as follows, a reversible thermochromic microcapsule pigment and a reversible thermochromic water-based ink composition were prepared under the same conditions as in Example 1, and the ink compositions of Application Examples A to C were obtained.

[0144] Application example A (magenta) A reversible thermochromic composition comprising 6.0 parts of 9-ethyl-(3-methylbutyl)amino-spiro[12H-benzo[a]xanthen-12,1'(3H)-isobenzofuran]-3'-one as the component (a), 15.0 parts of 4,4'-(2-ethylhexylidene)bisphenol as the component (b), and 50.0 parts of 4-benzyloxyphenylethyl caprate as the component (c).

[0145] Application example B (yellow) A reversible thermochromic composition comprising 3.0 parts of 4-[2,6-bis(2-ethoxyphenyl)-4-pyridinyl]-N,N-dimethylbenzenamine as component (A), 9.0 parts of 2,2-bis(4-hydroxyphenyl)hexafluoropropane as component (B), and 50.0 parts of 4-benzyloxyphenylethyl caprate as component (C).

[0146] Application example C (Black color) A reversible thermochromic composition comprising 7.0 parts of 2-(2-chloroanilino)-6-di-n-butylaminofluoran as component (a), 15.0 parts of 1,1'-bis(4'-hydroxyphenyl)-n-dodecane as component (b), and 50.0 parts of 4-benzyloxyphenylethyl caprate as component (c).

[0147] (Making multi-color ink cartridges) The inks prepared in Example 1 and Application Examples A to C were stored in a single ink cartridge, and a multi-color ink cartridge capable of ejecting inks of four colors, magenta, cyan, yellow, and black, was produced.

[0148] [Table 1] [Explanation of symbols]

[0149] t1 full color temperature t2 color development start temperature t3 decolorization start temperature t4 complete color erasure temperature T1 complete discoloration temperature T2 decolorization start temperature T3 color development temperature T4 full color temperature 1 Ink supply device 2 Ink storage compartment 3 Printer head 3a Ink outlet 3b Ink intake 3c Internal flow path 4a Ink supply channel 4b Ink recovery channel 5. Pump 6 Wiping method 7 nozzles 8 ink outlet 9. Ink composition

Claims

[Claim 1] The invention described in the specification.

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