Thermochromic color-memorizing composition and thermochromic color-memorizing material using the same

Abstract

To provide a thermochromic color memory composition that employs a specific ester compound and exhibits a color memory effect in a low temperature range.SOLUTION: A thermochromic color memory composition comprising at least: (i) an electron-donating chromogenic organic compound, (ii) an electron-accepting compound, and (iii) a specific reaction medium for controlling the chromogenic reaction of the component (i) and the component (ii), wherein the thermochromic color memory composition undergoes color change with a hysteresis width (ΔH) of 8 to 100°C in a color density-temperature curve, wherein a complete coloring temperature t1 is equal to or lower than -30°C, and a complete decolorizing temperature t4 is in a range of -25 to 15°C.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a thermochromic color-memory composition and a thermochromic color-memory material using the same. [Background technology]

[0002] Conventionally, thermochromic color-memory compositions and thermochromic color-memory microcapsule pigments encapsulating the same have been disclosed, which exhibit large hysteresis characteristics in response to temperature changes, resulting in reversible color changes of coloring and decoloring, and which alternately and reversibly maintain either the colored state or the decolored state even after the heat or cold required for the color change is removed (see, for example, Patent Documents 1 to 10). This type of thermochromic color-memory material, unlike conventional reversible thermochromic materials that change color just before or just after a color-change temperature, and of the two states before and after the color-change, only one specific state exists at room temperature, and the other state is maintained while the heat or cold required to manifest that state is applied, and returns to the state it exhibits at room temperature once the application of heat or cold is removed, can selectively maintain either the color on the lower side or the color on the higher side of the color-change temperature at room temperature, and can alternately maintain the color by applying heat or cold as needed, so it is used in a variety of fields such as temperature-sensitive recording materials, toys, decorations, and printing. In addition, a counterfeit prevention medium has been disclosed in which a reversible thermochromic layer using such a thermochromic color memory material changes color in response to a temperature increase or decrease, making it possible to detect counterfeits (see, for example, Patent Document 11). The above-mentioned anti-counterfeiting medium comprises a reversible thermochromic layer containing thermochromic color-memory compositions, one of which is colored and the other of which is colorless, and which exhibit large hysteresis characteristics; when the temperature rises or falls, both thermochromic color-memory compositions become colorless or colored, and it is difficult for one of the thermochromic color-memory compositions to return to its pre-color-change state in which it is colored; and it functions as a temperature control indicator that can irreversibly determine whether the temperature has deviated from a specified temperature range.

[0003] In recent years, the so-called cold chain logistics system has become widespread. This system maintains the appropriate temperature range for items with low optimum temperature ranges, such as fresh foods, frozen foods, and pharmaceuticals, throughout the production, transportation, and consumption distribution processes, enabling the items to be distributed over a wide area without deteriorating in quality. In the cold chain, temperature must be controlled so that it can be reliably determined whether the items have been stored in a temperature environment exceeding the appropriate temperature range during the distribution process. By using a material that changes color when the temperature exceeds a predetermined range, it is possible to easily detect whether the item has exceeded the appropriate temperature range. While the above-described counterfeit prevention medium functions as a temperature control indicator that can irreversibly determine whether an item has exceeded the normal temperature range using a thermochromic color-memory material, when used with items with a low optimum temperature range, i.e., items with an optimum temperature range in the low temperature range, it is difficult for the thermochromic color-memory material to selectively retain its color, making it difficult to irreversibly determine whether the item has exceeded the appropriate temperature range. Furthermore, no thermochromic color-memorizing material capable of selectively memorizing and retaining color in a low temperature range has been disclosed so far. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-1369 [Patent Document 2] Japanese Patent Application Laid-Open No. 2006-137886 [Patent Document 3] Japanese Patent Application Laid-Open No. 2006-188660 [Patent Document 4] Japanese Patent Application Laid-Open No. 2008-280523 [Patent Document 5] International Publication No. 2010 / 131684 Brochure [Patent Document 6] International Publication No. 2012 / 046837 Brochure [Patent Document 7] International Publication No. 2014 / 200053 Brochure [Patent Document 8] International Publication No. 2015 / 119161 Brochure [Patent Document 9] International Publication No. 2016 / 027664 Brochure [Patent Document 10] International Publication No. 2018 / 155583 Brochure [Patent Document 11] Japanese Patent Application Laid-Open No. 2017-170664 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention provides a thermosensitive color-changing color-memory composition that uses a specific ester compound and exhibits a color-memory effect in a low temperature range. [Means for solving the problem]

[0006] The present invention provides a thermochromic color-memory composition comprising at least (i) an electron-donating organic color-forming compound, (ii) an electron-accepting compound, and (iii) a reaction medium represented by the following formula (1) that controls the color reaction of the components (i) and (ii). The composition exhibits hysteresis characteristics in a color density-temperature curve, exhibiting alternation between a colored state and a decolored state. In the process of increasing temperature from the colored state, the composition begins to decolor when it reaches a decolorization initiation temperature t3, and reaches a complete decolorization temperature t4 that is higher than the temperature t3. The thermochromic color-memory composition is required to be in a temperature range of 8 to 100°C, in which the composition becomes completely decolorized in a temperature range of 4 or higher, and as the temperature decreases from the decolorized state, it begins to color when it reaches the color development starting temperature t2 and becomes completely colored in a temperature range of t1 or lower, which is lower than t2, and exhibits hysteresis characteristics, in which the composition changes color with a hysteresis width (ΔH) of 8 to 100°C in terms of color density-temperature curve, and the complete color development temperature t1 is -30°C or lower and the complete decolorization temperature t4 is in the range of -25 to 15°C. [ka] [wherein R1 represents a group represented by the following formula (2) or a cycloalkyl group, and R2 represents a linear or branched alkyl group having 1 to 13 carbon atoms] [ka] (wherein X represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms) Furthermore, the requirements are that the R1 is a group in which X is a hydrogen atom or a methyl group, or a cyclohexyl group, and that the R2 is a linear or branched alkyl group having 3 to 11 carbon atoms. Furthermore, the thermochromic color-memory material uses the thermochromic color-memory composition, and is a thermochromic color-memory microcapsule pigment that encapsulates the thermochromic color-memory composition, or a thermochromic color-memory resin particle in which the thermochromic color-memory composition is dispersed in a thermoplastic resin or a thermosetting resin. Furthermore, the present invention requires a thermochromic, color-memorizing liquid composition in which the thermochromic, color-memorizing material is dispersed in a vehicle. Furthermore, the present invention also requires a laminate in which a reversible thermochromic layer containing the thermochromic color-memorizing material is provided on a support. Furthermore, the present invention is also concerned with a thermochromic, color-memory molding resin composition obtained by melt-blending the thermochromic, color-memory material with a thermoplastic resin, a thermosetting resin, or a wax. [Effects of the Invention]

[0007] The present invention provides a thermochromic color-memory composition using a specific ester compound that exhibits a color-memory effect at low temperatures, and it allows for greater freedom in selecting a reaction medium, further increasing the utility of this type of thermochromic color-memory material. [Brief explanation of the drawings]

[0008] [Figure 1] 1 is a graph illustrating the hysteresis characteristics in the color density-temperature curve of the thermochromic color-memory composition of the present invention. [Figure 2] 1 is a graph illustrating an example of the color change behavior of a temperature control indicator to which the thermochromic color-memory composition of the present invention is applied. [Figure 3] 10 is a graph illustrating another example of the color change behavior of a temperature control indicator to which the thermochromic color-memory composition of the present invention is applied. [Figure 4] 10 is a graph illustrating another example of the color change behavior of a temperature control indicator to which the thermochromic color-memory composition of the present invention is applied. [Figure 5] 10 is a graph illustrating another example of the color change behavior of a temperature control indicator to which the thermochromic color-memory composition of the present invention is applied. [Figure 6] 1 is a longitudinal cross-sectional view illustrating an example of a temperature control indicator to which the thermochromic color-memory composition of the present invention is applied. [Figure 7] 1 is a longitudinal cross-sectional view illustrating an example of a reversible thermochromic layer in a temperature control indicator to which the thermochromic color-memory composition of the present invention is applied. [Figure 8] FIG. 10 is a longitudinal cross-sectional view illustrating another example of a temperature control indicator to which the thermochromic color-memory composition of the present invention is applied. [Figure 9] FIG. 10 is a longitudinal cross-sectional view illustrating another example of a temperature control indicator to which the thermochromic color-memory composition of the present invention is applied. [Figure 10] FIG. 10 is a longitudinal cross-sectional view illustrating another example of a temperature control indicator to which the thermochromic color-memory composition of the present invention is applied. [Figure 11] FIG. 10 is a longitudinal cross-sectional view illustrating another example of a temperature control indicator to which the thermochromic color-memory composition of the present invention is applied. [Figure 12] 1 is a longitudinal cross-sectional view illustrating an example of a reversible thermochromic molded body in a temperature control indicator to which the thermochromic color-memory composition of the present invention is applied. [Figure 13] FIG. 10 is a longitudinal cross-sectional view illustrating another example of a temperature control indicator to which the thermochromic color-memory composition of the present invention is applied. [Figure 14] FIG. 10 is a longitudinal cross-sectional view illustrating another example of a temperature control indicator to which the thermochromic color-memory composition of the present invention is applied. [Figure 15] FIG. 10 is a longitudinal cross-sectional view illustrating another example of a temperature control indicator to which the thermochromic color-memory composition of the present invention is applied. [Figure 16] FIG. 10 is a longitudinal cross-sectional view illustrating another example of a temperature control indicator to which the thermochromic color-memory composition of the present invention is applied. [Figure 17] FIG. 10 is a longitudinal cross-sectional view illustrating another example of a temperature control indicator to which the thermochromic color-memory composition of the present invention is applied. DETAILED DESCRIPTION OF THE INVENTION

[0009] In this invention, the "low temperature range" refers to a temperature range that includes the appropriate temperature range for items to which the cold chain is applied, such as fresh foods, frozen foods, and pharmaceuticals, and is the temperature range that can be reached by cooling devices commonly used in everyday living environments, such as refrigerators and freezers, specifically a temperature range above -30°C and below 10°C. In addition, the "ultra-low temperature range" refers to a temperature range lower than the low temperature range, which is difficult to reach using cooling devices commonly used in everyday living environments, specifically a temperature range of -30°C or below.

[0010] The hysteresis characteristics in the color density-temperature curve of the thermochromic color-memory composition (reversible thermochromic composition having color memory properties) applied to the present invention will be described below. In Figure 1, the vertical axis represents color density and the horizontal axis represents temperature. The change in color density due to temperature changes progresses along the arrows. Here, A represents the density at temperature t4 (hereinafter referred to as the complete decolorization temperature) at which the completely decolorized state is reached, B represents the density at temperature t3 (hereinafter referred to as the decolorization onset temperature) at which the completely colored state can be maintained, C represents the density at temperature t2 (hereinafter referred to as the color development onset temperature) at which the completely decolorized state can be maintained, and D represents the density at temperature t1 (hereinafter referred to as the complete color development temperature) at which the completely colored state is reached. The discoloration temperature range is the temperature range between the complete color development temperature t1 and the complete decolorization temperature t4, in which either the colored state or the decolorized state can be maintained, and the temperature range between the color development start temperature t2 and the decolorization start temperature t3, which is the region where the difference in color density is large, is the actual discoloration temperature range. Specifically, a thermochromic color-memory composition in a decolorized state can be cooled to a temperature below the color-development initiation temperature t2 to begin changing to a colored state, and can be brought to a fully colored state by cooling to a temperature below the full color-development temperature t1, and this state can be maintained unless the temperature of the thermochromic color-memory composition is raised to the decolorization initiation temperature t3. In addition, by applying heat to a thermochromic color-memory composition in a colored state and heating it to a temperature equal to or higher than the decolorization starting temperature t3, the change to the decolorized state can be initiated, and by heating it to a temperature equal to or higher than the complete decolorization temperature t4, the composition can be brought to a completely decolorized state, and this state can be maintained unless the temperature of the thermochromic color-memory composition is lowered to the color development starting temperature t2. The length of the line segment EF is a measure of the contrast of the discoloration, and the length of the line segment HG passing through the midpoint of the line segment EF is a temperature range indicating the degree of hysteresis (hereinafter referred to as the hysteresis range (ΔH)). The larger ΔH is, the easier it is to maintain the states before and after discoloration. ΔH, which allows the states before and after discoloration to be maintained, is 8°C or higher, specifically in the range of 8 to 100°C. Since this makes it even easier to maintain the states before and after discoloration, ΔH is preferably 20 to 100°C, and more preferably 30 to 100°C. Here, Δt, which is the difference between the complete discoloration temperature t4 and the discoloration onset temperature t3, or the difference between the color development onset temperature t2 and the complete color development temperature t1, is a measure of the sensitivity to discoloration. A range of Δt = 1 to 20°C is practical, and Δt = 1 to 15°C is preferred, and Δt = 1 to 10°C is more preferred. In the present invention, the thermochromic color-memory material uses a thermochromic color-memory composition, and the hysteresis characteristics in the color density-temperature curve of the thermochromic color-memory material are the hysteresis characteristics in the color density-temperature curve of the thermochromic color-memory composition.

[0011] The color-memory effect exhibited by thermochromic color-memory materials is only exhibited in systems that use specific compounds as constituents selected from esters, ketones, ethers, etc., which control the color reaction. The present invention aims to provide a thermochromic color-memory composition that uses a specific ester compound and exhibits a color-memory effect in the low temperature range, and aims to increase the freedom of selection of reaction media and further increase the utility of this type of thermochromic color-memory material.

[0012] 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. 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, a phenylindolyl azaphthalide compound and a derivative thereof are preferred. Examples of the fluoran compound include aminofluoran compounds, alkoxyfluoran compounds, and derivatives thereof.

[0013] Examples of the electron-donating color-forming organic compound include: 3,3-bis(4-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-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-isoamylamino)-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, 9-ethyl-(3-methylbutyl)amino-spiro[12H-benzo[a]xanthen-12,1′(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] Examples include: 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.

[0014] Component (b), ie, the electron accepting compound, is a compound that accepts electrons from component (a) and functions as a developer for component (a). The electron-accepting compound may be selected from a group of compounds having an active proton, a group of pseudo-acidic compounds (a group of compounds that are not acids but act as acids in the thermochromic color-memory composition to cause the component (A) to develop color), and a group of compounds having an electron vacancy, etc. Among the above-mentioned component (B), a compound selected from a group of compounds having an active proton is preferred.

[0015] 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 the 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.

[0016] 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. The compound having a phenolic hydroxyl group preferably has at least two benzene rings. In addition, the compound having a phenolic hydroxyl group may have a substituent such as an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, a carboxyl group and its ester or amide group, or a halogen atom.

[0017] 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.

[0018] 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:

[0019] 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:

[0020] 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-octylphenyl) sulfide, bis(5-chloro-2-hydroxyphenyl) sulfide, bis(3-cyclohexyl-4-hydroxyphenyl) sulfide, bis(4-hydroxyphenylthioethoxy)methane, 1,5-(4-hydroxyphenylthio)-3-oxypentane, 1,8-bis(4-hydroxyphenylthio)-3,6-dioxaoctane Examples include:

[0021] Examples of compounds having three phenolic hydroxyl groups include pyrogallol, phloroglucinol, phloroglucinolcarboxylic acid, gallic acid, octyl gallate, and dodecyl gallate.

[0022] 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'-[(4-ethoxy-3-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:

[0023] 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:

[0024] Examples of carboxylic acids and derivatives thereof include: 3,5-di(α-methylbenzyl)salicylic acid, 4-(2-p-methoxyphenyloxyethoxy)salicylic acid, 4-hydroxyphenylbenzoic acid, 4-chlorobenzoic acid, 4-[2-(p-methoxyphenoxy)ethyloxy]salicylic acid, 4-[3-(p-tolylsulfonyl)propyloxy]salicylic acid, 5-[p-(2-p-methoxyphenoxyethoxy)cumyl]salicylic acid, 4-octyloxycarbonylaminosalicylic acid, 3,5-distyrenated salicylic acid, N-(p-toluenesulfonyl)-glycine, N-(p-toluenesulfonyl)-alanine, N-(p-toluenesulfonyl)-β-alanine, N-phenylaminocarbonyl-glycine, N-phenylaminocarbonyl-valine, N-(m-tolylaminocarbonyl)-phenylalanine, N-(m-tolylaminocarbonyl)-cysteine-S-benzyl, N-(m-tolylaminocarbonyl)-methionine, N-(m-tolylaminocarbonyl)-tyrosine, N-(p-tolylaminocarbonyl)-phenylalanine, N-(p-tolylaminocarbonyl)-cysteine-S-benzyl, N-(p-tolylaminocarbonyl)-methionine, N-(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:

[0025] 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.

[0026] As component (b), a compound having a phenolic hydroxyl group is preferred because it can more effectively exhibit thermochromic properties, but it may also be a compound selected from aromatic carboxylic acids, aliphatic carboxylic acids having 2 to 5 carbon atoms, carboxylic acid metal salts, acidic phosphate esters and their metal salts, or 1,2,3-triazole and its derivatives.

[0027] In the present invention, by using an ester compound of a specific structure as component (c), i.e., a reaction medium that reversibly induces an electron donor / acceptor reaction between the above components (a) and (b) in a specific temperature range, a thermochromic color-memory composition having a color change temperature in a low temperature range can be obtained. The ester compound applicable to the present invention is a compound represented by formula (1).

[0028] The ester compound represented by formula (1) will be described. [ka] [wherein R1 represents a group represented by the following formula (2) or a cycloalkyl group, and R2 represents a linear or branched alkyl group having 1 to 13 carbon atoms] [ka] (wherein X represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms)

[0029] The ester compound represented by formula (1) can be obtained by an esterification reaction between an alcohol selected from benzyl alcohol, alkylbenzyl alcohol having a linear or branched alkyl group having 1 to 3 carbon atoms, or cycloalkylmethanol, and a carboxylic acid having 2 to 14 carbon atoms.

[0030] Specific examples of alkylbenzyl alcohols having a linear or branched alkyl group having 1 to 3 carbon atoms include 2-methylbenzyl alcohol, 3-methylbenzyl alcohol, 4-methylbenzyl alcohol, 2-ethylbenzyl alcohol, 3-ethylbenzyl alcohol, 4-ethylbenzyl alcohol, 2-n-propylbenzyl alcohol, 3-n-propylbenzyl alcohol, 4-n-propylbenzyl alcohol, 2-isopropylbenzyl alcohol, 3-isopropylbenzyl alcohol, and 4-isopropylbenzyl alcohol. In the alkylbenzyl alcohol having a linear or branched alkyl group having 1 to 3 carbon atoms, the substitution position of the alkyl group is not particularly limited, but from the viewpoints of availability and cost, alkylbenzyl alcohol in which the alkyl group is substituted at the 4-position (para-position) is preferably used.

[0031] Specific examples of cycloalkylmethanol include cyclopropanemethanol, cyclobutanemethanol, cyclopentanemethanol, cyclohexanemethanol, cycloheptanemethanol, and cyclooctanemethanol.

[0032] Specific examples of carboxylic acids having 2 to 14 carbon atoms include acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, pivalic acid, hydroangelic acid, isovaleric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, and myristic acid.

[0033] Among the ester compounds represented by formula (1), specific examples of ester compounds obtained by an esterification reaction between benzyl alcohol and a carboxylic acid having 2 to 14 carbon atoms include benzyl acetate, benzyl butyrate, benzyl caproate, benzyl caprylate, benzyl caprate, benzyl laurate, and benzyl myristate. Specific examples of ester compounds obtained by esterification of alkylbenzyl alcohols having a linear or branched alkyl group with 1 to 3 carbon atoms with carboxylic acids having 2 to 14 carbon atoms include 2-methylbenzyl acetate, 3-methylbenzyl acetate, 4-methylbenzyl acetate, 2-ethylbenzyl acetate, 3-ethylbenzyl acetate, 4-ethylbenzyl acetate, 2-n-propylbenzyl acetate, 3-n-propylbenzyl acetate, 4-n-propylbenzyl acetate, 2-methylbenzyl butyrate, 3-methylbenzyl butyrate, 4-methylbenzyl butyrate, and 2-ethylbenzyl butyrate. Benzyl, 3-ethylbenzyl butyrate, 4-ethylbenzyl butyrate, 2-n-propylbenzyl butyrate, 3-n-propylbenzyl butyrate, 4-n-propylbenzyl butyrate, 2-methylbenzyl caproate, 3-methylbenzyl caproate, 4-methylbenzyl caproate, 2-ethylbenzyl caproate, 3-ethylbenzyl caproate, 4-ethylbenzyl caproate, 2-n-propylbenzyl caproate, 3-n-propylbenzyl caproate, 4-n-propylbenzyl caproate, 2-methylbenzyl caprylate, 3-methylbenzyl caprylate, 4-Methylbenzyl caprylate, 2-ethylbenzyl caprylate, 3-ethylbenzyl caprylate, 4-ethylbenzyl caprylate, 2-n-propylbenzyl caprylate, 3-n-propylbenzyl caprylate, 4-n-propylbenzyl caprylate, 2-methylbenzyl caprate, 3-methylbenzyl caprate, 4-methylbenzyl caprate, 2-ethylbenzyl caprate, 3-ethylbenzyl caprate, 4-ethylbenzyl caprate, 2-n-propylbenzyl caprate, 3-n-propylbenzyl caprate, 4-n- Propyl benzyl, 2-methyl benzyl laurate, 3-methyl benzyl laurate, 4-methyl benzyl laurate, 2-ethyl benzyl laurate, 3-ethyl benzyl laurate, 4-ethyl benzyl laurate, 2-n-propyl benzyl laurate, 3-n-propyl benzyl laurate, 4-n-propyl benzyl laurate, 2-methyl benzyl myristate, 3-methyl benzyl myristate, 4-methyl benzyl myristate, 2-ethyl benzyl myristate, 3-ethyl benzyl myristate, 4-ethyl benzyl myristate,Examples include 2-n-propylbenzyl myristate, 3-n-propylbenzyl myristate, and 4-n-propylbenzyl myristate. Specific examples of ester compounds obtained by the esterification reaction of a cycloalkylmethanol with a carboxylic acid having 2 to 14 carbon atoms include cyclopropylmethyl acetate, cyclobutylmethyl acetate, cyclopentylmethyl acetate, cyclohexylmethyl acetate, cycloheptylmethyl acetate, cyclooctylmethyl acetate, cyclopropylmethyl butyrate, cyclobutylmethyl butyrate, cyclopentylmethyl butyrate, cyclohexylmethyl butyrate, cycloheptylmethyl butyrate, cyclooctylmethyl butyrate, cyclopropylmethyl caproate, cyclobutylmethyl caproate, cyclopentylmethyl caproate, cyclohexylmethyl caproate, cycloheptylmethyl caproate, cyclooctylmethyl caproate, cyclopropylmethyl caprylate, cyclobutylmethyl caprylate ... Examples include cyclopropylmethyl caprylate, cyclohexylmethyl caprylate, cycloheptylmethyl caprylate, cyclooctylmethyl caprylate, cyclopropylmethyl caprate, cyclobutylmethyl caprate, cyclopentylmethyl caprate, cyclohexylmethyl caprate, cycloheptylmethyl caprate, cyclooctylmethyl caprate, cyclopropylmethyl laurate, cyclobutylmethyl laurate, cyclopentylmethyl laurate, cyclohexylmethyl laurate, cycloheptylmethyl laurate, cyclooctylmethyl laurate, cyclopropylmethyl myristate, cyclobutylmethyl myristate, cyclopentylmethyl myristate, cyclohexylmethyl myristate, cycloheptylmethyl myristate, and cyclooctylmethyl myristate.

[0034] With respect to R1, it is preferable that X is a hydrogen atom or a methyl group, or a cyclohexyl group, since this makes it easier to obtain a compound with a larger hysteresis width (ΔH). R2 is preferably a linear or branched alkyl group having 3 to 11 carbon atoms, more preferably a linear or branched alkyl group having 5 to 9 carbon atoms, and even more preferably a linear or branched alkyl group having 7 carbon atoms, since this makes it easier to obtain a compound with a discoloration temperature in a lower range.

[0035] In formula (1), it is preferable that R1 is a group represented by formula (2) or a cycloalkyl group, and R2 is a linear or branched alkyl group having 3 to 11 carbon atoms, because this makes it easier to obtain a compound with a lower discoloration temperature and a larger hysteresis width. In the above structure, it is preferable that R1 is a group in which X is a hydrogen atom or a methyl group, or a cyclohexyl group. Furthermore, it is more preferable that R1 is a group represented by formula (2) or a cycloalkyl group, and R2 is a linear or branched alkyl group having 5 to 9 carbon atoms. In the above structure, it is preferable that R1 is a group in which X is a hydrogen atom or a methyl group, or a cyclohexyl group. Furthermore, in formula (1), it is more preferable that R1 is a group represented by formula (2) or a cycloalkyl group, and R2 is a linear or branched alkyl group having 7 carbon atoms, and the compound is an ester compound represented by the following formula (3). [ka] [wherein R1 represents a group represented by the following formula (4) or a cycloalkyl group] [ka] (wherein X represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms)

[0036] Specific examples of the ester compound represented by formula (3) include benzyl caprylate, 2-methylbenzyl caprylate, 3-methylbenzyl caprylate, 4-methylbenzyl caprylate, 2-ethylbenzyl caprylate, 3-ethylbenzyl caprylate, 4-ethylbenzyl caprylate, 2-n-propylbenzyl caprylate, 3-n-propylbenzyl caprylate, 4-n-propylbenzyl caprylate, 2-isopropylbenzyl caprylate, 3-isopropylbenzyl caprylate, 4-isopropylbenzyl caprylate, cyclopropylmethyl caprylate, cyclobutylmethyl caprylate, cyclopentylmethyl caprylate, cyclohexylmethyl caprylate, cycloheptylmethyl caprylate, and cyclooctylmethyl caprylate. In formula (3), R1 is preferably a group in which X is a hydrogen atom or a methyl group, or a cyclohexyl group, and specific examples thereof include benzyl caprylate, 2-methylbenzyl caprylate, 3-methylbenzyl caprylate, 4-methylbenzyl caprylate, and cyclohexylmethyl caprylate.

[0037] The thermochromic color-memory composition exhibits a reversible color change (coloring and decoloring) and exhibits a wide hysteresis width (ΔH) in the color density-temperature curve during this reversible color change. Furthermore, by containing an ester compound with a specific structure, the color change temperature is in a low range, and the composition can alternately memorize and retain both colors below and above the color change temperature. By heating or cooling as needed, the composition can effectively exhibit the ability to reversibly reproduce and memorize either color. This provides a thermochromic color-memory composition that is highly applicable to a variety of applications, such as thermochromic display, decoration, and teaching tools, as well as a thermochromic color-memory microcapsule pigment encapsulating the composition, and a thermochromic color-memory resin particle containing the thermochromic color-memory composition.

[0038] The component (c) may be a combination of two or more ester compounds represented by formula (1) or formula (3). The component (c) may further contain a conventionally known component (c), such as an ester other than that represented by formula (1) or formula (3), an alcohol, a carboxylic acid, a ketone, or an amide. When compounds other than those represented by formulas (1) and (3) are contained, their content is preferably 1 to 30 mass %, more preferably 2 to 25 mass %, and even more preferably 3 to 20 mass %, of the total amount of component (c).

[0039] The composition ratio of components (a), (b), and (c) in the thermochromic color-memory composition depends on the concentration, color change temperature, color change form, and type of each component, but generally, the component ratio that will give the desired properties is 1 part of component (a) to 1 part of component (b), preferably 0.1 to 100, more preferably 0.1 to 50, even more preferably 0.5 to 20, and particularly preferably 2 to 20, and 1 to 800, more preferably 5 to 200, even more preferably 5 to 100, and particularly preferably 10 to 100, of component (c) (all of the above ratios are in parts by mass).

[0040] Although the thermochromic color-memory composition can be used as a thermochromic color-memory material by being encapsulated in microcapsules to form a thermochromic color-memory microcapsule pigment (hereinafter sometimes referred to as a "microcapsule pigment"), or by being dispersed in a thermoplastic resin or a thermosetting resin to form thermochromic color-memory resin particles (hereinafter sometimes referred to as "resin particles"), it is preferable to encapsulate the thermochromic color-memory composition in microcapsules to use it as a microcapsule pigment. This is because encapsulation in microcapsules makes it possible to form a chemically and physically stable pigment, and furthermore, the thermochromic color-memory composition can maintain the same composition and exhibit the same effects under various use conditions.

[0041] Microencapsulation can be performed by known methods such as interfacial polymerization, in situ polymerization, liquid curing coating, phase separation from an aqueous solution, phase separation from an organic solvent, melt-dispersion cooling, air suspension coating, spray drying, etc., and can be appropriately selected depending on the application. Furthermore, a secondary resin film can be provided on the surface of the microcapsules depending on the purpose to impart durability or to modify the surface properties for practical use. In addition, by blending a non-thermochromic colorant such as a general dye or pigment during microencapsulation, an alternating color change from color (1) to color (2) can be achieved. The thermochromic color-memory microcapsule pigment preferably has a mass ratio of inclusions to wall film of 7:1 to 1:1, and by having the mass ratio of inclusions to wall film within the above range, it is possible to prevent a decrease in color density and clarity during color development. More preferably, the mass ratio of inclusions to wall film is 6:1 to 1:1.

[0042] The average particle size of the microencapsulated pigment or resin particles is preferably 0.1 to 50 μm, more preferably 0.1 to 30 μm, and even more preferably 0.5 to 20 μm. If the average particle size of the microencapsulated pigment or resin particles exceeds 50 μm, dispersion stability and processability tend to be poor. On the other hand, if the average particle size is less than 0.1 μm, it becomes difficult to achieve high-density color development. Furthermore, by micronizing the microencapsulated pigment or resin particles, it is possible to increase ΔH relative to ΔH of the three-component composition. The average particle size was measured by determining the particle area using image analysis particle size distribution measurement software (manufactured by Mountec Co., Ltd., product name: MacView), calculating the diameter equivalent to a circle with a projected area (Heywood diameter) from the area of ​​the particle area, and measuring the average particle size of particles equivalent to a sphere with the same volume using this value. Furthermore, if the particle size of all or the majority of particles exceeds 0.2 μm, it is also possible to measure the average particle size of particles equivalent to an equal volume sphere using the Coulter method using a particle size distribution analyzer (product name: Multisizer 4e, manufactured by Beckman Coulter, Inc.). Furthermore, the volumetric particle size and average particle size may be measured using a calibrated laser diffraction / scattering particle size distribution analyzer (manufactured by HORIBA, Ltd., product name: LA-300) based on values ​​measured using the above software or a measuring device using the Coulter method.

[0043] The above-mentioned microcapsule pigment or resin particles can be dispersed in a vehicle to form an ink composition (hereinafter sometimes referred to as "ink"), which can be used as a temperature-sensitive color-changing, color-memory liquid composition such as a printing ink used in screen printing, offset printing, process printing, gravure printing, coater printing, and pad printing, or a paint used in brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, and dip coating.

[0044] The above vehicle may also contain additives such as resins, crosslinking agents, curing agents, drying agents, plasticizers, viscosity modifiers, dispersants, ultraviolet absorbers, infrared absorbers, antioxidants, light stabilizers, dissolution aids, anti-settling agents, smoothing agents, gelling agents, matting agents, penetrating agents, pH adjusters, foaming agents, coupling agents, moisturizing agents, antifungal agents, preservatives, and rust inhibitors, as required.

[0045] When applying or printing the above-mentioned thermochromic color-memorizing liquid composition, the substrate is not particularly limited, and examples thereof include paper, synthetic paper, fibers, knitted fabrics, woven fabrics, nonwoven fabrics, synthetic leather, leather, plastics, glass, elastomers, rubber, ceramics, metals, wood, stone, etc., and the form may be uneven, but flat, sheet, or film forms are preferred. Furthermore, a reversible thermochromic layer containing a thermochromic color-memory composition, a thermochromic color-memory microcapsule pigment, or resin particles can be provided on the support to obtain a laminate (printed material). In the case where a non-thermochromic layer (including an image) is pre-formed on the support, the non-thermochromic layer can be made to appear or disappear by a reversible thermochromic layer due to a change in temperature, thereby further diversifying the appearance of the change. Furthermore, the thermochromic, color-memory microcapsule pigment or resin particles can be melt-blended with thermoplastic resins, thermosetting resins, waxes, etc., and used as a thermochromic, color-memory molding resin composition in the form of pellets, powder, or paste, and molded articles in the form of three-dimensional objects of any shape, such as films, sheets, plates, filaments, rods, pipes, etc. can be obtained by general-purpose injection molding, extrusion molding, blow molding, cast molding, etc. In addition, by blending a non-thermochromic colorant such as a general dye or pigment into the above liquid composition or resin composition, an alternating color change from color (1) to color (2) can be brought about.

[0046] A transparent protective layer can be provided on the laminate or a molded article formed using the resin composition to impart scratch resistance, or a layer containing a light stabilizer or a transparent metallic luster pigment can be provided on the laminate or a molded article formed using the resin composition to impart light resistance. Examples of light stabilizers include ultraviolet absorbers, antioxidants, antiaging agents, singlet oxygen quenchers, superoxide anion quenchers, ozone quenchers, visible light absorbers, and infrared absorbers. Examples of transparent metallic luster pigments include pigments having a core material such as natural mica, synthetic mica, glass pieces, alumina, or transparent film pieces whose surface is coated with a metal oxide such as titanium oxide. Light resistance can be imparted by providing a layer in which these light stabilizers or transparent metallic luster pigments are fixed in a dispersed state.

[0047] Specific examples of products using the thermochromic, color-memory composition and the thermochromic, color-memory microcapsule pigment containing the same, or the thermochromic, color-memory resin particles include various printed materials such as labels, cards, recording materials, and anti-counterfeiting media; storage containers such as transport containers and packaging containers for items that require refrigeration or freezing, such as food, seafood, fresh flowers, blood, chemicals, pharmaceuticals, precision machinery, and artwork; ice packs, ice packs, temperature control indicators, etc.

[0048] The temperature control indicator of the present invention is configured so that within the appropriate temperature range of an item requiring temperature control or its storage container, the color of the first thermochromic color-memory material (thermochromic color-memory material A) in a colored state is visible (initial state), and when the temperature control indicator in its initial state is placed in a temperature environment exceeding the appropriate temperature range, the first thermochromic color-memory material loses its color, and the color of the first thermochromic color-memory material in a decolored state is visible (State 1). Once a temperature control indicator is placed in a temperature environment exceeding the appropriate temperature range, it is difficult to return it to its initial state, making it possible to irreversibly determine that the temperature has deviated from the appropriate temperature range.

[0049] The appropriate temperature range for items requiring temperature control, such as fresh foods, frozen foods, and pharmaceuticals, to which the cold chain applies, is in the low temperature range; from the standpoint of hygiene management, fresh foods are set at 0 to 10°C, and frozen foods are set at -18°C or below, preferably -25°C or below. Pharmaceuticals are mainly set at 10°C or below, particularly 2 to 8°C. The appropriate temperature range varies depending on the item, but the appropriate temperature range for most items to which the cold chain applies is above -30°C and is in the low temperature range of 10°C or below, and they are distributed and stored in a refrigerated or frozen state. The above-mentioned items or their storage containers, whose appropriate temperature range is in the low temperature range, are stored in warehouses or cooling devices such as refrigerators or freezers classified under the Warehousing Business Act as Class F1 (temperature range of above -30°C to below -20°C), Class C1 (temperature range of above -20°C to below -10°C), Class C2 (temperature range of above -10°C to below 0°C), or Class C3 (temperature range of above 0°C to below 10°C), and can be stored within the appropriate temperature range by appropriately selecting from cooling devices commonly used in everyday living environments, such as cooling devices that use Peltier elements, cooling devices filled with refrigerants such as cold water or ice chips, refrigerators, and freezers, depending on the appropriate temperature range of the item or its storage container.

[0050] By setting the complete decolorization temperature t4 of the first thermosensitive color-changing color memory property applied to the present invention within the range of -25 to 15°C, the temperature management indicator of the present invention can be effectively functioned for temperature management within the appropriate temperature range of an article that requires temperature management or its storage container. When the temperature management indicator in which the first thermosensitive color-changing color memory material is in a colored state is placed in a temperature environment exceeding the appropriate temperature range, the first thermosensitive color-changing color memory material in the colored state decolorizes and the temperature management indicator changes color, so that it can be detected that the article or its storage container has deviated from the temperature environment exceeding the appropriate temperature range. Also, in order to determine that the article or its storage container has deviated from the temperature environment exceeding the appropriate temperature range by the color change of the temperature management indicator, the complete decolorization temperature t4 of the first thermosensitive color-changing color memory material and the upper limit temperature T of the appropriate temperature range of the above article or its storage container satisfy T < t4. Further, since the temperature management of the article or its storage container can be strictly performed, the difference between the temperature t4 and the temperature T [ΔT = (complete decolorization temperature t4) - (upper limit temperature T of the appropriate temperature range)] is preferably 0°C < ΔT ≦ 3°C, more preferably 0°C < ΔT ≦ 2°C, and even more preferably 0°C < ΔT ≦ 1°C.

[0051] Since the complete coloring temperature t1 of the first thermosensitive color-changing color memory material applied to the present invention is -30°C or lower, based on the Warehouse Business Act used for storing an article that requires temperature management or its storage container within the appropriate temperature range, the first thermosensitive color-changing color memory material is not easily colored by a warehouse or a cooling device classified as Class F1 or Classes C1 to 3, specifically, by a cooling tool generally used in daily living environments. That is, in order to color the first thermosensitive color-changing color memory material, a warehouse or a cooling device capable of cooling in an ultra-low temperature range, which is a temperature range lower than the appropriate temperature range, is required. Examples of such a warehouse or a cooling device include warehouses or cooling devices such as refrigerators classified as Class F2 (-40°C or higher and -30°C or lower temperature range), Class F3 (-50°C or higher and -40°C or lower temperature range), and Class F4 (-50°C or lower temperature range) based on the Warehouse Business Act, and examples thereof include cooling tools filled with refrigerants such as alcohol and liquid nitrogen, and dry ice. A temperature control indicator in which a first thermochromic color-memory material is brought into a colored state by using a warehouse or cooling device classified as Class F2 to Class C1 to Class C4 under the Warehousing Business Act can maintain the first thermochromic color-memory material in a colored state in a temperature range below the complete discoloration temperature t4 of the first thermochromic color-memory material, and since the complete discoloration temperature t4 is in the range of -25 to 15°C, the temperature control indicator can also be maintained in its initial state by using a warehouse or cooling device classified as Class F1 or Class C1 to Class C3 under the Warehousing Business Act, which is used to store items or their storage containers that require temperature control.

[0052] Therefore, by setting the complete color development temperature t1 of the first thermochromic color-memory material at -30°C or below, the temperature control indicator of the present invention can be cooled in an ultra-low temperature range using a warehouse or cooling device classified as Class F2 to 4 under the Warehousing Business Act to cause the first thermochromic color-memory material to develop color, and the color of the first thermochromic color-memory material in the colored state can be visually recognized (initial state). Furthermore, because the initial state can be maintained in a temperature environment below the complete color-disappearance temperature t4 of the first thermochromic color-memory material, the temperature control indicator can be maintained in its initial state by using cooling devices commonly used in everyday living environments, specifically warehouses or cooling devices classified as Class F1 or Class C1 to C3 under the Warehousing Business Act. Furthermore, by setting the complete decolorization temperature t4 of the first thermochromic color-memory material in the range of -25 to 15°C, it is possible to control the temperature of an article or its storage container, which has an appropriate temperature range in the low temperature range. When the temperature control indicator in its initial state is placed in a temperature environment that exceeds the appropriate temperature range, the first thermochromic color-memory material in its colored state will decolorize, and the color of the thermochromic color-memory material in its decolorized state will become visible (State 1). Therefore, because the temperature control indicator exhibits a color change when changing from the initial state to State 1, it is possible to detect that the temperature control indicator has deviated from the appropriate temperature range. Even if a temperature control indicator in State 1 is stored again in the warehouse or cooling device where the item or its storage container was stored, the first thermochromic color-memory material will not change color and will remain in a decolorized state. This is because the temperature control indicator of the present invention has a full color change temperature t1 of the first thermochromic color-memory material in the ultra-low temperature range (below -30°C), and cooling devices commonly used in everyday living environments cannot cool the temperature control indicator to the temperature required to return it to its initial state. Therefore, it is difficult to return the temperature control indicator to its initial state, making it possible to irreversibly determine whether the temperature has exceeded the appropriate temperature range.

[0053] Furthermore, in a temperature control indicator in which the first thermochromic color-memory material is in a decolorized state, the first thermochromic color-memory material remains in the decolorized state unless cooled to a temperature below the full color-developing temperature t1, so that, for example, the first thermochromic color-memory material is in the decolorized state in a room temperature (25°C) environment. Furthermore, because the full color-developing temperature t1 of the first thermochromic color-memory material is -30°C or lower, it is difficult to cause the first thermochromic color-memory material to develop color using cooling devices commonly used in everyday living environments. In other words, in a room temperature environment, the color shown by the first thermochromic color memory material in its colored state is not visible, and only when it is cooled to an ultra-low temperature range does the color of the first thermochromic color memory material in its colored state become visible, making it possible to use it as an anti-counterfeiting medium that has anti-counterfeiting functions.

[0054] The complete discoloration temperature t4 of the first thermochromic color-memory material is preferably in the range of −25 to 5° C., more preferably in the range of −25 to 0° C. When the complete discoloration temperature t4 is within the above temperature range, the temperature control indicator of the present invention can function effectively in articles or their storage containers that have an appropriate temperature range in a lower temperature range.

[0055] Once the temperature control indicator is initialized using a warehouse or cooling device classified as Class F2 to 4 under the Warehousing Business Act, the warehouse or cooling device is no longer required. Therefore, by not placing the warehouse or cooling device that can initialize the temperature control indicator adjacent to the warehouse or cooling device that controls the temperature of items that require temperature control or their storage containers, it becomes easier to prevent tampering by cooling the temperature control indicator again to return it to its initial state after it has been exposed to a temperature environment that exceeds the appropriate temperature range and the first thermochromic color-memory material has become discolored. Furthermore, the environment in which the temperature control indicator can be reset to its initial state and the environment in which the temperature of the items or their storage containers that require temperature control are controlled are located far apart, and the temperature control indicator that has been reset to its initial state in a warehouse or cooling device classified as Class F2 to Class F4 under the Warehousing Business Act is transported to a warehouse or cooling device that controls the temperature of the items or their storage containers while maintaining its initial state, thereby controlling the temperature of the items or their storage containers.This is advantageous because it makes it easier to prevent tampering by cooling the temperature control indicator again to return it to its initial state after it has fallen into a temperature environment that exceeds the appropriate temperature range and the first thermochromic color memory material has become discolored.

[0056] The complete color development temperature t1 of the first thermochromic color memory material is preferably −40° C. or lower, and more preferably −50° C. or lower. When the complete color development temperature t1 is within the above temperature range, it becomes more difficult to return a temperature control indicator in which the first thermochromic color memory material has become discolored due to deviation from an appropriate temperature environment beyond the appropriate temperature range to its initial state using a cooling device commonly used in everyday living environments. This makes it easier to irreversibly determine that the temperature control indicator has deviated from the appropriate temperature range, and also makes it easier to prevent tampering by cooling the temperature control indicator again to return it to its initial state.

[0057] The hysteresis width (ΔH) of the first thermochromic color-memory material is preferably 20 to 100° C., more preferably 30 to 100° C., even more preferably 30 to 80° C., and particularly preferably 30 to 60° C. When the hysteresis width (ΔH) is within the above range, the temperature control indicator can more easily function effectively in temperature control of an article or its storage container whose appropriate temperature range is in the low temperature range.

[0058] In the temperature control indicator of the present invention, the first thermochromic color-memory material preferably has a hysteresis width (ΔH) of 20 to 100°C, a complete color-developing temperature t1 of -40°C or less, and a complete discoloration temperature t4 in the range of -25 to 15°C, and more preferably a hysteresis width (ΔH) of 30 to 100°C. This makes it easier to maintain the states before and after discoloration, makes it easier to irreversibly determine if the temperature environment has exceeded the appropriate temperature range, and makes it more difficult to tamper with the temperature control indicator by cooling it again to return it to its initial state. Furthermore, it is more preferable that the first thermochromic color-memory material has a hysteresis width (ΔH) of 20 to 100°C, a complete color-developing temperature t1 of -50°C or less, and a complete discoloration temperature t4 in the range of -25 to 15°C, and more preferably a hysteresis width (ΔH) of 30 to 100°C.

[0059] The temperature control indicator of the present invention may further comprise a second thermochromic color-memory material (thermochromic color-memory material B) in addition to the first thermochromic color-memory material described above. The second thermochromic color-memory material has a color-change temperature in the low temperature range, similar to the first thermochromic color-memory material described above, and is a thermochromic color-memory microcapsule pigment encapsulating a thermochromic color-memory composition consisting of at least components (a), (b), and (c), or a thermochromic color-memory resin particle in which the thermochromic color-memory composition is dispersed in a thermoplastic resin or a thermosetting resin. Complete decolorization temperature t of the second thermochromic color-memory material 4′is in the range of -25 to 15°C and is less than the complete decolorization temperature t4 of the first thermosensitive discoloring color memory material, that is, t 4′ <satisfies t4, and further, regarding the difference between the complete decolorization temperature t4 and the complete decolorization temperature t 4′ 〔Δt4 = (complete decolorization temperature t4) - (complete decolorization temperature t 4′ )〕, 5 ≤ Δt4 ≤ 40 is satisfied. Thereby, the temperature management indicator can function effectively for temperature management within the appropriate temperature range of an article that requires temperature management or its storage container, and it can be irreversibly determined that it has been placed in a specific temperature range within the appropriate temperature range, and a temperature management indicator having a temperature management function in the specific temperature range can be obtained.

[0060] A temperature management indicator comprising a second thermosensitive discoloring color memory material has, at a temperature t 4′ less than, a color in which the colors of the thermosensitive discoloring color memory materials in the coloring state are mixed is visually recognized (initial state). When the temperature management indicator in the initial state is placed in a specific temperature range (temperature t 4′ or more and less than the temperature t4), the second thermosensitive discoloring color memory material in the coloring state decolorizes, and the color by the first thermosensitive discoloring color memory material in the coloring state is visually recognized (state 2). Further, when the temperature management indicator is placed in a temperature environment exceeding the appropriate temperature range, the first thermosensitive discoloring color memory material in the coloring state decolorizes, and the colors of the thermosensitive discoloring color memory materials in the decolorized state are visually recognized (state 3). And once the temperature management indicator placed in the specific temperature range or once placed in a temperature environment exceeding the appropriate temperature range is difficult to return to the initial state, it can be irreversibly detected that it has been placed in the specific temperature range or deviated from the temperature environment exceeding the appropriate temperature range.

[0061] The complete coloring temperature t of the second thermosensitive discoloring color memory material 1′Because the temperature is -30°C or below, the second thermochromic color-memory material exhibits the same thermochromic behavior as the first thermochromic color-memory material, and the second thermochromic color-memory material does not easily change color in a warehouse or refrigeration equipment classified as Class F1 or Class C1-3 under the Warehousing Business Act, which is used to store temperature-controlled items or their storage containers at an appropriate temperature range. In other words, to cause the second thermochromic color-memory material to change color, a warehouse or refrigeration equipment classified as Class F2-4 under the Warehousing Business Act is required. By using such a warehouse or refrigeration equipment, it is possible to cause both the first thermochromic color-memory material and the second thermochromic color-memory material to change color. In a warehouse or cooling device classified as Class F2 to Class F4 under the Warehousing Business Act, a temperature control indicator in which a first thermochromic color-memory material and a second thermochromic color-memory material are in a colored state is maintained at a temperature t 4′ Since each thermochromic color-memory material can be maintained in its colored state in a temperature range below 100°C, the temperature control indicator can be maintained in its initial state even when using a warehouse or cooling device classified as Class F1 or Class C1 to C3 under the Warehousing Business Act, which is used to store items or their storage containers that require temperature control.

[0062] Therefore, the temperature control indicator further comprising the second thermochromic color-memorizing material has a complete color-developing temperature t1 of the first thermochromic color-memorizing material and a complete color-developing temperature t2 of the second thermochromic color-memorizing composition. 1′ By setting both of the temperatures to -30°C or lower, the thermochromic color-memory materials can be cooled in an ultra-low temperature range using a warehouse or cooling device classified as Class F2 to Class 4 under the Warehousing Business Law, and the respective thermochromic color-memory materials can be colored together, so that a color obtained by mixing the colors of the respective thermochromic color-memory materials in the colored state can be visually recognized (initial state). 4′ It can maintain its initial state in a temperature environment below the complete decolorization temperature t 4′Since the temperature is in the range of -25 to 15°C, the temperature control indicator can be maintained in its initial state by using cooling equipment commonly used in everyday living environments, specifically, a warehouse or cooling device classified as Class F1 or Class C1 to C3 under the Warehousing Business Act. The second thermochromic color memory material completely loses its color at a temperature t 4′ is in the range of -25 to 15°C and is less than the complete decolorization temperature t4 of the first thermochromic color memory material, and the complete decolorization temperature t4 and the complete decolorization temperature t 4′ By satisfying 5≦Δt4≦40 for the difference (Δt4) between the temperature control indicator and the temperature control indicator, the temperature control function in the specific temperature range of the item or its storage container, which has an appropriate temperature range in the low temperature range, can be achieved. 4′ When the temperature control indicator is placed in a temperature environment below temperature t4, the second thermochromic color memory material in the colored state loses its color, and the color of the first thermochromic color memory material in the colored state becomes visible (state 2). Therefore, since the color change occurs when the temperature control indicator changes from the initial state to state 2, it can be detected that the temperature control indicator has been placed in a specific temperature range. Even if the temperature control indicator in State 2 is stored again in the warehouse or cooling device in which the article or its storage container was stored, the second thermochromic color-memory material does not change color and remains in a decolorized state. This is because the temperature control indicator of the present invention does not change color until the complete color-changing temperature t 1′ This is because the temperature is in the ultra-low temperature range (below -30°C), and cooling devices commonly used in everyday living environments cannot cool the temperature to the level required to reset the temperature control indicator to its initial state, making it difficult to return the temperature control indicator to its initial state. Therefore, it is possible to irreversibly determine that the indicator has been placed in a specific temperature range within the appropriate temperature range. When a temperature control indicator in State 2 is placed in a temperature environment that exceeds the appropriate temperature range, the first thermochromic color memory material in the colored state loses its color, and the color of each thermochromic color memory material in the decolored state becomes visible (State 3). Also, even if a temperature control indicator in its initial state is placed in a temperature environment that exceeds the appropriate temperature range, all of the thermochromic color memory materials in the colored state lose their color, and it similarly enters State 3. Therefore, because the temperature control indicator exhibits a color change when it changes from the initial state to State 3 or from State 2 to State 3, it can be detected that the temperature control indicator has deviated from the appropriate temperature range. Even if the temperature control indicator in State 3 is stored again in the warehouse or cooling device where the article or its storage container was stored, each thermochromic color-memory material does not change color and remains in a decolorized state. This is because the temperature control indicator of the present invention has a temperature difference between the complete color development temperature t1 of the first thermochromic color-memory composition and the complete color development temperature t2 of the second thermochromic color-memory composition. 1′ This is because the temperature is in the ultra-low temperature range (below -30°C), and cooling devices commonly used in everyday living environments cannot cool the temperature to the temperature required to reset the temperature control indicator to its initial state, making it difficult to return the temperature control indicator to its initial state. Therefore, it is possible to irreversibly determine if the temperature environment has exceeded the appropriate temperature range.

[0063] Such a temperature control indicator can be used, for example, at a full color temperature t 4′ Frozen goods that have been distributed or stored within the appropriate temperature range below are classified as frozen goods within a specific temperature range (temperature t 4′ This can be used for temperature control when thawing at temperatures above t4 (but below t5). When a frozen product or its storage container is placed in a specific temperature range, the temperature control indicator in its initial state changes from the initial state to State 2 and exhibits a color change, making it possible to detect that the product has been placed in the specific temperature range and to determine that the frozen product has been thawed in the specific temperature range.

[0064] In addition, a temperature control indicator in which both the first thermochromic color memory material and the second thermochromic color memory material are in a decolorized state has a full-color development temperature t1 and a full-color development temperature t 1′ Unless cooled below, each thermochromic color memory material is maintained in a decolorized state. For example, in a room temperature (25 °C) environment, each thermochromic color memory material is in a decolorized state. Also, the full-color development temperature t1 of the first thermochromic color memory material and the full-color development temperature t 1′ of the second thermochromic color memory material are -30 °C or lower, so it is difficult to cause each thermochromic color memory material to develop color with a cooling tool generally used in daily life environments. That is, in a room temperature environment, the colors shown by each thermochromic color memory material in a colored state are not visible, and only by cooling to an ultra-low temperature range, the color by the first thermochromic color memory material in a colored state or the color by the second thermochromic color memory material in a colored state becomes visible. Therefore, it can be used as an anti-counterfeiting medium having a function as anti-counterfeiting. Here, the temperature t1 and the temperature t 1′ are not substantially the same (for example, t 1′ < t1 is satisfied), when the temperature exceeds t 1′ and the first thermochromic color memory material develops color in the temperature range of t1 or lower, and the color by the first thermochromic color memory material in a colored state is visible, and the second thermochromic color memory material develops color in the temperature range of t 1′ or lower, and a color in which the colors by each thermochromic color memory material in a colored state are mixed becomes visible. That is, since a difference occurs in the visible color at a specific temperature (a temperature exceeding t 1′ and lower than t1), it can be used as an anti-counterfeiting medium with enhanced anti-counterfeiting function. Note that "substantially the same" means that the temperature t1 and the temperature t 1′ are exactly the same temperature, and in the present invention, the absolute value (|Δt1|) of the difference (Δt1) between the temperature t1 and the temperature t1 satisfies |Δt1 = (full-color development temperature t1 of the first thermochromic color memory material) - (full-color development temperature t 1′ ) of the second thermochromic color memory material| ≦ 3 °C.

[0065] Complete decolorization temperature t of the second thermochromic color-memory material 4′ The complete decolorization temperature t is preferably in the range of -25 to 5°C, and more preferably in the range of -25 to 0°C. 4′ When the temperature is within the above-mentioned range, the temperature control indicator of the present invention can function effectively for articles or storage containers thereof having an appropriate temperature range in a lower range.

[0066] Complete color fading temperature t4 and complete color fading temperature t 4′ The difference (Δt4) is preferably 5≦Δt4≦30, and more preferably and practically 5≦Δt4≦20. When Δt4 is in the above range, the temperature control indicator can more easily function effectively in temperature control within a specific temperature range of an item or its storage container whose appropriate temperature range is in the low temperature range.

[0067] Furthermore, even in the case of a temperature control indicator comprising a second thermochromic color-memory material, once it has been initialized using a warehouse or cooling device classified as Class F2 to Class F4 under the Warehousing Business Act, the warehouse or cooling device is no longer required. Therefore, by not placing the warehouse or cooling device that can initialize the temperature control indicator adjacent to the warehouse or cooling device that manages the temperature of items or their storage containers that require temperature management, it becomes easier to prevent tampering by cooling a temperature control indicator that has been placed in a specific temperature range and the second thermochromic color-memory material has become discolored, or that has been placed in a temperature environment that exceeds the appropriate temperature range and both thermochromic color-memory materials have become discolored, and then returning it to its initial state. Furthermore, the environment in which the temperature control indicator can be reset to its initial state and the environment in which the temperature of the items or their storage containers that require temperature control are controlled are located far apart, and the temperature control indicator that has been reset to its initial state in a warehouse or cooling device classified as Class F2 to 4 under the Warehousing Business Act is transported to a warehouse or cooling device that controls the temperature of the items or their storage containers while maintaining its initial state, thereby controlling the temperature of the items or their storage containers.This is advantageous because it makes it easier to prevent tampering by cooling a temperature control indicator that has been placed in a specific temperature range and the second thermochromic color memory material has become discolored, or that has been placed in a temperature environment that exceeds the appropriate temperature range and both thermochromic color memory materials have become discolored, and then returning it to its initial state.

[0068] The complete color development temperature t of the second thermochromic color memory material 1′ The complete color development temperature t is preferably −40° C. or lower, and more preferably −50° C. or lower. 1′ By being within the above temperature range, it becomes more difficult to return a temperature control indicator that has been placed in a specific temperature range and the second thermochromic color memory material has become discolored, or that has been placed in a temperature environment that exceeds the appropriate temperature range and both thermochromic color memory materials have become discolored, to its initial state using a cooling device that is commonly used in everyday living environments.This makes it easier to irreversibly determine that the temperature control indicator has been placed in a specific temperature range or that it has been placed in a temperature environment that exceeds the appropriate temperature range, and also makes it easier to prevent tampering by cooling the temperature control indicator again to return it to its initial state.

[0069] The hysteresis width (ΔH′) of the second thermochromic color-memory material is preferably 20 to 100° C., more preferably 30 to 100° C., even more preferably 30 to 80° C., and particularly preferably 30 to 60° C. When the hysteresis width (ΔH′) is within the above range, the temperature control indicator can more easily function effectively in temperature control within a specific temperature range of an article or its storage container whose appropriate temperature range is in the low temperature range.

[0070] When the temperature control indicator further comprises a second thermochromic color-memory material, the hysteresis width (ΔH′) of the second thermochromic color-memory material is 20 to 100°C, and the complete color-changing temperature t 1′ is below -40°C, and the complete decolorization temperature t 4′ is in the range of -25 to 15°C and is less than the complete decolorization temperature t4 of the first thermochromic color memory material, and the temperature t4 and the temperature t 4′ The difference (Δt4) between the temperature and the temperature change preferably satisfies 5≦Δt4≦40, and the hysteresis width (ΔH′) is preferably 30 to 100°C. This makes it easier to maintain the states before and after the color change, makes it easier to irreversibly determine whether the indicator has been placed in a specific temperature range or has been placed in a temperature environment that exceeds the appropriate temperature range, and makes it more difficult to tamper with the temperature control indicator by cooling it again to return it to its initial state. Furthermore, the hysteresis width (ΔH′) of the second thermochromic color-memory material is 20 to 100°C, the complete color development temperature t1 is -50°C or less, and the complete decolorization temperature t 4′ is in the range of -25 to 15°C and is less than the complete decolorization temperature t4 of the first thermochromic color memory material, and the complete decolorization temperature t4 and the complete decolorization temperature t 4′ It is more preferable that the difference (Δt4) between the temperature and the temperature satisfies 5≦Δt4≦40, and the hysteresis width (ΔH) is preferably 30 to 100°C.

[0071] When the temperature control indicator of the present invention further comprises a second thermochromic color-memory material, if the component (A) of each thermochromic color-memory material is the same, each thermochromic color-memory material will show the same color in the colored state, so the color seen in the temperature control indicator in the initial state and the color seen in the temperature control indicator in State 2, where only the first thermochromic color-memory material is in the colored state, will be the same color. The color seen in the initial state is more intense than the color seen in State 2, but the visible change when the temperature control indicator changes from the initial state to State 2 is a change in shade, and the temperature control indicator will change color when it is in a specific temperature range (temperature t 4′Therefore, it may be difficult to determine whether the first thermochromic color memory material and the second thermochromic color memory material have been placed at a temperature lower than t4. Therefore, it is preferable that the first thermochromic color memory material and the second thermochromic color memory material have different component (A), i.e., electron-donating color-forming organic compound, and it is more preferable that each thermochromic color memory material exhibits a different color in the colored state.

[0072] When the components (A) of each thermochromic color-memory material are different from each other and show different colors in the color-developing state, the color seen in the temperature control indicator in the initial state where all the thermochromic color-memory materials are in the color-developing state is different from the color seen in the temperature control indicator in State 2 where only the first thermochromic color-memory material is in the color-developing state. Therefore, the visible change when the temperature control indicator changes from the initial state to State 2 is a change in hue, and the temperature control indicator changes in the specific temperature range (temperature t 4′ As a result, it is possible to clearly and easily determine whether the temperature is lower than t4.

[0073] The temperature control indicator of the present invention has a first thermochromic color-memory material having a complete color-developing temperature t1, a color-developing start temperature t2, and a color-discoloring start temperature t3, and a second thermochromic color-memory material having a complete color-developing temperature t4, 1′ , color onset temperature t 2′ , and decolorization start temperature t 3′ The temperatures t1 and t2 may be "almost the same." 1′ , t2 and t 2′ , t3 and t 3′ ) are the same temperature, and in the present invention, the absolute value (|Δt'|) of the difference (Δt') between the temperatures of the first thermochromic color memory material and the second thermochromic color memory material is 3°C or less, specifically, |Δt' = [temperatures (t1, t2, t3) of the first thermochromic color memory material] - [temperatures (t 1′ , t 2′ , t 3′ ))|≦3℃.

[0074] The complete color development temperature t1 of the first thermochromic color memory material and the complete color development temperature t of the second thermochromic color memory material 1′ , the color development start temperature t2 of the first thermochromic color memory material and the color development start temperature t 2′ , the first thermochromic color memory material's color-fading initiation temperature t3 and the second thermochromic color memory material's color-fading initiation temperature t 3′ The color change behavior of the temperature control indicators, which are substantially identical, is shown in Figure 2. In Figure 2, the solid line is the color density-temperature curve of the first thermochromic color-memory material, and the dashed line is the color density-temperature curve of the second thermochromic color-memory material. In the initial state, the temperature control indicator is visible as a mixture of the colors of the thermochromic color-memory materials in the color-developing state. 4′ The initial temperature control indicator is maintained at a temperature below t 4′ When the second thermochromic color memory material is placed in a temperature environment below temperature t4, the color of the second thermochromic color memory material disappears. 1′ In the temperature range exceeding temperature t1 and below temperature t4, the color of the first thermochromic color memory material in the colored state is visible (state 2). When placed in a temperature environment of temperature t4 or higher, the first thermochromic color memory material in the colored state disappears, and the color disappears at temperatures t1 and t2. 1′ Within the temperature range exceeding 100°C, the color of each thermochromic color memory material in the decolorized state is visually recognized (state 3). The temperature control indicators are designed to change the temperature from the initial state when each thermochromic color-memory material is in a colored state to a specific temperature range within the appropriate temperature range (temperature t 4′When placed at a temperature below t4, the second thermosensitive discoloring color memory material in the colored state fades, changing to a color different from the color of the temperature control indicator in the initial state. Therefore, it is possible to detect that an article that requires temperature control or its storage container has been placed in a specific temperature range within the appropriate temperature range, and it has a temperature control function. Also, when placed in a temperature environment exceeding the appropriate temperature range (temperature t4 or higher) from this state, the first thermosensitive discoloring color memory material in the colored state fades, and within the appropriate temperature range, it changes to a color different from the color in the initial state and the color when placed in the specific temperature range. Therefore, it is possible to easily detect that it has deviated to a temperature environment exceeding the appropriate temperature range. Note that even when the complete coloring temperature t1 of the first thermosensitive discoloring color memory material and the complete coloring temperature t of the second thermosensitive discoloring color memory material 1′ , the starting coloring temperature t2 of the first thermosensitive discoloring color memory material and the starting coloring temperature t of the second thermosensitive discoloring color memory material 2′ are not substantially the same, it shows the same color change behavior as described above. When temperature t1 and temperature t 1′ are not substantially the same and t1 < t 1′ is satisfied, the temperature control indicator in state 2 exceeds temperature t 1′ and only the color by the first thermosensitive discoloring color memory material in the colored state is visible within the temperature range exceeding temperature t and below temperature t4. The temperature control indicator in state 3 has the color of each thermosensitive discoloring color memory material in the faded state visible within the temperature range exceeding temperature t 1′ . Also, when temperature t1 and temperature t 1′ are not substantially the same and t 1′ < t1 is satisfied, the temperature control indicator in state 2 exceeds temperature t 1′ and only the color by the first thermosensitive discoloring color memory material in the colored state is visible within the temperature range exceeding temperature t and below temperature t4. The temperature control indicator in state 3 has the color of each thermosensitive discoloring color memory material in the faded state visible within the temperature range exceeding temperature t1.

[0075] The complete coloring temperature t1 of the first thermosensitive discoloring color memory material and the complete coloring temperature t of the second thermosensitive discoloring color memory material 1′, the color development start temperature t2 of the first thermochromic color memory material and the color development start temperature t 2′ are approximately the same, and the color-fading starting temperature t3 of the first thermochromic color-memory material and the color-fading starting temperature t 3′ are not substantially the same, and the decolorization starting temperature t3 of the first thermochromic color memory material is equal to or lower than the complete decolorization temperature t 4′ The color change behavior of the temperature control indicator in the following cases is shown in Figures 3 and 4. In Figures 3 and 4, the solid line represents the color density-temperature curve of the first thermochromic color-memory material, and the dashed line represents the color density-temperature curve of the second thermochromic color-memory material. The temperature control indicator is a temperature difference between the first thermochromic color memory material and the second thermochromic color memory material, as shown in FIG. 3′ The temperature control device exhibits the same color change behavior as when the temperature is approximately the same, and can detect that an item requiring temperature control or its storage container has been placed in a specific temperature range within the appropriate temperature range.The device has a temperature control function and can easily detect when the item has deviated from the appropriate temperature range and is in a temperature environment that exceeds the appropriate temperature range.

[0076] The complete color development temperature t1 of the first thermochromic color memory material and the complete color development temperature t of the second thermochromic color memory material 1′ , the color development start temperature t2 of the first thermochromic color memory material and the color development start temperature t 2′ are approximately the same, and the color-fading starting temperature t3 of the first thermochromic color-memory material and the color-fading starting temperature t 3′ are not substantially the same, and the decolorization starting temperature t3 of the first thermochromic color memory material is equal to or lower than the complete decolorization temperature t 4′ The color change behavior of the temperature control indicator when the temperature is greater than 100°C is shown in Figure 5. In Figure 5, the solid line represents the color density-temperature curve of the first thermochromic color-memory material, and the dashed line represents the color density-temperature curve of the second thermochromic color-memory material. The temperature control indicator is shown in Figure 2, and is the temperature at which the first thermochromic color-memory material starts to fade (t3) and the temperature at which the second thermochromic color-memory material starts to fade (t4). 3′ The temperature control device exhibits the same color change behavior as when the temperature is approximately the same, and can detect that an item requiring temperature control or its storage container has been placed in a specific temperature range within the appropriate temperature range.The device has a temperature control function and can easily detect when the item has deviated from the appropriate temperature range and is in a temperature environment that exceeds the appropriate temperature range.

[0077] The temperature control indicators shown in Figures 2 to 5 are in an initial state where the color of each thermochromic color-memory material in a color-developing state is mixed and visible, and are in a specific temperature range (temperature t 4′ When the temperature control indicator is placed in a temperature range exceeding the appropriate temperature range (below t4), the color of the first thermochromic color memory material in its colored state is visible, but in the temperature control indicators shown in Figures 2 to 4, the first thermochromic color memory material begins to fade in the specific temperature range, and the color visible in the temperature control indicator is lighter than the color of the first thermochromic color memory material in its fully colored state. Therefore, the change from the color of the first thermochromic color memory material in its colored state, which is visible when the temperature control indicator is placed in the specific temperature range, to the color of each thermochromic color memory material in its faded state, which is visible when the temperature control indicator is placed in a temperature environment exceeding the appropriate temperature range, may be unclear. 5, in the specific temperature range, the first thermochromic color-memory material is in a fully colored state and the second thermochromic color-memory material is in a fully decolorized state, so the color seen in the temperature control indicator in State 2 is the color of the first thermochromic color-memory material in a fully colored state. Therefore, there is a clear change from the color seen when the temperature control indicator is placed in the specific temperature range due to the first thermochromic color-memory material in a colored state to the color seen when each thermochromic color-memory material is in a decolorized state when the temperature environment exceeds the appropriate temperature range. From the above, the complete color development temperature t1 of the first thermochromic color memory material and the complete color development temperature t 1′, the color development start temperature t2 of the first thermochromic color memory material and the color development start temperature t 2′ are approximately the same, and the color-fading starting temperature t3 of the first thermochromic color-memory material and the color-fading starting temperature t 3′ are not substantially the same, and the decolorization starting temperature t3 of the first thermochromic color memory material is equal to or lower than the complete decolorization temperature t 4′ Larger is preferred.

[0078] As shown in Figure 6, the temperature control indicator of the present invention can be configured by providing a reversible thermochromic layer (2) containing a thermochromic color-memory material such as a thermochromic color-memory microcapsule pigment or resin particles on a support (3). The reversible thermochromic layer (2) can be a first reversible thermochromic layer (reversible thermochromic layer A) (21) containing a first thermochromic color-memory material (thermochromic color-memory material A). Furthermore, when the temperature management indicator of the present invention comprises a second thermochromic color memory material, the reversible thermochromic layer may be, as shown in Figure 7, a configuration in which a second reversible thermochromic layer (reversible thermochromic layer B) (22) containing a second thermochromic color memory material (thermochromic color memory material B) is provided on a first reversible thermochromic layer (21), a configuration in which a first reversible thermochromic layer (21) is provided on the second reversible thermochromic layer (22), or a reversible thermochromic layer (23) containing a first thermochromic color memory material and a second thermochromic color memory material. As shown in Figure 8, a non-thermochromic layer (4) containing a non-thermochromic colorant such as a general dye or pigment may be provided between the support and the reversible thermochromic layer, or a non-thermochromic colorant may be contained in the reversible thermochromic layer provided on the support. By using a thermochromic color-memory material in combination with a non-thermochromic colorant, an enantiochromatic color change from color (1) to color (2) can be achieved.

[0079] When a reversible thermochromic layer is provided on a support, a thermochromic color-memory liquid composition such as ink or paint in which a thermochromic color-memory material is dispersed in a vehicle containing a binder resin can be printed or applied onto the support by a printing method such as screen printing, offset printing, gravure printing, coater, or transfer printing, or by a coating method such as brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, or dip coating, to provide a reversible thermochromic layer on the support.

[0080] The support is not particularly limited, and examples thereof include paper, synthetic paper, fabrics such as fibers, knitted fabrics, woven fabrics, and nonwoven fabrics, synthetic leather, leather, plastics, glass, elastomers, rubber, ceramics, metals, wood, and stone. The support may have an uneven shape, but flat, sheet, or film shapes are preferred.

[0081] The binder resin is not particularly limited as long as it does not affect the coloring, fading, discoloration, etc. of the thermochromic color-memory material, and examples thereof include general-purpose resins, such as ionomer resins, isobutylene-maleic anhydride copolymer resins, acrylonitrile-acrylic styrene copolymer resins, acrylonitrile-styrene copolymer resins, acrylonitrile-butadiene-styrene copolymer resins, acrylonitrile-chlorinated polyethylene-styrene copolymer resins, ethylene-vinyl chloride copolymer resins, ethylene-vinyl acetate copolymer resins, ethylene-vinyl acetate-vinyl chloride graft copolymer resins, vinylidene chloride resins, vinyl chloride resins, chlorinated vinyl chloride resins, vinyl chloride-vinylidene chloride copolymer resins, chlorinated polyethylene, chlorinated polypropylene, polyamide, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polystyrene, high-impact polystyrene, polypropylene, polymethylstyrene, polyacrylic esters, and polymethyl methacrylate. , epoxy acrylate resin, alkylphenol resin, rosin-modified phenolic resin, rosin-modified alkyd resin, phenolic resin-modified alkyd resin, epoxy resin-modified alkyd resin, styrene-modified alkyd resin, acrylic-modified alkyd resin, aminoalkyd resin, vinyl chloride-vinyl acetate resin, styrene-butadiene resin, epoxy resin, unsaturated polyester, saturated polyester, polyurethane, alkyd resin, natural rubber, polyisobutylene, butyl rubber, polyvinyl alkyl ether, rosin, rosin ester, rosin derivative, polyterpene, oil-soluble phenolic resin, petroleum-based hydrocarbon resin, shellac, cyclized rubber, vinyl acetate-based emulsion resin, styrene-butadiene-based emulsion resin, acrylic acid ester-based emulsion resin, water-soluble alkyd resin, water-soluble melamine resin, water-soluble urea resin, water-soluble phenolic resin, water-soluble epoxy resin, water-soluble polybutadiene, cellulose acetate, cellulose nitrate, ethyl cellulose, and the like.

[0082] Furthermore, the temperature control indicator of the present invention can be easily attached to an object, such as an item requiring temperature control or its storage container, by providing an adhesive layer on the surface that comes into contact with the object. For example, in a configuration in which a reversible thermochromic layer is provided on a support, an adhesive layer (5) can be provided on the surface of the support (3) opposite to the surface on which the reversible thermochromic layer (2) is provided, as shown in FIG. 9. Furthermore, when the support is transparent, an adhesive layer (5) can be provided on the surface of the support (3) opposite to the surface on which the reversible thermochromic layer (2) is provided, as shown in FIG. 10. A temperature control indicator having an adhesive layer and having the above configuration can be used by adhering to an item requiring temperature control or its storage container.

[0083] In the configuration shown in Fig. 9, the adhesive used in the adhesive layer is not particularly limited as long as it can be attached to an article requiring temperature control or its storage container. Also, in the configuration shown in Fig. 10, the adhesive used in the adhesive layer is not particularly limited as long as it does not affect the coloring, fading, discoloration, etc. of the thermochromic color memory material and can be attached to an article requiring temperature control or its storage container. Examples of adhesives include acrylic resins, urethane resins, ethylene-vinyl acetate copolymer resins, rubber resins, silicone resins, and epoxy resins. Considering that the temperature control indicator of the present invention is used in low or ultra-low temperature ranges, it is preferable that the adhesive be one whose adhesiveness does not easily decrease in low or ultra-low temperature ranges, and acrylic resins, rubber resins, silicone resins, and epoxy resins are suitable.

[0084] Furthermore, when the temperature control indicator shown in Figure 10 is attached to an item requiring temperature control or its storage container, the transparent support functions as a transparent protective layer, so that the reversible thermochromic layer can be made durable without providing a transparent protective layer on top of the reversible thermochromic layer, and the thermosensitive color-memory composition contained in the adjacent reversible thermochromic layer can be protected from physical impact. The transparent support is not particularly limited as long as it is transparent, and examples thereof include plastic, glass, elastomer, rubber, etc. in the form of a plane, sheet, film, etc. Furthermore, the support may be colorless and transparent or colored and transparent. Considering that the temperature control indicator of the present invention will be used in low or ultra-low temperature ranges, it is preferable that the transparent support is one that is not easily embrittled in low or ultra-low temperature ranges, and a support made of a resin such as polyethylene, polyethylene terephthalate, or acrylonitrile-butadiene-styrene copolymer resin is suitable. Transparency refers to the property of transmitting light with wavelengths in the visible light region (the wavelength region of 380 to 780 nm specified in JIS B 7079). The light transmittance (visible light transmittance) in the visible light region of a transparent support is preferably 5% or more, more preferably 10% or more, and even more preferably 20% or more, so that the adjacent reversible thermochromic layer can be easily seen, and the color and color change exhibited by the reversible thermochromic layer can be seen. The visible light transmittance can be determined by placing a transparent support on a transparent substrate that transmits light with wavelengths in the visible light region, measuring the transmittance in the wavelength region from 380 nm to 780 nm using a spectrophotometer (Hitachi, Ltd., product name: U-3210), and calculating the intermediate value between the maximum and minimum values.

[0085] The temperature control indicator of the present invention has a configuration in which a reversible thermochromic layer is provided on a support, and the support can be a tamper-proof member (7) provided with an adhesive layer, and the reversible thermochromic layer (2) is provided on the tamper-proof member, as shown in Figure 11. By attaching a temperature control indicator with the above configuration to an object such as an item that requires temperature control or its storage container, if the item or its storage container is exposed to a temperature environment that exceeds the appropriate temperature range or is placed in a specific temperature range, it is possible to prevent tampering, such as peeling off the temperature control indicator, cooling it, and re-attaching it, or replacing it with a new temperature control indicator.

[0086] The tamper-preventing member exhibits a tamper-preventing function by being configured to provide an adhesive layer on the outermost layer of a laminated member. Examples of tamper-proof members that can be used include tamper-proof labels, tapes, or stickers, and examples of such tamper-proof members include those that, when attached to an adherend and then peeled off, have a tamper-proof function in which the adhesive layer is transferred to the adherend in the form of letters due to intra-layer peeling of the laminated structure. Other examples of tamper-proof members that have tamper-proof properties include a type in which, when peeled off after being stuck to an adherend, separation occurs at the interface of the laminated structure, and the layers deform, leaving no residue on the adherend, but the letters stand out on the tamper-proof member; and a type in which, by using a base material made of a fragile material, the base material is destroyed when peeled off after being stuck to an adherend, leaving traces of peeling on the adherend.

[0087] The temperature control indicator of the present invention may also use a reversible thermochromic molded body (8) having a configuration in which a thermochromic color-memory material is contained in a support. Examples of the reversible thermochromic molded body include a first reversible thermochromic molded body (reversible thermochromic molded body A) (81) containing a first thermochromic color-memory material (thermochromic color-memory material A) in a support. When the temperature control indicator of the present invention comprises a second thermochromic color-memory material, the reversible thermochromic molded body (8) may be, as shown in FIG. 12, a first reversible thermochromic molded body (81) containing a first thermochromic color-memory material in a support, and a second reversible thermochromic molded body (reversible thermochromic molded body B) (8) containing a second thermochromic color-memory material (thermochromic color-memory material B) in a transparent support. 2') laminated on a second reversible thermochromic molded body (82) containing a second thermochromic color-memory material in a support, a first reversible thermochromic molded body (81') containing a first thermochromic color-memory material in a transparent support laminated on the second reversible thermochromic molded body (82) containing a second thermochromic color-memory material in a support, and a reversible thermochromic molded body (83) containing a first thermochromic color-memory material and a second thermochromic color-memory material in a support. In addition, when the reversible thermochromic molded body is configured by laminating a first reversible thermochromic molded body and a second reversible thermochromic molded body, an adhesive layer described below can be provided on either side of one of the first reversible thermochromic molded body and the second reversible thermochromic molded body, and one reversible thermochromic molded body and the other reversible thermochromic molded body can be attached via the adhesive layer to form a reversible thermochromic molded body. The support may also contain a thermochromic color-memorizing material and a non-thermochromic colorant. The combined use of a thermochromic color-memorizing material and a non-thermochromic colorant can produce an alternating color change from color (1) to color (2).

[0088] A reversible thermochromic molded body containing a thermochromic color-memory material in a support can be obtained by molding a thermochromic color-memory molding resin composition prepared by melt-blending the above-mentioned thermochromic color-memory material into a molding resin selected from thermoplastic resins or thermosetting resins, using a general-purpose molding method such as injection molding, extrusion molding, blow molding, or cast molding. Examples of molding resins include linear low-density polyethylene, low-density polyethylene, medium-high-density polyethylene, ultra-high-density polyethylene, chlorinated polyethylene, polypropylene, chlorinated polypropylene, polyisobutylene, polybutadiene, polymethylpentene, polystyrene, polyethylene terephthalate, polybutylene terephthalate, polycyclohexylene-dimethylene-terephthalate, polyvinyl acetate, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, polyacrylic acid ester, polymethacrylic acid ester, polyamide, copolymer, Polymer polyamide, polyamideimide, polyacetal, polyvinyl formal, polyvinyl butyral, polyarylate, polyetherimide, polyether ether ketone, polycarbonate, polyphenylene ether, polyphenylene sulfide, polysulfone, fluororesin, ionomer resin, ethylene-propylene copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl alcohol copolymer resin, ethylene-acrylic acid ester copolymer resin, ethylene-methacrylic acid ester copolymer resin, ethylene-vinyl chloride copolymer resin, Vinyl chloride-propylene copolymer resin, vinyl chloride-vinylidene chloride copolymer resin, styrene-butadiene copolymer resin, acrylonitrile-vinylidene chloride copolymer resin, acrylonitrile-styrene copolymer resin, acrylonitrile-ethylene-styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, acrylonitrile-chlorinated polyethylene-styrene copolymer resin, acrylonitrile-acrylate-styrene copolymer resin, ethylene-vinyl acetate resin-vinyl chloride graft copolymer resin, methyl methacrylate-butadiene- Thermoplastic resins such as styrene copolymer resins, styrene-based thermoplastic elastomers, olefin-based thermoplastic elastomers, urethane-based thermoplastic elastomers, polyester-based thermoplastic elastomers, 1,2-polybutadiene-based thermoplastic elastomers, vinyl chloride-based thermoplastic elastomers, petroleum-based hydrocarbon resins, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, nitrocellulose, low molecular weight polyethylene, low molecular weight polypropylene, polybutene, coumarone-indene copolymers, and phenoxy plastics; Examples of thermosetting resins include epoxy resins, xylene resins, toluene resins, guanamine resins, epoxy acrylates, phenolic resins, unsaturated polyesters, furan resins, polyimides, poly(p-hydroxybenzoic acid), polyurethanes, urea resins, melamine resins, and silicone resins.

[0089] A reversible thermochromic molded body containing a thermochromic color-memory material in a transparent support can be obtained by molding a thermochromic color-memory molding resin composition prepared by melt-blending the above-mentioned thermochromic color-memory material into a transparent molding resin selected from a transparent thermoplastic resin or a thermosetting resin, using a general-purpose molding method such as injection molding, extrusion molding, blow molding, or cast molding. Examples of transparent molding resins include thermoplastic resins such as polyethylene, polypropylene, polyisobutylene, polybutadiene, polymethylpentene, polystyrene, polyethylene terephthalate, polybutylene terephthalate, polycyclohexylene-dimethylene-terephthalate, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, acrylic acid ester resin, methacrylic acid ester resin, polyvinyl butyral, polyarylate, polyetherimide, polycarbonate, polysulfone, ionomer resin, ethylene-propylene copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl alcohol copolymer resin, ethylene-acrylic acid ester copolymer resin, ethylene-methacrylic acid ester copolymer resin, acrylonitrile-styrene copolymer resin, and cycloolefin copolymer; Examples of the thermosetting resin include epoxy resin, epoxy acrylate, phenol resin, unsaturated polyester resin, urea resin, aryl resin, and silicone resin.

[0090] Furthermore, the temperature control indicator of the present invention can be easily attached to an object such as an article requiring temperature control or its storage container by providing an adhesive layer on the surface that comes into contact with the object. For example, in a configuration in which a thermochromic color-memory material is contained in a support, as shown in Figure 13, an adhesive layer (5) can be provided on either surface of a reversibly thermochromic molded product (8) and attached to the article requiring temperature control or its storage container. The adhesive used in the adhesive layer is not particularly limited as long as it does not affect the coloring, fading, or discoloration of the thermochromic color memory material and can be attached to an item or its storage container that requires temperature control. Examples of adhesives include acrylic resins, urethane resins, ethylene-vinyl acetate copolymer resins, rubber resins, silicone resins, and epoxy resins. Considering that the temperature control indicator of the present invention is used in low or ultra-low temperature ranges, it is preferable that the adhesive be one whose adhesiveness does not easily decrease in low or ultra-low temperature ranges, and acrylic resins, rubber resins, silicone resins, and epoxy resins are suitable.

[0091] Furthermore, a transparent protective layer can be provided on the reversible thermochromic layer or the reversible thermochromic molded body to impart durability, or a layer containing a light stabilizer or a transparent metallic luster pigment can be provided to impart light resistance. The transparent protective layer has the role of protecting the adjacent reversible thermochromic layer or the thermosensitive color-memory composition contained in the reversible thermochromic molded body from physical impact, and can be formed by printing or applying a solution containing a resin or a solution containing a resin emulsion, or by adhering plastic, elastomer, rubber, etc. in the form of a flat surface, sheet, film, etc. Considering that the temperature control indicator of the present invention is used in low or ultra-low temperature ranges, it is preferable that the transparent protective layer is one that is not easily embrittled in low or ultra-low temperature ranges, and a transparent protective layer made of a resin such as polyethylene, polyethylene terephthalate, or acrylonitrile-butadiene-styrene copolymer resin is suitable. The transparent protective layer can be provided by a conventional lamination process, such as dry lamination or hot melt lamination, or by interposing a heat-sealing film between the transparent protective layer and the adjacent reversible thermochromic layer or reversible thermochromic molded article and then heat-pressing them together. Transparency refers to the property of transmitting light with wavelengths in the visible light region (the wavelength region of 380 to 780 nm specified in JIS B 7079). When the light transmittance (visible light transmittance) in the visible light region of the transparent protective layer is preferably 5% or more, more preferably 10% or more, and even more preferably 20% or more, the adjacent reversible thermochromic layer or reversible thermochromic molded body can be easily seen, and the color and color change exhibited by the reversible thermochromic layer or reversible thermochromic molded body can be seen. The visible light transmittance can be determined by providing a transparent protective layer on a transparent substrate that transmits light with wavelengths in the visible light region, measuring the transmittance in the wavelength region from 380 nm to 780 nm using a spectrophotometer (Hitachi, Ltd., product name: U-3210), and calculating the intermediate value between the maximum and minimum values.

[0092] Examples of light stabilizers include ultraviolet absorbers, antioxidants, antiaging agents, singlet oxygen quenchers, superoxide anion quenchers, ozone quenchers, visible light absorbers, and infrared absorbers, and examples of transparent metallic luster pigments include pigments having a core material such as natural mica, synthetic mica, glass pieces, alumina, or transparent film pieces whose surface is coated with a metal oxide such as titanium oxide. Light resistance can be imparted by providing a layer in which these light stabilizers or transparent metallic luster pigments are fixed in a dispersed state.

[0093] In addition to the above-described configurations, the temperature control indicator comprising the first and second thermochromic color-memory materials may also be configured by laminating, for example, a first reversible thermochromic laminate (reversible thermochromic laminate A) having a first reversible thermochromic layer (reversible thermochromic layer A) on a support, and a second reversible thermochromic laminate (reversible thermochromic laminate B) having a second reversible thermochromic layer (reversible thermochromic laminate B) on a support. In this case, the support constituting one reversible thermochromic laminate provided on the other reversible thermochromic laminate is transparent. In the above configuration, the temperature control indicator can also be configured by providing the aforementioned adhesive layer between one reversible thermochromic laminate and the other reversible thermochromic laminate, and attaching one reversible thermochromic laminate to the other reversible thermochromic laminate via the adhesive layer. The thermochromic laminate may also be a laminate of a first reversible thermochromic laminate and a second reversible thermochromic molded body, or a laminate of a first reversible thermochromic molded body and a second reversible thermochromic laminate, in which case the support constituting the reversible thermochromic molded body provided on the reversible thermochromic laminate, or the support constituting the reversible thermochromic laminate provided on the reversible thermochromic molded body, is transparent. In the above configuration, the aforementioned adhesive layer may be provided between the reversible thermochromic laminate and the reversible thermochromic molded body, and the reversible thermochromic laminate and the reversible thermochromic molded body may be attached via the adhesive layer to form a temperature control indicator. It may also be a structure in which a second reversible thermochromic layer is provided on a first reversible thermochromic molded body, or a structure in which a first reversible thermochromic layer is provided on a second reversible thermochromic molded body. Furthermore, the present invention may have a configuration in which a first reversible thermochromic layer is provided on one side of a transparent support, and a second reversible thermochromic layer is provided on the other side of the support (the side of the support opposite to the side on which the first reversible thermochromic layer is provided).

[0094] The temperature control indicator comprising the first thermochromic color-memory material can be used, for example, as follows. First, using a device capable of cooling in the ultra-low temperature range, such as an ultra-low temperature storage unit, the temperature control indicator is set to its initial state, in which the first thermochromic color-memory material is in a colored state. The temperature control indicator in its initial state continues to maintain its initial state in a temperature environment below the complete decolorization temperature t4 of the thermochromic color-memory material. Next, the temperature control indicator in its initial state is laminated or attached to an item or its storage container that is temperature-controlled within an appropriate temperature range using a cooling device such as a refrigerator or freezer commonly used in everyday living environments, making it possible to detect temperature changes in the item or its storage container. In this state, it is possible to detect from the color change of the temperature control indicator whether the item or storage container has reached a temperature environment exceeding the appropriate temperature range. When the first thermochromic color-memory material has become discolored and the temperature control indicator laminated on the item or its storage container has changed color (State 1), it is possible to detect that the item or its storage container has reached a temperature environment exceeding the appropriate temperature range. In order to return a temperature control indicator in state 1 to its initial state again, it must be cooled to a temperature below the full color change temperature t1 of the thermochromic color memory material. However, cooling devices such as refrigerators and freezers that control the temperature of the above-mentioned items or storage containers are unable to cool to a temperature below the full color change temperature t1 of the thermochromic color memory material, and the temperature control indicator remains in state 1, making it possible to irreversibly determine that the temperature has deviated from the appropriate temperature range.

[0095] The temperature control indicator comprising the first thermochromic color-memory material and the second thermochromic color-memory material can be used, for example, as follows. First, using a device capable of cooling in an ultra-low temperature range, such as an ultra-low temperature storage, the temperature control indicator is set to an initial state in which each thermochromic color memory material is in a colored state. The temperature control indicator in the initial state is set to the complete decolorization temperature t 4′ The initial state is maintained in a temperature environment below 100°C. Next, the temperature control indicator in the initial state is laminated or attached to an item or its storage container that is temperature-controlled within an appropriate temperature range using a cooling device such as a refrigerator or freezer that is commonly used in everyday living environments, so that the temperature change of the item or its storage container can be detected. In this state, the item or storage container is kept in a specific temperature range (temperature t 4′ The color change of the temperature control indicator can detect whether the item or its storage container has been placed in a temperature range above t4 (or below t5), or whether the temperature has deviated from the appropriate temperature range. When the second thermochromic color memory material becomes discolored and the temperature control indicator laminated on the item or its storage container changes color (state 2), it can be detected that the item or its storage container has been placed in a specific temperature range. In order to return the temperature control indicator in the state 2 to the initial state again, the second thermochromic color memory material must be heated to the full color temperature t 1′ However, in a cooling device such as a refrigerator or a freezer that controls the temperature of the above-mentioned items or storage containers, the second thermochromic color-memory material must be cooled to a temperature below the full color-changing temperature t 1′ Since the temperature cannot be cooled to a temperature below this level and the temperature control indicator remains in state 2, it can irreversibly determine that the device has been placed in a specific temperature range, and the device has a temperature control function. Furthermore, when the first thermochromic color memory material becomes discolored and the temperature control indicator laminated on the item or its storage container changes color (state 3), it can be detected that the item or its storage container has fallen into a temperature environment that exceeds the appropriate temperature range. In order to return the temperature control indicator in the state 3 to the initial state again, the first thermochromic color-memory composition has a complete color-developing temperature t1 and the second thermochromic color-memory composition has a complete color-developing temperature t2. 1′ However, in cooling devices such as refrigerators and freezers that control the temperature of the above items or storage containers, the complete color-changing temperature t1 and the complete color-changing temperature t 1′Since it is not possible to cool the temperature below this temperature, and the temperature control indicator remains in state 3, it is possible to irreversibly determine that the temperature environment has deviated from the appropriate temperature range. [Example]

[0096] Examples are given below, but the present invention is not limited thereto. In the examples, "parts" means "parts by mass."

[0097] Example 1 Preparation of thermosensitive color-changing and color-memory microcapsule pigments A thermochromic color-memory composition consisting of 1.5 parts of 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide as component (A), 5 parts of 2,2-bis(4-hydroxyphenyl)hexafluoropropane as component (B), and 50 parts of 4-methylbenzyl caprylate as component (C) was added to a mixed solution consisting of 30 parts of an aromatic isocyanate prepolymer as a wall material and 50 parts of a cosolvent, and then emulsified and dispersed in a 6% aqueous polyvinyl alcohol solution. After heating and stirring, 2.5 parts of a water-soluble aliphatic modified amine was added and further stirring was continued to prepare a microcapsule dispersion. A thermochromic color-memory microcapsule pigment with an average particle size of 4.6 μm was obtained from the above microcapsule dispersion by centrifugation.

[0098] Preparation of samples for measuring discoloration temperature A thermochromic color-memorizing ink was uniformly dispersed in the above-mentioned microcapsule pigment (40 parts), ethylene-vinyl acetate copolymer resin emulsion (50 parts), leveling agent (1 part), antifoaming agent (1 part), viscosity modifier (0.5 parts), and water (7.5 parts). A solid print was then made on high-quality paper, and the ink was dried and cured to form a reversible thermochromic layer. Next, a 16 μm thick transparent PET film having an adhesive layer was attached onto the reversible thermochromic layer via the adhesive layer, followed by lamination, to prepare a measurement sample.

[0099] Discoloration temperature measurement The measurement sample was immersed in a glass container filled with ethanol, and the glass container was placed in an ultra-low temperature aluminum block thermostatic chamber Cryoporter (manufactured by Synix Corporation, product name: CS-80C). Furthermore, the temperature-sensing part of a general-purpose semi-solid / liquid temperature sensor (manufactured by Anritsu Meter Co., Ltd., product name: BS-21E-010) connected to a digital thermometer (manufactured by Anritsu Meter Co., Ltd., product name: HFT-50) was placed in the glass container. The temperature of the measurement sample immersed in ethanol was then changed in 1°C increments between room temperature (25°C) and -90°C, and the color change of the thermochromic color-memory composition was visually observed. The temperature at which the thermochromic color-memory composition changed color was measured using a digital thermometer to measure the complete color development temperature t1, the color development start temperature t2, the color disappearance start temperature t3, and the complete color disappearance temperature t4, and the hysteresis width [ΔH = (intermediate temperature between t3 and t4) - (intermediate temperature between t1 and t2)]. The thermochromic color-memory composition of Example 1 had a complete color development temperature t1 of -55°C, a color development start temperature t2 of -45°C, a color fade start temperature t3 of -10°C, a complete fade temperature t4 of -6°C, and a ΔH of 32°C, and reversibly changed from blue to colorless with temperature change.

[0100] Fabrication of temperature control indicator (see Figure 14) A thermochromic color-memorizing ink, which was a uniform dispersion of 30 parts of the above-mentioned microcapsule pigment, 62 parts of a urethane emulsion, 2 parts of a thickener, 0.5 parts of a leveling agent, 0.5 parts of an antifoaming agent, and 5 parts of a crosslinking agent, was solid-printed onto a white synthetic paper substrate (3) using a 120-mesh screen, and then dried and cured to form a reversible thermochromic layer (2). Next, a transparent PET film having a thickness of 16 μm and having an adhesive layer was attached onto the reversible thermochromic layer via the adhesive layer to provide a transparent protective layer (9), thereby producing a temperature control indicator.

[0101] Temperature control during the distribution and storage of fresh fish (the proper temperature range is -7°C or below, and it is determined whether the temperature has deviated from the proper temperature range) The above temperature control indicator was placed in an ultra-low temperature stocker (classified as F4 class under the Warehouse Business Act) set to -55°C, and when the temperature control indicator was cooled to cause the thermochromic color-memory material to change color, a blue temperature control indicator was visible (initial state). Next, while maintaining the temperature control indicator in its initial state, it was transferred to a freezer (classified as Class C1 under the Warehousing Business Act) set to -15°C where fresh fish is stored, and stacked on top of a storage container containing fresh fish.Since the temperature inside the freezer was lower than the complete discoloration temperature t4 of the thermochromic color-memory material, the temperature control indicator maintained its initial state and the blue color was visible. When the storage container was placed in a temperature environment of -6°C or higher, the thermochromic color-memory material lost its color, causing the temperature control indicator to change color, leaving only the white color of the support visible (State 1). Furthermore, even when the storage container was returned to the freezer set to -15°C, the temperature control indicator could not return to its initial state, and only the white color was visible. Therefore, once the temperature control indicator stacked on a storage container containing fresh fish changes color from its initial state, it cannot easily return to its initial state, making it possible to irreversibly determine that the storage container has fallen into a temperature environment that exceeds the appropriate temperature range. To return the temperature control indicator to its initial state, it needs to be cooled to below -55°C, but this is difficult to achieve in freezers commonly used in everyday living environments. Furthermore, by placing the environment in which the temperature control indicator is reset to its initial state by using a thermochromic color-memory material to change color and the environment in which the temperature of fresh fish is controlled far away from each other, and by transporting the temperature control indicator, which has been reset to its initial state using an ultra-low temperature stocker, to an environment without an ultra-low temperature stocker while maintaining its initial state, and controlling the temperature of fresh fish, it was possible to prevent tampering by cooling the temperature control indicator again to return it to its initial state when the temperature control indicator reached state 1. Furthermore, the difference (ΔT) between the complete decolorization temperature t4 of the thermochromic color-memory material and the upper limit temperature T of the appropriate temperature range was 1°C, allowing for strict temperature control. Furthermore, in everyday living environments, the above-mentioned temperature control indicator only shows the white color of the support, but when cooled to -55°C or below, the thermochromic color memory material changes color and turns blue, making it possible to use it as an anti-counterfeiting medium with anti-counterfeiting functions.

[0102] Example 2 Preparation of thermosensitive color-changing and color-memory microcapsule pigments A thermochromic color-memory composition consisting of 1.5 parts of 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide as component (A), 5 parts of 1,1-bis(4-hydroxyphenyl)-2-ethylhexane as component (B), and 50 parts of benzyl caprate as component (C) was added to a mixed solution consisting of 30 parts of an aromatic isocyanate prepolymer as a wall material and 50 parts of a cosolvent, and then emulsified and dispersed in a 6% aqueous polyvinyl alcohol solution. After heating and stirring, 2.5 parts of a water-soluble aliphatic modified amine was added and further stirring was continued to prepare a microcapsule dispersion. From the above microcapsule dispersion, a thermochromic color-memory microcapsule pigment with an average particle size of 5.2 μm was obtained by centrifugation.

[0103] Preparation of samples for measuring discoloration temperature Measurement samples were prepared in the same manner as in Example 1.

[0104] Discoloration temperature measurement Using the same method as in Example 1, the complete color development temperature t1, color development start temperature t2, color fade start temperature t3, and complete fade temperature t4 of the thermochromic color-memory composition were measured, and the hysteresis width [ΔH = (intermediate temperature between t3 and t4) - (intermediate temperature between t1 and t2)] was calculated. The thermochromic color-memory composition of Example 2 had a complete color development temperature t1 of -45°C, a color development start temperature t2 of -40°C, a color fade start temperature t3 of -8°C, a complete fade temperature t4 of -5°C, and ΔH of 36°C, and reversibly changed from blue to colorless with temperature change.

[0105] Fabrication of temperature control indicator (see Figure 15) A non-thermochromic ink consisting of 0.5 parts of a pink non-thermochromic colorant, 91.5 parts of a urethane emulsion, 2 parts of a thickener, 0.5 parts of a leveling agent, 0.5 parts of an antifoaming agent, and 5 parts of a crosslinking agent was uniformly dispersed on white synthetic paper as a support (3) using a 120-mesh screen stencil, and then dried and cured to form a non-thermochromic layer (4). Next, a thermochromic color-memory ink consisting of 30 parts of the above-mentioned microcapsule pigment as a thermochromic color-memory material, 62 parts of a urethane emulsion, 2 parts of a thickener, 0.5 parts of a leveling agent, 0.5 parts of an antifoaming agent, and 5 parts of a crosslinking agent was uniformly dispersed on the non-thermochromic layer by solid printing using a 120 mesh screen, and then dried and hardened to form a reversible thermochromic layer (2). Next, a transparent PET film having a thickness of 16 μm and having an adhesive layer was attached onto the reversible thermochromic layer via the adhesive layer to provide a transparent protective layer (9), thereby producing a temperature control indicator.

[0106] Temperature control during the distribution and storage of frozen foods (determine whether the appropriate temperature range is below -5°C and whether the temperature environment has exceeded the appropriate temperature range) The above temperature control indicator was placed in an ultra-low temperature stocker (classified as F3 under the Warehouse Business Act) set to -45°C, and the temperature control indicator was cooled to cause the thermochromic color memory material to change color.The purple temperature control indicator was visible (initial state), a mixture of the pink color from the non-thermochromic layer and the blue color from the reversible thermochromic layer. Next, while maintaining the temperature control indicator in its initial state, it was moved to a freezer (classified as Class C1 under the Warehousing Business Act) set to -10°C where frozen foods are stored, and stacked on top of a packaging container containing the frozen foods.Since the temperature inside the freezer was lower than the complete discoloration temperature t4 of the thermochromic color-memory material, the temperature control indicator maintained its initial state and the purple color was visible. When the packaging container was placed in a temperature environment of -5°C or higher, the thermochromic color-memory material lost its color, causing the temperature control indicator to change color, leaving only the pink color of the non-thermochromic layer visible (State 1). Furthermore, even when the packaging container was returned to the freezer set to -10°C, the temperature control indicator could not return to its initial state, and only the pink color remained visible. Therefore, once the temperature control indicator stacked on a packaging container containing frozen food changes color from its initial state, it cannot easily return to its initial state, making it possible to irreversibly determine that the packaging container has fallen into a temperature environment that exceeds the appropriate temperature range. To return the temperature control indicator to its initial state, it needs to be cooled to below -45°C, but this is difficult to achieve in freezers commonly used in everyday living environments. Furthermore, by placing the environment in which the temperature control indicator is reset to its initial state by using a thermochromic color-memory material to change color and the environment in which the temperature of frozen foods is controlled far apart, and transporting the temperature control indicator, which has been reset to its initial state using an ultra-low temperature stocker, to an environment without an ultra-low temperature stocker while maintaining its initial state, and controlling the temperature of frozen foods, it was possible to prevent tampering by cooling the temperature control indicator again to return it to its initial state when the temperature control indicator reached State 1. Furthermore, the difference (ΔT) between the complete decolorization temperature t4 of the thermochromic color-memory material and the upper limit temperature T of the appropriate temperature range was 0°C < ΔT ≦ 1°C, allowing for even stricter temperature control. In addition, in everyday living environments, the above-mentioned temperature control indicator only shows the pink color of the non-thermochromic layer, but when cooled to below -45°C, the thermochromic color memory material changes color, and the pink color of the non-thermochromic layer and the blue color of the reversible thermochromic layer mix to form purple, making it usable as an anti-counterfeiting medium with anti-counterfeiting functions.

[0107] Example 3 Preparation of thermosensitive color-changing and color-memory microcapsule pigments A thermochromic color-memory composition consisting of 3 parts of 9-ethyl-(3-methylbutyl)amino-spiro[12H-benzo[a]xanthen-12,1'(3'H)-isobenzofuran]-3'-one as component (A), 5 parts of 2,2-bis(4-hydroxyphenyl)hexafluoropropane as component (B), and 50 parts of cyclohexylmethyl laurate as component (C) was added to a mixed solution consisting of 30 parts of an aromatic isocyanate prepolymer as a wall material and 50 parts of a cosolvent, and then emulsified and dispersed in a 6% aqueous polyvinyl alcohol solution. After heating and stirring, 2.5 parts of a water-soluble aliphatic modified amine was added and further stirring was continued to prepare a microcapsule dispersion. A thermochromic color-memory microcapsule pigment with an average particle size of 5.5 μm was obtained from the above microcapsule dispersion by centrifugation.

[0108] Preparation of samples for measuring discoloration temperature Measurement samples were prepared in the same manner as in Example 1.

[0109] Discoloration temperature measurement Using the same method as in Example 1, the complete color development temperature t1, color development start temperature t2, color fade start temperature t3, and complete fade temperature t4 of the thermochromic color-memory composition were measured, and the hysteresis width [ΔH = (intermediate temperature between t3 and t4) - (intermediate temperature between t1 and t2)] was calculated. The thermochromic color-memory composition of Example 3 had a complete color development temperature t1 of -37°C, a color development start temperature t2 of -30°C, a color fade start temperature t3 of 3°C, a complete fade temperature t4 of 8°C, and ΔH of 39°C, and reversibly changed from magenta to colorless with temperature change.

[0110] Fabrication of temperature control indicator (see Figure 16) A thermochromic color-memory ink, consisting of 30 parts of the above-mentioned microcapsule pigment as a thermochromic color-memory material, 62 parts of a urethane emulsion, 2 parts of a thickener, 0.5 parts of a leveling agent, 0.5 parts of an antifoaming agent, and 5 parts of a crosslinking agent, was solid-printed onto a 25 μm-thick white transparent polyester film as a support (3) using a 120-mesh screen, and then dried and cured to form a reversible thermochromic layer (2). Next, a 16 μm thick transparent PET film with an adhesive layer was attached to the reversible thermochromic layer via the adhesive layer to form a transparent protective layer (9), and further, an adhesive made of an acrylic resin was applied to the surface of the support opposite to the surface on which the reversible thermochromic layer was formed to form an adhesive layer (5), thereby producing a temperature control indicator.

[0111] Temperature control during the distribution and storage of vegetables (the appropriate temperature range is between 0°C and 5°C, and it is determined whether the temperature environment has deviated from the appropriate range) The above temperature control indicator was placed in an ultra-low temperature stocker (classified as F2 class under the Warehouse Business Act) set to -37°C, and when the temperature control indicator was cooled to cause the thermochromic color-memory material to change color, a magenta colored temperature control indicator was visible (initial state). Next, while maintaining the temperature control indicator in its initial state, it was moved to a refrigerator (classified as Class C3 under the Warehouse Business Act) set to 2°C where vegetables are stored, and attached to a packaging container containing the vegetables.Since the temperature inside the refrigerator was lower than the complete discoloration temperature t4 of the thermochromic color-memory composition, the temperature control indicator maintained its initial state and the magenta color was visible. When the packaging container was placed in a temperature environment of 8°C or higher, the thermochromic color-memory material lost its color, causing the temperature control indicator to change color, leaving only the white color of the support visible (state 1). Furthermore, even when the packaging container was returned to the refrigerator set to 2°C, the temperature control indicator could not return to its initial state, and only the white color was visible. Therefore, once the temperature control indicator attached to the packaging container containing vegetables changes color from its initial state, it cannot easily be returned to its initial state, making it possible to irreversibly determine that the packaging container has deviated from the appropriate temperature range into a temperature environment. To return the temperature control indicator to its initial state, it needs to be cooled to below -37°C, but this is difficult to achieve in refrigerators commonly used in everyday living environments. Furthermore, by placing the environment in which the temperature control indicator is reset to its initial state by using a thermochromic color-memory material to change color and the environment in which the temperature of vegetables is controlled at a distance, and then transporting the temperature control indicator, which has been reset to its initial state using an ultra-low temperature stocker, to an environment without an ultra-low temperature stocker while maintaining its initial state, and then controlling the temperature of vegetables, it was possible to prevent tampering by cooling the temperature control indicator again to return it to its initial state when the temperature control indicator reached state 1. Furthermore, the difference (ΔT) between the complete decolorization temperature t4 of the thermochromic color-memory material and the upper limit temperature T of the appropriate temperature range was 3°C, allowing for strict temperature control. Furthermore, in everyday living environments, the above-mentioned temperature control indicator only shows the white color of the support, but when cooled to -37°C or below, the thermochromic color memory material changes color to magenta, making it possible to use it as an anti-counterfeiting medium with anti-counterfeiting functions.

[0112] Example 4 Preparation of thermosensitive color-changing and color-memory microcapsule pigments A thermochromic color-memory composition consisting of 1.5 parts of 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide (component (A)), 5 parts of 2,2-bis(4-hydroxyphenyl)hexafluoropropane (component (B)), and 49 parts of cyclohexylmethyl caprate and 1 part of 4-benzyloxyphenylethyl palmitate (component (C)) was added to a mixed solution consisting of 30 parts of an aromatic isocyanate prepolymer as a wall material and 50 parts of a cosolvent. The mixture was then emulsified and dispersed in a 6% aqueous polyvinyl alcohol solution. After heating and stirring, 2.5 parts of a water-soluble aliphatic modified amine was added and further stirring was continued to prepare a microcapsule dispersion. A thermochromic color-memory microcapsule pigment with an average particle size of 3.9 μm was obtained from the microcapsule dispersion by centrifugation.

[0113] Preparation of samples for measuring discoloration temperature Measurement samples were prepared in the same manner as in Example 1.

[0114] Measurement of discoloration temperature Using the same method as in Example 1, the complete color development temperature t1, color development start temperature t2, color fade start temperature t3, and complete fade temperature t4 of the thermochromic color-memory composition were measured, and the hysteresis width [ΔH = (intermediate temperature between t3 and t4) - (intermediate temperature between t1 and t2)] was calculated. The thermochromic color-memory composition of Example 4 had a complete color development temperature t1 of -45°C, a color development start temperature t2 of -30°C, a color fade start temperature t3 of -16°C, a complete fade temperature t4 of -10°C, and a ΔH of 24.5°C, and reversibly changed from blue to colorless with temperature change.

[0115] Fabrication of a temperature control indicator with tamper-proof function (see Figure 17) A thermochromic color-memory ink, consisting of 30 parts of the above-mentioned microcapsule pigment, 62 parts of a urethane emulsion, 2 parts of a thickener, 0.5 parts of a leveling agent, 0.5 parts of an antifoaming agent, and 5 parts of a crosslinking agent, was uniformly dispersed on the side opposite the adhesive side of an 80 μm thick tamper-evident label made of white polypropylene film (manufactured by Lintec Corporation, product name: TE80W PAT1 8K) as the tamper-evident member (support) (7), using a 120-mesh screen stencil to print in solid form. The ink was then dried and cured to form a reversible thermochromic layer (2). Next, a 16 μm thick transparent PET film with an adhesive layer was attached to the reversible thermochromic layer via the adhesive layer to provide a transparent protective layer (9), thereby producing a temperature control indicator with tamper-proof function.

[0116] Temperature control during the distribution and storage of bread dough (the appropriate temperature range is between -20°C and -10°C, and it is determined whether the temperature environment has deviated from the appropriate temperature range) The above temperature control indicator was placed in an ultra-low temperature stocker (classified as F3 under the Warehouse Business Act) set to -45°C, and when the temperature control indicator was cooled to cause the thermochromic color-memory material to change color, a blue temperature control indicator was visible (initial state). Next, while maintaining the temperature control indicator in its initial state, it was transferred to a freezer (classified as Class C1 under the Warehouse Business Act) set to -18°C where the bread dough was stored, and attached to the storage container containing the bread dough.Since the temperature inside the freezer was lower than the complete discoloration temperature t4 of the thermochromic color-memory material, the temperature control indicator maintained its initial state and the blue color was visible. When the storage container was placed in a temperature environment of -10°C or higher, the thermochromic color-memory material lost its color, causing the temperature control indicator to change color, leaving only the white color of the support visible (State 1). Furthermore, even when the storage container was returned to the freezer set to -18°C, the temperature control indicator could not return to its initial state, and only the white color was visible. Therefore, once the temperature control indicator attached to the storage container containing the bread dough changes color from its initial state, it cannot be easily returned to its initial state, making it possible to irreversibly determine that the storage container has deviated from the appropriate temperature range into a temperature environment. To return the temperature control indicator to its initial state, it needs to be cooled to below -45°C, but this is difficult to do in freezers commonly used in everyday living environments. Furthermore, by placing the environment in which the temperature control indicator is reset to its initial state by changing the color of the thermochromic color-memory material and the environment in which the temperature of the bread dough is controlled far apart and transporting the temperature control indicator, which has been reset to its initial state using an ultra-low temperature stocker, to an environment without an ultra-low temperature stocker while maintaining its initial state, and controlling the temperature of the bread dough, it was possible to prevent tampering by cooling the temperature control indicator again to return it to its initial state when the temperature control indicator reached State 1. Furthermore, when the temperature control indicator was peeled off from the storage container in an attempt to replace it in order to prevent any record of the dough being exposed to a temperature environment that exceeded the appropriate temperature range, the base material of the tamper-proof label was destroyed, leaving a peeled-off mark on the storage container. Therefore, the temperature control indicator had the function of preventing tampering due to replacement. Furthermore, the difference (ΔT) between the complete decolorization temperature t4 of the thermochromic color-memory material and the upper limit temperature T of the appropriate temperature range was 0°C < ΔT ≦ 1°C, allowing for even stricter temperature control. Furthermore, in everyday living environments, the above-mentioned temperature control indicator only shows the white color of the support, but when cooled to -45°C or below, the thermochromic color memory material changes color and turns blue, making it possible to use it as an anti-counterfeiting medium with anti-counterfeiting functions.

[0117] Example 5 Preparation of thermosensitive color-changing and color-memory microcapsule pigments A thermochromic color-memory composition consisting of 1.5 parts of 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide as component (A), 5 parts of 2,2-bis(4-hydroxyphenyl)hexafluoropropane as component (B), and 50 parts of cyclohexylmethyl laurate as component (C) was added to a mixed solution consisting of 30 parts of an aromatic isocyanate prepolymer as a wall film material and 50 parts of a cosolvent, and then emulsified and dispersed in a 6% aqueous polyvinyl alcohol solution. After heating and stirring, 2.5 parts of a water-soluble aliphatic modified amine was added and further stirring was continued to prepare a microcapsule dispersion. A thermochromic color-memory microcapsule pigment with an average particle size of 4.9 μm was obtained from the above microcapsule dispersion by centrifugation.

[0118] Preparation of samples for measuring discoloration temperature Measurement samples were prepared in the same manner as in Example 1.

[0119] Discoloration temperature measurement Using the same method as in Example 1, the complete color development temperature t1, color development start temperature t2, color fade start temperature t3, and complete fade temperature t4 of the thermochromic color-memory composition were measured, and the hysteresis width [ΔH = (intermediate temperature between t3 and t4) - (intermediate temperature between t1 and t2)] was calculated. The thermochromic color-memory composition of Example 5 had a complete color development temperature t1 of -36°C, a color development start temperature t2 of -32°C, a color fade start temperature t3 of 4°C, a complete color fade temperature t4 of 8°C, and ΔH of 40°C, and reversibly changed from blue to colorless with temperature change.

[0120] Fabrication of temperature control indicator As a thermochromic color-memory material, 10 parts of the above microcapsule pigment, 1 part of dispersant, and 89 parts of polypropylene homopolymer were melt-mixed at 180°C in an extruder to obtain a thermochromic color-memory molding resin composition. Next, the above resin composition was molded into a plate shape using an injection molding machine at a cylinder temperature of 180°C to prepare a temperature control indicator (a support containing a thermochromic color-memory composition).

[0121] Temperature control during the distribution and storage of vegetables (the appropriate temperature range is between 0°C and 5°C, and it is determined whether the temperature environment has deviated from the appropriate range) The above temperature control indicator was placed in an ultra-low temperature stocker (classified as F2 class under the Warehouse Business Act) set to -36°C, and when the temperature control indicator was cooled to cause the thermochromic color-memory material to change color, a blue temperature control indicator was visible (initial state). Next, while the temperature control indicator was maintained in its initial state, it was moved to a refrigerator (classified as Class C3 under the Warehouse Business Act) set to 3°C, where vegetables are stored, and stacked on top of the packaging container containing the vegetables.Since the temperature inside the refrigerator was lower than the complete discoloration temperature t4 of the thermochromic color-memory material, the temperature control indicator maintained its initial state and the blue color was visible. When the packaging container was placed in a temperature environment of 8°C or higher, the thermochromic color-memory material lost its color, causing the temperature control indicator to change color, and only the packaging container on which the temperature control indicator was placed could be seen (State 1). Furthermore, even when the packaging container was returned to the refrigerator set to 3°C, the temperature control indicator could not be restored to its initial state, and only the packaging container could be seen. Therefore, once the temperature control indicator attached to the packaging container containing vegetables changes color from its initial state, it cannot easily be returned to its initial state, making it possible to irreversibly determine that the packaging container has deviated from the appropriate temperature range into a temperature environment. To return the temperature control indicator to its initial state, it needs to be cooled to below -36°C, but this is difficult to achieve in refrigerators commonly used in everyday living environments. Furthermore, by placing the environment in which the temperature control indicator is initialized by the color-changing thermochromic color-memory material and the environment in which the temperature of vegetables is controlled at a distance, and then transporting the temperature control indicator, which has been initialized using an ultra-low temperature stocker, to an environment without an ultra-low temperature stocker while maintaining its initial state, and controlling the temperature of vegetables, it was possible to prevent tampering by cooling the temperature control indicator again to return it to its initial state when the temperature control indicator reached State 1. Furthermore, the difference (ΔT) between the complete decolorization temperature t4 of the thermochromic color-memory material and the upper limit temperature T of the appropriate temperature range was 3°C, allowing for strict temperature control. Furthermore, in everyday living environments, the temperature control indicator only shows the visible color of the packaging container, but when cooled to -36°C or below, the thermochromic color-memory material changes color and turns blue, making it possible to use it as an anti-counterfeiting medium with anti-counterfeiting functions.

[0122] Example 6 Fabrication of temperature control indicator (see Figure 14) A thermochromic color-memorizing ink, which was a uniform dispersion of 30 parts of the microcapsule pigment of Example 3, 62 parts of a urethane emulsion, 2 parts of a thickener, 0.5 parts of a leveling agent, 0.5 parts of an antifoaming agent, and 5 parts of a crosslinking agent, was solid-printed onto a white synthetic paper substrate (3) using a 120-mesh screen, and the ink was dried and cured to form a reversible thermochromic layer (2). Next, a transparent PET film having a thickness of 16 μm and having an adhesive layer was attached onto the reversible thermochromic layer via the adhesive layer to provide a transparent protective layer (9), thereby producing a temperature control indicator.

[0123] Temperature control during vaccine distribution and storage (ensuring that the appropriate temperature range is 5°C or less and determining whether the temperature environment has deviated from the appropriate range) The above temperature control indicator was placed in an ultra-low temperature stocker (classified as F2 class under the Warehouse Business Act) set to -37°C, and when the temperature control indicator was cooled to cause the thermochromic color-memory material to change color, a magenta colored temperature control indicator was visible (initial state). Next, while maintaining the temperature control indicator in its initial state, it was transferred to a freezer (classified as F1 class under the Warehousing Business Act) set to -20°C where the vaccine was stored, and stacked on top of the storage container containing the vaccine.Since the temperature inside the freezer was lower than the complete discoloration temperature t4 of the thermochromic color-memory material, the temperature control indicator maintained its initial state and the magenta color was visible. When the storage container was placed in a temperature environment of 8°C or higher, the thermochromic color-memory material lost its color, causing the temperature control indicator to change color, leaving only the white color of the support visible (State 1). Furthermore, even when the storage container was returned to the freezer set to -20°C, the temperature control indicator could not return to its initial state, and only the white color was visible. Therefore, once the temperature control indicator layered on the storage container containing the vaccine changes color from its initial state, it cannot easily return to its initial state, making it possible to irreversibly determine that the storage container has fallen into a temperature environment that exceeds the appropriate temperature range. To return the temperature control indicator to its initial state, it needs to be cooled to below -37°C, but this is difficult to achieve in freezers commonly used in everyday living environments. Furthermore, by placing the environment in which the temperature control indicator is reset to its initial state by using the thermochromic color-memory material to change color and the environment in which the vaccine's temperature is controlled far apart, and by transporting the temperature control indicator, which has been reset to its initial state using an ultra-low temperature stocker, to an environment without an ultra-low temperature stocker while maintaining its initial state, and controlling the vaccine's temperature, it was possible to prevent tampering by cooling the temperature control indicator again to return it to its initial state when the temperature control indicator reached State 1. Furthermore, the difference (ΔT) between the complete decolorization temperature t4 of the thermochromic color-memory material and the upper limit temperature T of the appropriate temperature range was 3°C, allowing for strict temperature control. Furthermore, in everyday living environments, the above-mentioned temperature control indicator only shows the white color of the support, but when cooled to -37°C or below, the thermochromic color memory material changes color to magenta, making it possible to use it as an anti-counterfeiting medium with anti-counterfeiting functions.

[0124] Example 7 Fabrication of temperature control indicator (see Figure 9) A thermochromic color-memory ink consisting of 15 parts of the microcapsule pigment of Example 3 as the first thermochromic color-memory material, 15 parts of the microcapsule pigment of Example 4 as the second thermochromic color-memory material, 62 parts of a urethane emulsion, 2 parts of a thickener, 0.5 parts of a leveling agent, 0.5 parts of an antifoaming agent, and 5 parts of a crosslinking agent was solid-printed onto a 25 μm thick white transparent polyester film as a support (3) using a 120 mesh screen, and then dried and cured to form a reversible thermochromic layer (2). Next, an adhesive made of an acrylic resin was applied to the surface of the support opposite to the surface on which the reversible thermochromic layer was to be provided, to provide an adhesive layer (5), thereby producing a temperature control indicator.

[0125] Temperature control during the distribution and storage of meat products (determining whether the appropriate temperature range is below 8°C and whether the temperature environment has exceeded the appropriate temperature range) The above temperature control indicator was placed in an ultra-low temperature stocker (classified as F3 under the Warehouse Business Act) set to -45°C, and the temperature control indicator was cooled to cause the first thermochromic color memory material and the second thermochromic color memory material to develop color.A purple temperature control indicator was visible, which was a mixture of the magenta color from the first thermochromic color memory material and the blue color from the second thermochromic color memory material (initial state). Next, while maintaining the temperature control indicator in its initial state, the indicator is transferred to a freezer (classified as C1 class under the Warehousing Business Act) where meat products are stored and set at -18°C, and the indicator is attached to a packaging container containing the meat products. When the temperature in the freezer reaches the complete decolorization temperature t 4′ Since the temperature was lower than the initial value, the temperature control indicator maintained its initial state and a purple color was visible. When the packaging container was placed in a temperature environment (specific temperature range) above -10°C and below 8°C, the second thermochromic color-memory material lost its color, causing the temperature control indicator to change color, with only the magenta color of the first thermochromic color-memory material in its colored state being visible (State 2). Even when the packaging container was returned to the freezer set to -18°C, the temperature control indicator could not be restored to its initial state, and only the magenta color was visible. Furthermore, when the packaging container was placed in a temperature environment of 8°C or higher, the first thermochromic color-memory material lost its color, the temperature control indicator changed color, and only the white color of the support was visible (State 3). Even when the packaging container was returned to the freezer set to -18°C, the temperature control indicator could not be returned to State 2 or its initial state, and only the white color was visible. Therefore, once the temperature control indicator affixed to a packaging container containing meat products changes color from its initial state to state 2, it cannot be easily returned to its initial state thereafter, making it possible to irreversibly determine that the packaging container has been placed in a specific temperature range, and providing a temperature control function within that specific temperature range. Also, once the temperature control indicator changes color from state 2 to state 3, it cannot be easily returned to state 2 or its initial state thereafter, making it possible to irreversibly determine that the packaging container has deviated from the appropriate temperature range into a temperature environment. To return the temperature control indicator to its initial state, it needs to be cooled to below -45°C, but this is difficult to do in freezers commonly used in everyday living environments. Furthermore, by placing the environment in which the temperature control indicator is initialized by changing the color of each thermochromic color-memory material and the environment in which the meat product's temperature is controlled far away from each other, and by transporting the temperature control indicator, which has been initialized using an ultra-low temperature stocker, to an environment without an ultra-low temperature stocker while maintaining its initial state, and controlling the temperature of the meat product, it is possible to prevent tampering by cooling the temperature control indicator again to return it to its initial state when the temperature control indicator reaches state 2 or 3. Furthermore, the difference (ΔT) between the complete decolorization temperature t4 of the first thermochromic color-memory material and the upper limit temperature T of the appropriate temperature range was 0°C < ΔT ≦ 1°C, allowing for even stricter temperature control. In addition, the temperature control indicator only shows the white color of the support in an everyday living environment, but when cooled to a temperature above -45°C and below -37°C, the first thermochromic color memory material changes color to magenta, making it usable as an anti-counterfeiting medium.Furthermore, when cooled to below -45°C, the second thermochromic color memory material changes color to purple, a mixture of the magenta color of the first thermochromic color memory material in the colored state and the blue color of the second thermochromic color memory material in the colored state, making it usable as an anti-counterfeiting medium with even better anti-counterfeiting functionality.

[0126] Comparative Example 1 Preparation of thermosensitive color-changing and color-memory microcapsule pigments A thermochromic color-memory composition consisting of 1.5 parts of 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide as component (A), 5 parts of 2,2-bis(4-hydroxyphenyl)hexafluoropropane as component (B), and 50 parts of 4-methylbenzyl stearate as component (C) was added to a mixed solution consisting of 30 parts of an aromatic isocyanate prepolymer as a wall material and 50 parts of a cosolvent, and then emulsified and dispersed in a 6% aqueous polyvinyl alcohol solution. After heating and stirring, 2.5 parts of a water-soluble aliphatic modified amine was added and further stirring was continued to prepare a microcapsule dispersion. A thermochromic color-memory microcapsule pigment with an average particle size of 4.5 μm was obtained from the above microcapsule dispersion by centrifugation.

[0127] Preparation of samples for measuring discoloration temperature A thermochromic color-memorizing ink was uniformly dispersed in the above-mentioned microcapsule pigment (40 parts), ethylene-vinyl acetate copolymer resin emulsion (50 parts), leveling agent (1 part), antifoaming agent (1 part), viscosity modifier (0.5 parts), and water (7.5 parts). A solid print was then made on high-quality paper, and the ink was dried and cured to form a reversible thermochromic layer. Next, a 16 μm thick transparent PET film having an adhesive layer was attached onto the reversible thermochromic layer via the adhesive layer, followed by lamination, to prepare a measurement sample.

[0128] Discoloration temperature measurement The above measurement sample was placed in the measurement section of a color difference meter (Tokyo Denshoku Co., Ltd., product name: TC-3600), and the sample section was heated and cooled at a rate of 2°C per minute. The lightness value was measured as the color density at each temperature, and a color density-temperature curve was created. The complete color development temperature t1, color development onset temperature t2, color fade onset temperature t3, and complete fade temperature t4 were measured from the color density-temperature curve, and the hysteresis width [ΔH = (intermediate temperature between t3 and t4) - (intermediate temperature between t1 and t2)] was calculated. The thermochromic color-memory composition of Comparative Example 1 had a complete color development temperature t1 of 6°C, a color development start temperature t2 of 12°C, a color fade start temperature t3 of 36°C, a complete fade temperature t4 of 46°C, and ΔH of 32°C, and reversibly changed from blue to colorless with temperature change.

[0129] Fabrication of temperature control indicator (see Figure 14) A thermochromic color-memorizing ink, which was a uniform dispersion of 30 parts of the above-mentioned microcapsule pigment, 62 parts of a urethane emulsion, 2 parts of a thickener, 0.5 parts of a leveling agent, 0.5 parts of an antifoaming agent, and 5 parts of a crosslinking agent, was solid-printed onto a white synthetic paper substrate (3) using a 120-mesh screen, and then dried and cured to form a reversible thermochromic layer (2). Next, a transparent PET film having a thickness of 16 μm and having an adhesive layer was attached onto the reversible thermochromic layer via the adhesive layer to provide a transparent protective layer (9), thereby producing a temperature control indicator.

[0130] Temperature control during the distribution and storage of fresh fish (the proper temperature range is -7°C or below, and it is determined whether the temperature has deviated from the proper temperature range) The above temperature control indicator was placed in an ultra-low temperature stocker (classified as F4 under the Warehouse Business Act) set to -55°C, and the temperature control indicator was cooled to cause the thermochromic color-memory composition to develop color, and a blue temperature control indicator was visible (initial state). Next, while maintaining the temperature control indicator in its initial state, it was transferred to a freezer (classified as Class C1 under the Warehousing Business Act) set to -15°C where fresh fish is stored, and stacked on top of a storage container containing fresh fish.Since the temperature inside the freezer was lower than the complete discoloration temperature t4 of the thermochromic color-memory material, the temperature control indicator maintained its initial state and the blue color was visible. Even when the storage container was placed in a temperature environment above -7°C and below 46°C, the temperature was lower than the complete discoloration temperature t4 of the thermochromic color-memory material, so the temperature control indicator maintained its initial state, the blue color was visible, and it was not possible to detect that the temperature had fallen outside the appropriate temperature range. Furthermore, when the storage container was placed in a temperature environment of 46°C or higher, the thermochromic color-memory material lost its color, causing the temperature control indicator to change color, leaving only the white color of the support visible (State 1). When the storage container was returned to the freezer set to -15°C, the temperature control indicator returned to its initial state, and the blue color was visible, meaning that it could be easily returned to its initial state in a freezer commonly used in everyday living environments. Therefore, the temperature control indicator stacked on the storage container for fresh fish maintains its initial state even when placed in a specific temperature environment that exceeds the appropriate temperature range, and a temperature control indicator that has changed from its initial state to state 1 can easily return to its initial state, making it impossible to irreversibly determine that the fresh fish has deviated from the temperature environment that exceeds the appropriate temperature range. In addition, the difference (ΔT) between the complete decolorization temperature t4 of the thermochromic color-memory material and the upper limit temperature T of the appropriate temperature range was 53°C, and because ΔT was large, strict temperature control was not possible.

[0131] Application example 1 Five parts of the thermochromic, color-memory microcapsule pigment of Example 1, 0.1 parts of a yellow non-thermochromic colorant, 1 part of a dispersant, and 93.9 parts of a polypropylene homopolymer were melt-mixed in an extruder at 180°C to obtain a thermochromic, color-memory molding resin composition. Next, the resin composition was injection molded using a flower-shaped mold to obtain a petal-shaped molded article, and the molded articles were stacked to produce an artificial flower (decorative article). When this artificial flower was cooled to -55°C or below, the thermochromic, color-memory microencapsulated pigment developed its color, and a green color was visually recognized, a mixture of the blue from the microencapsulated pigment and the yellow from the non-thermochromic colorant. Furthermore, at temperatures below the complete decolorization temperature t4, the microencapsulated pigment maintained its color, remaining green. When the artificial flowers were then placed in a temperature environment above -6°C, the microcapsule pigments lost their color and the yellow color of the non-thermochromic colorant became visible. When the artificial flowers were cooled again to below -55°C, the green color became visible.

[0132] Application example 2 A thermochromic, color-memory ink, consisting of 30 parts of the thermochromic, color-memory microcapsule pigment of Example 1, 62 parts of a urethane emulsion, 2 parts of a thickener, 0.5 parts of a leveling agent, 0.5 parts of an antifoaming agent, and 5 parts of a crosslinking agent, was solid-printed onto a white synthetic paper substrate using a 120-mesh screen, and then dried and cured to form a reversible thermochromic layer. Next, a 16 μm thick transparent PET film having an adhesive layer was attached to the reversible thermochromic layer via the adhesive layer to form a transparent protective layer, and further, an adhesive made of an acrylic resin was applied to the surface of the support opposite to the surface on which the reversible thermochromic layer was formed to form an adhesive layer, thereby producing a laminate. The adhesive surface of the laminate was attached to the vicinity of the scooping portion of an ice cream scooper. When the disher with the laminate attached was cooled to -55°C or below, the thermochromic color-memory microcapsule pigment developed its color, and the laminate turned blue. The laminate maintained its color development and remained blue at temperatures below the complete decolorization temperature t4. Furthermore, when the disher was placed in a temperature environment of -6°C or higher, the microcapsule pigment was decolorized and the laminate turned white. When the disher was cooled again to -55°C or lower, the laminate turned blue.

[0133] The disher was cooled to below -55°C to allow the laminate to develop its color, and then it was moved and stored in a showcase at -25°C where ice cream is stored.The microcapsule pigment continued to maintain its color, and the laminate remained blue. Ice cream generally contains air and begins to melt at around -5°C. Once melted, the air inside the ice cream escapes, resulting in a poor texture and potentially a loss of quality. Therefore, care must be taken when serving ice cream to prevent it from melting too much. In the case of a disher with the above-described microcapsule pigment laminate attached, the microcapsule pigment maintains its colored state and the laminate appears blue unless the disher is placed in a temperature environment of -6°C or higher. At temperatures above -6°C, the microcapsule pigment loses its color and the laminate appears white. Therefore, the disher can be used while checking the color of the laminate attached to the disher, and the disher can be used as a training tool to ensure that ice cream is served carefully so that it does not melt too much and lose its quality.

[0134] Application example 3 A thermochromic, color-memory ink, consisting of 30 parts of the thermochromic, color-memory microcapsule pigment of Example 4, 62 parts of a urethane-based emulsion resin, 2 parts of a thickener, 0.5 parts of a leveling agent, 0.5 parts of an antifoaming agent, and 5 parts of a crosslinking agent, was solid-printed onto a white synthetic paper substrate using a 120-mesh screen, and the ink was dried and cured to form a reversible thermochromic layer, thereby obtaining an anti-counterfeiting medium. In the anti-counterfeiting medium, the microcapsule pigment was in a decolorized state under normal living conditions (e.g., 25°C), and the white color of the support was visible. When the anti-counterfeiting medium was cooled to -45°C or below, the microcapsule pigment developed a color and a blue color was visible, demonstrating that the medium had an anti-counterfeiting function. Furthermore, the anti-counterfeiting medium maintained a visible blue color in a temperature range below -10°C.

[0135] Application example 4 A thermochromic, color-memory ink consisting of 30 parts of the thermochromic, color-memory microcapsule pigment of Example 1 (thermochromic, color-memory microcapsule pigment A), 62 parts of a urethane-based emulsion resin, 2 parts of a thickener, 0.5 parts of a leveling agent, 0.5 parts of an antifoaming agent, and 5 parts of a crosslinking agent was solid-printed onto a white synthetic paper substrate using a 120-mesh screen, and then dried and cured to form a first reversible thermochromic layer (reversible thermochromic layer A). Next, a thermochromic, color-memory ink consisting of 30 parts of the thermochromic, color-memory microcapsule pigment of Example 3 (thermochromic, color-memory microcapsule pigment B), 62 parts of a urethane-based emulsion resin, 2 parts of a thickener, 0.5 parts of a leveling agent, 0.5 parts of an antifoaming agent, and 5 parts of a crosslinking agent was solid-printed onto the first reversible thermochromic layer using a 120-mesh screen, and then dried and cured to form a second reversible thermochromic layer (reversible thermochromic layer B), thereby obtaining an anti-counterfeiting medium. In the anti-counterfeiting medium, under everyday living conditions (e.g., 25°C), each of the thermochromic, color-memory microcapsule pigments was in a decolorized state, and the white color of the support was visible. When the anti-counterfeiting medium was cooled to a temperature above -55°C and below -37°C, one of the microcapsule pigments (microcapsule pigment B) developed a color, resulting in a visible magenta color, demonstrating anti-counterfeiting functionality. Furthermore, when the anti-counterfeiting medium was cooled below -55°C, the other microcapsule pigment (microcapsule pigment A) developed a color, resulting in a visible purple color, a mixture of the blue color of the colored microcapsule pigment A and the magenta color of the colored microcapsule pigment B. This demonstrated that the anti-counterfeiting medium had superior anti-counterfeiting functionality. Furthermore, the anti-counterfeiting medium maintained a visible purple color at temperatures below -6°C. [Explanation of symbols]

[0136] t1: the complete color development temperature of the thermochromic color-memory composition or the first thermochromic color-memory material t2: Color development start temperature of the thermochromic color-memory composition or the first thermochromic color-memory material t3: the temperature at which the thermochromic color-memory composition or the first thermochromic color-memory material begins to fade t4 Complete decolorization temperature of the thermochromic color-memory composition or the first thermochromic color-memory material t 1′ Complete color development temperature of the second thermochromic color memory material t 2′ Color development start temperature of the second thermochromic color memory material t 3′ The color-fading starting temperature of the second thermochromic color-memory material t 4′ Complete decolorization temperature of the second thermochromic color-memory material ΔH Hysteresis width 1 Temperature control indicator 2. Reversible thermochromic layer 21 First reversible thermochromic layer 22 Second reversible thermochromic layer 23 Reversible thermochromic layer containing a first thermochromic color-memory material and a second thermochromic color-memory material 3 Support 4. Non-thermochromic layer 5 Adhesive layer 6. Transparent support 7. Tamper-proof material with adhesive layer 8. Reversible thermochromic moldings 81 First reversible thermochromic molded body containing a first thermochromic color-memory material in a support 81' A first reversible thermochromic molded body containing a first thermochromic color-memory material in a transparent support 82 A second reversible thermochromic molded body containing a second thermochromic color-memory material in a support 82' A second reversible thermochromic molded body containing a second thermochromic color-memory material in a transparent support. 83 Reversible thermochromic molded body containing a first thermochromic color-memory material and a second thermochromic color-memory material in a support 9 Transparent protective layer

Claims

1. A thermochromic color-memorizing composition comprising at least (a) an electron-donating organic color-forming compound, (b) an electron-accepting compound, and (c) a reaction medium represented by the following formula (1) that controls the color reaction of the components (a) and (b), wherein the composition exhibits hysteresis characteristics in a color density-temperature curve, exhibiting alternation between a colored state and a decolored state, and in the process of increasing the temperature from the colored state, the decolorization starting temperature t ３ When the temperature reaches t ３ Higher complete bleaching temperature t ４ In the above temperature range, the color is completely lost. In the process of decreasing the temperature from the lost color state, the coloring start temperature t ２ When the temperature reaches t ２ Lower full color temperature t １ The color density vs. temperature curve shows a hysteresis width (ΔH) of 8 to 100°C, and the color changes at the temperature t １ is -30°C or less, and the complete decolorization temperature t ４ The thermochromic color-memorizing composition has a temperature of -25 to 15°C. 【Chemistry 1】 [In the formula, R １ represents a group represented by the following formula (2) or a cycloalkyl group, and R ２ represents a linear or branched alkyl group having 1 to 13 carbon atoms. 【Chemistry 2】 (wherein X represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms)

2. The R １ 2. The thermochromic color-memory composition according to claim 1, wherein X is a hydrogen atom, a methyl group, or a cyclohexyl group.

3. The R ２ 3. The thermochromic color-memory composition according to claim 1, wherein is a linear or branched alkyl group having 3 to 11 carbon atoms.

4. A thermosensitive color-changing color-memory material using the thermosensitive color-changing color-memory composition described in any one of claims 1 to 3, which is a thermosensitive color-changing color-memory microcapsule pigment encapsulating the thermosensitive color-memory composition, or a thermosensitive color-memory resin particle in which the thermosensitive color-memory composition is dispersed in a thermoplastic resin or a thermosetting resin.

5. A thermochromic, color-memorizing liquid composition comprising the thermochromic, color-memorizing material according to claim 4 dispersed in a vehicle.

6. A laminate comprising a support and a reversible thermochromic layer comprising the thermochromic color memory material of claim 4 provided on the support.

7. 5. A thermochromic, color-memory molding resin composition, comprising the thermochromic, color-memory material according to claim 4, melt-blended with a thermoplastic resin, a thermosetting resin, or a wax.

8. A molded article obtained by molding the thermochromic, color-memory molding resin composition according to claim 7.

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