Thermochromic color memory composition and thermochromic color memory 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-memorizing composition and a thermochromic color-memorizing material using the same. [Background technology]

[0002] Conventionally, thermosensitive color-changing color-memory compositions and thermosensitive color-memory microcapsule pigments encapsulating the same have been disclosed, which show large hysteresis characteristics in response to temperature changes, undergoing reversible color changes of coloring and fading, and which alternately and reversibly retain either a colored state or a faded 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 thermosensitive color-changing color-memory material, unlike conventional reversible thermochromic materials that change color just before and just after a color-changing temperature, and of the two states before and after the color-changing, only one specific state exists at room temperature, and the other state is maintained as long as the heat or cold required to manifest that state is applied, and returns to the state it exhibits at room temperature when the application of heat or cold is removed, can selectively retain either the color on the lower or higher side of the color-changing temperature at room temperature, and can alternately retain the colors by applying heat or cold as necessary, and is therefore applied 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 an increase or decrease in temperature, making it possible to detect counterfeits (see, for example, Patent Document 11). The above-mentioned anti-counterfeiting medium is provided with a reversible thermochromic layer containing each thermochromic color-memory composition, one of which is colored and the other of which is colorless, and which exhibits 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 management indicator that can irreversibly determine whether or not a specified temperature range has been exceeded.

[0003] In recent years, a logistics method known as cold chain has become widespread, which allows goods such as fresh food, frozen food, and medicines, whose proper temperature range is low, to be distributed over a wide area without deteriorating in quality by maintaining the proper temperature range during the distribution process from production to transportation to consumption. In the cold chain, it is necessary to control the temperature so that it is possible to reliably determine whether the goods have been kept in a temperature environment exceeding the proper temperature range during the distribution process without ever departing from the temperature environment exceeding the proper temperature range. By using a material that changes color when it deviates from a predetermined temperature range, it is possible to easily detect whether the goods have deviated from the proper temperature range. Although the above-mentioned counterfeit prevention medium has a function as a temperature control indicator that can irreversibly determine whether the goods have deviated from the normal temperature range by using a thermochromic color-memorizing material, when used for goods with a low proper temperature range, i.e., goods whose proper temperature range is in the low temperature range, it is difficult for the thermochromic color-memorizing material to alternatively memorize and retain the color, and it is difficult to irreversibly determine whether the goods have deviated from the temperature environment exceeding the proper temperature range. Further, no thermosensitive color-memorizing material capable of selectively memorizing and retaining a color in a low temperature range has been disclosed so far. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2005-1369 A [Patent Document 2] JP 2006-137886 A [Patent Document 3] JP 2006-188660 A [Patent Document 4] JP 2008-280523 A [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] JP 2017-170664 A Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention provides a thermosensitive color-changing color-memory composition which 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 thermosensitive color-changing 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) for controlling the color reaction of the components (a) and (b). The composition exhibits hysteresis characteristics in a color density-temperature curve, and exhibits alternation between a colored state and a decolored state. In the process of increasing temperature from the colored state, the composition starts to decolor when it reaches a decolorization initiation temperature t3, and reaches a complete decolorization temperature t4 higher than the temperature t3. The thermosensitive color-changing color-memory composition is required to have a temperature-sensitive color-changing property in which the composition becomes completely colorless in a temperature range of t1 or higher than t2, and in the process of decreasing temperature from the colorless state, the composition begins to color when it reaches a color-development starting temperature t2, and becomes completely colored in a temperature range of t1 or lower that is lower than t2. The composition exhibits hysteresis characteristics in which the composition changes color while showing a hysteresis width (ΔH) of 8 to 100°C in terms of the color density-temperature curve, and the composition has a complete color-development temperature t1 of -30°C or lower and a complete color-discharging temperature t4 in the range of -25 to 15°C. [ka] [In the formula, 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] (In the formula, X represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms.) Further, the above-mentioned R1 is a group in which X is a hydrogen atom or a methyl group, or a cyclohexyl group, and the above-mentioned R2 is a linear or branched alkyl group having 3 to 11 carbon atoms. Furthermore, the present invention requires a temperature-sensitive color-changing color-memory material using the above-mentioned temperature-sensitive color-changing color-memory composition, which is a temperature-sensitive color-changing color-memory microcapsule pigment that encapsulates the temperature-sensitive color-changing color-memory composition, or a temperature-sensitive color-changing color-memory resin particle in which the temperature-sensitive color-changing color-memory composition is dispersed in a thermoplastic resin or a thermosetting resin. Furthermore, the present invention is characterized in that the thermosensitive color changing color memory liquid composition is prepared by dispersing the thermosensitive color changing color memory material in a vehicle. Furthermore, the present invention also requires a laminate in which a reversible thermochromic layer containing the above-mentioned thermochromic color memory material is provided on a support. Further, the present invention is characterized in that the thermochromic, color-memorizing molding resin composition is prepared by melt-blending the thermochromic, color-memorizing material with a thermoplastic resin, a thermosetting resin, or a wax. Effect of the Invention

[0007] The present invention provides a thermochromic color-memorizing composition that uses a specific ester compound and exhibits a color-memorizing effect in a low temperature range, and can increase the freedom of selecting a reaction medium, thereby further increasing the utility of this type of thermochromic color-memorizing material. [Brief description of the drawings]

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

[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 medicines, and refers to 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 characteristic in the color density-temperature curve of the thermochromic color-memory composition (reversible thermochromic composition having color memory property) applied to the present invention will be described below. In Fig. 1, the vertical axis represents color density, and the horizontal axis represents temperature. The change in color density due to temperature change progresses along the arrow. Here, A is a point indicating the density at temperature t4 (hereinafter referred to as the complete decolorization temperature) at which the completely decolorized state is reached, B is a point indicating the density at temperature t3 (hereinafter referred to as the decolorization onset temperature) at which the completely colored state can be maintained, C is a point indicating 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 is a point indicating 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 region 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 onset temperature t2 and the decolorization onset temperature t3, which is the region in which the difference in color density is large, is the actual discoloration temperature region. Specifically, a thermochromic color-memory composition in a decolorized state can be caused to start changing to a colored state by cooling it to a temperature below the color development start temperature t2, and can be brought to a fully colored state by cooling it to a temperature below the complete color development temperature t1, and this state can be maintained unless the temperature of the thermochromic color-memory composition is raised to the decolorization start temperature t3. In addition, by applying heat to a thermosensitive color-changing color-memory composition in a colored state and heating it to a temperature equal to or higher than the color-changing start temperature t3, the change to the color-decolored state can be initiated, and by heating it to a temperature equal to or higher than the complete color-decoloring temperature t4, the composition can be brought to a completely color-decolored state, and this state can be maintained unless the temperature of the thermosensitive color-changing color-memory composition is lowered to the color-decoloring start temperature t2. The length of the line segment EF is a scale showing 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 showing the degree of hysteresis [hereinafter referred to as hysteresis range (ΔH)], and the larger ΔH is, the easier it is to maintain each state before and after the discoloration. ΔH at which each state before and after the discoloration can be maintained is 8°C or more, specifically in the range of 8 to 100°C. Since it is even easier to maintain each state before and after the discoloration, ΔH is preferably 20 to 100°C, more preferably 30 to 100°C. Here, Δt, which is the difference between the complete decolorization temperature t4 and the decolorization start temperature t3, or the difference between the color development start temperature t2 and the complete color development temperature t1, is a scale showing the sensitivity of the discoloration, and a range of Δt=1 to 20°C is practical, and further, Δt=1 to 15°C is preferable, and Δt=1 to 10°C is more preferable. In the present invention, the thermosensitive color-changing color-memory material uses a thermosensitive color-memory composition, and the hysteresis characteristics in the color density-temperature curve of the thermosensitive color-memory material are the hysteresis characteristics in the color density-temperature curve of the thermosensitive color-memory composition.

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

[0012] Components (a), (b), and (c) will be specifically described below. Component (A), i.e., the electron-donating organic color-forming compound, is the component that determines the color, and is a compound that develops color by donating electrons to component (B), which is a color developer. Examples of the electron-donating organic color-forming compound include phthalide compounds, fluoran compounds, styrinquinoline compounds, diazarhodamine lactone compounds, pyridine compounds, quinazoline compounds, and bisquinazoline compounds. Among these, phthalide compounds and fluoran compounds are preferred. Examples of the phthalide compound include a diphenylmethane phthalide compound, a phenylindolyl phthalide compound, an indolyl phthalide compound, a diphenylmethane azaphthalide compound, a phenylindolyl azaphthalide compound, and derivatives thereof. Among these, the phenylindolyl azaphthalide compound and its derivatives are preferred. Examples of the fluoran compound include aminofluoran compounds, alkoxyfluoran compounds, and derivatives thereof.

[0013] Examples of the electron donating organic color former 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-butoxyfluoran, 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]xanthen]-3-one, 3',6'-bis[phenyl(3-ethylphenyl)amino]spiro[isobenzofuran-1(3H),9'-[9H]xanthen]-3-one, 2,6-bis(2′-ethyloxyphenyl)-4-(4′-dimethylaminophenyl)pyridine, 2,6-bis(2′,4′-diethyloxyphenyl)-4-(4′-dimethylaminophenyl)pyridine, 2-(4′-dimethylaminophenyl)-4-methoxyquinazoline, 4,4'-Ethylenedioxy-bis[2-(4-diethylaminophenyl)quinazoline] Examples include: In addition, the fluorans may be compounds having a substituent on the phenyl group forming the xanthene ring, or may be compounds having a substituent on the phenyl group forming the xanthene ring and also having a substituent (e.g., 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, which exhibit a blue or black color.

[0014] Component (b), ie, an 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-memorizing 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 phosphoric 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. As the carboxylic acids and derivatives thereof, aromatic carboxylic acids and derivatives thereof, or aliphatic carboxylic acids having 2 to 5 carbon atoms and derivatives thereof are preferred. 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 phosphates, 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 since they can more effectively exhibit the thermochromic properties. Compounds having a phenolic hydroxyl group include a wide range of compounds from monophenol compounds to polyphenol compounds, and further include bisphenol compounds, trisphenol compounds, phenol-aldehyde condensation resins, etc. Compounds having a phenolic hydroxyl group preferably have at least two benzene rings. Compounds having a phenolic hydroxyl group may also have substituents such as alkyl groups, aryl groups, acyl groups, alkoxycarbonyl groups, carboxyl groups and their esters or amide groups, halogen atoms, etc.

[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, o-Methylphenylethyl 4-hydroxybenzoate, 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 the bisphenol compound 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)butyl propionate, 2,2-bis(4-hydroxy-3-methylphenyl)methylpropionate, 2,2-bis(4-hydroxyphenyl)ethyl propionate, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 2,2-bis(4-hydroxyphenyl)-4-methylhexane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 2,2-bis(3,5-dihydroxymethyl-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)butane, 2,2-bis(4-hydroxy-3-isopropylphenyl)propane, 2,2-bis(3-sec-butylphenyl-4-hydroxy)propane, 2,2-bis(4-hydroxy-3-phenylphenyl)propane, 2,2-bis(3-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(3-fluoro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dihydroxymethyl-4-hydroxyphenyl)propane, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, 1,4-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, 3,3-bis(4-hydroxyphenyl)oxindole, 3,3-bis(4-hydroxy-3-methylphenyl)oxindole, bis(2-hydroxyphenyl)methane, Bis(2-hydroxy-5-methylphenyl)methane, Bis(2-hydroxy-3-hydroxymethyl-5-methyl)methane, 4,4'-[1,4-phenylenebis(1-methylethylidene)]bis(2-methylphenol), 1,1-bis(4-hydroxy-3-phenylphenyl)cyclohexane, 3,3-ethyleneoxydiphenol, 1,4-bis(4-hydroxybenzoate)-3-methylbenzene, 4,4″-dihydroxy-3″-methyl-p-terphenyl, 4,4″-dihydroxy-3″-isopropyl-p-terphenyl, 2,2-dimethyl-1,3-bis(4-hydroxybenzoyloxy)propane, 2,2′-biphenol, 4,4′″-dihydroxy-p-quaterphenyl, 4,4-dihydroxydiphenyl ether, bis(4-hydroxyphenylthioethyl) ether, bis(4-hydroxyphenyl)sulfone, 4-benzyloxy-4′-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, phloroglucinol carboxylic 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″-ethylidynetris(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 their derivatives include: 3,5-di(α-methylbenzyl)salicylic acid, 4-(2-p-methoxyphenyloxyethoxy)salicylic acid, 4-Hydroxyphenylbenzoic acid, 4-chlorobenzoic acid, 4-[2-(p-methoxyphenoxy)ethyloxy]salicylic acid, 4-[3-(p-tolylsulfonyl)propyloxy]salicylic acid, 5-[p-(2-p-methoxyphenoxyethoxy)cumyl]salicylic acid, 4-octyloxycarbonylaminosalicylic acid, 3,5-distyrenated salicylic acid, N-(p-toluenesulfonyl)-glycine, N-(p-toluenesulfonyl)-alanine, N-(p-toluenesulfonyl)-β-alanine, N-phenylaminocarbonyl-glycine, N-phenylaminocarbonyl-valine, N-(m-tolylaminocarbonyl)-phenylalanine, N-(m-tolylaminocarbonyl)-cysteine-S-benzyl, N-(m-tolylaminocarbonyl)-methionine, N-(m-tolylaminocarbonyl)-tyrosine, N-(p-tolylaminocarbonyl)-phenylalanine, N-(p-tolylaminocarbonyl)-cysteine-S-benzyl, N-(p-tolylaminocarbonyl)-methionine, N-(phenylaminocarbonyl)-methionine, N-(p-tolylaminocarbonyl)-tyrosine, 2-O-(phenylaminocarbonyl)-mandelic acid, 2-O-(p-tolylaminocarbonyl)-mandelic acid, 2-O-(m-tolylaminocarbonyl)-mandelic acid, 2-O-(o-tolylaminocarbonyl)-mandelic acid, 2-O-(1-naphthylaminocarbonyl)-mandelic acid, 2-O-(3-isopropenyl-α,α-dimethylbenzylaminocarbonyl)-mandelic acid, 2-O-(benzylaminocarbonyl)-mandelic acid, 2-O-(phenethylaminocarbonyl)-mandelic acid, 2-O-(phenylaminocarbonyl)-lactic acid, 2-O-(p-tolylaminocarbonyl)-lactic acid, 2-O-(m-tolylaminocarbonyl)-lactic acid, 2-O-(o-tolylaminocarbonyl)-lactic acid, 2-O-(1-naphthylaminocarbonyl)-lactic acid, 2-O-(3-isopropenyl-α,α-dimethylbenzylaminocarbonyl)-lactic acid, 2-O-(benzylaminocarbonyl)-lactic acid, 2-O-(Phenethylaminocarbonyl)-lactic acid Examples include:

[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, bis(2-ethylhexyl)phosphate, and the like.

[0026] As component (b), a compound having a phenolic hydroxyl group is preferable because it can more effectively exhibit the thermal discoloration 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 having 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 thermosensitive color-changing color-memory composition having a color-changing 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] [In the formula, 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] (In the formula, 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 straight-chain 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. However, in terms of availability and cost, an alkylbenzyl alcohol having an alkyl group 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 the ester compounds obtained by 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 having 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, 2-ethylbenzyl butyrate, and , 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 esterification of cycloalkylmethanol with a carboxylic acid having 2 to 14 carbon atoms include cyclopropyl methyl acetate, cyclobutyl methyl acetate, cyclopentyl methyl acetate, cyclohexyl methyl acetate, cycloheptyl methyl acetate, cyclooctyl methyl acetate, cyclopropyl methyl butyrate, cyclobutyl methyl butyrate, cyclopentyl methyl butyrate, cyclohexyl methyl butyrate, cycloheptyl methyl butyrate, cyclooctyl methyl butyrate, cyclopropyl methyl caproate, cyclobutyl methyl caproate, cyclopentyl methyl caproate, cyclohexyl methyl caproate, cycloheptyl methyl caproate, cyclooctyl methyl caproate, cyclopropyl methyl caproate, cyclobutyl methyl caproate, cyclopentyl methyl caproate, cyclohexyl methyl caproate, cycloheptyl methyl caproate, cyclooctyl methyl caproate, cyclopropyl methyl caprylate, cyclobutyl methyl caprylate ... Examples of the cyclopropyl methyl ester include cyclopropyl methyl ester, cyclohexyl methyl caprylate, cycloheptyl methyl caprylate, cyclooctyl methyl caprylate, cyclopropyl methyl caprate, cyclobutyl methyl caprate, cyclopentyl methyl caprate, cyclohexyl methyl caprate, cycloheptyl methyl caprate, cyclooctyl methyl caprate, cyclopropyl methyl laurate, cyclobutyl methyl laurate, cyclopentyl methyl laurate, cyclohexyl methyl laurate, cycloheptyl methyl laurate, cyclooctyl methyl laurate, cyclopropyl methyl myristate, cyclobutyl methyl myristate, cyclopentyl methyl myristate, cyclohexyl methyl myristate, cycloheptyl methyl myristate, and cyclooctyl methyl myristate.

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

[0035] In formula (1), since it is easy to obtain a compound with a lower discoloration temperature and a larger hysteresis width, 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, and 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, and 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. Further, in the formula (1), it is more preferable that R1 is a group represented by the 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] [In the formula, R1 represents a group represented by the following formula (4) or a cycloalkyl group] [ka] (In the formula, 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. Specific examples include benzyl caprylate, 2-methylbenzyl caprylate, 3-methylbenzyl caprylate, 4-methylbenzyl caprylate, and cyclohexylmethyl caprylate.

[0037] The thermosensitive color-changing color-memorizing composition causes a reversible color change of coloring and decoloring, and shows a wide hysteresis width (ΔH) in the color concentration-temperature curve during this reversible color change. By containing an ester compound with a specific structure, the color change temperature is in a low temperature range, and both colors on the lower side and higher side of the color change temperature can be alternately stored and retained, and by heating or cooling as necessary, it is possible to effectively express the property of reversibly reproducing and storing either color. Therefore, it is possible to provide a thermosensitive color-memorizing composition that is excellent in applicability to various applications such as thermochromism, decoration, and teaching tools, and a thermosensitive color-memorizing microcapsule pigment containing the thermosensitive color-memorizing composition, or a thermosensitive color-memorizing resin particle containing the thermosensitive color-memorizing composition.

[0038] The component (c) may be an ester compound represented by formula (1) or (3) that is used in combination as appropriate. The component (c) may further contain a conventionally known component (c) such as an ester other than that represented by formula (1) or (3), an alcohol, a carboxylic acid, a ketone, or an amide. When the component (iii) contains compounds other than those represented by formulae (1) and (3), the content of the compounds other than those represented by formulae (1) and (3) 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 the component (iii).

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

[0040] The thermochromic color-memorizing composition can be used as a thermochromic color-memorizing material by encapsulating it in a microcapsule to form a thermochromic color-memorizing microcapsule pigment (hereinafter sometimes referred to as a "microcapsule pigment"), or by dispersing it in a thermoplastic resin or a thermosetting resin to form a thermochromic color-memorizing resin particle (hereinafter sometimes referred to as a "resin particle"), but it is preferable to encapsulate the thermochromic color-memorizing composition in a microcapsule to use it as a microcapsule pigment. This is because by encapsulating it in a microcapsule, a chemically and physically stable pigment can be formed, and further, the thermochromic color-memorizing composition can be maintained in the same composition under various use conditions and can exert the same action and effect.

[0041] Microencapsulation can be appropriately selected according to the application, from 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. Furthermore, a secondary resin film can be provided on the surface of the microcapsules according to 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 brought about. The thermosensitive color-changing color-memorizing 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, the dispersion stability and processing suitability tend to be poor. On the other hand, if the average particle size is less than 0.1 μm, it becomes difficult to exhibit high-concentration color development. Furthermore, by micronizing the microencapsulated pigment or resin particles, it is possible to increase ΔH relative to the ΔH of the three-component composition. The average particle size was measured by determining the particle region using image analysis particle size distribution measurement software (manufactured by Mountec Corporation, product name: MacView), calculating the projected area equivalent circle diameter (Heywood diameter) from the area of ​​the particle region, and measuring the average particle size of particles equivalent to a sphere of equal volume using this value. In addition, when the particle size of all or the majority of the particles exceeds 0.2 μm, it is also possible to measure the average particle size of particles equivalent to an equal volume sphere by the Coulter method using a particle size distribution measuring device (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-memorizing liquid composition such as a printing ink used in screen printing, offset printing, process printing, gravure printing, coater printing, pad printing, etc., or a paint used in brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, dip coating, etc.

[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 thermosensitive color changing, color-memorizing liquid composition, the support is not particularly limited, and examples thereof include paper, synthetic paper, fiber, knitted fabric, woven fabric, nonwoven fabric and other fabrics, synthetic leather, leather, plastic, glass, elastomer, rubber, ceramics, metal, wood, stone, etc., and the like. The form may be uneven, but flat, sheet or film forms are preferred. Furthermore, a reversible thermochromic layer containing a thermochromic color-memorizing composition, a thermochromic color-memorizing 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 disappear or appear by a reversible thermochromic layer due to a change in temperature, thereby making it possible to further diversify the appearance of the change. Furthermore, the thermosensitive color-changing, color-memorizing microcapsule pigment or resin particles can be melt-blended with thermoplastic resins, thermosetting resins, or waxes, and used as a thermosensitive color-changing, color-memorizing molding resin composition in the form of pellets, powder, or paste, and molded articles in the form of three-dimensional objects of any shape, films, sheets, plates, filaments, rods, pipes, etc. can be obtained by general-purpose injection molding, extrusion molding, blow molding, cast molding, or other means. In addition, by blending a non-thermochromic colorant such as a general dye or pigment in 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 on 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 on 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 in which the surface of a core material such as natural mica, synthetic mica, glass pieces, alumina, or transparent film pieces 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 thermosensitive color-changing, color-memorizing composition and the thermosensitive color-changing, color-memorizing microcapsule pigment encapsulating the same, or the thermosensitive color-changing, color-memorizing resin particles include various printed matter 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, and temperature control indicators.

[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 the 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 the temperature control indicator is placed in a temperature environment exceeding the appropriate temperature range, it is difficult to return it to its initial state, so that it is possible to irreversibly determine that it has deviated from the temperature environment exceeding the appropriate temperature range.

[0049] The appropriate temperature range for items requiring temperature control, such as fresh foods, frozen foods, and medicines, to which the cold chain is applied, is in the low temperature range, and from the standpoint of hygiene control, fresh foods are set at 0 to 10°C, and frozen foods are set at -18°C or lower, preferably -25°C or lower. Medicines are mainly set at 10°C or lower, particularly 2 to 8°C. The appropriate temperature range differs depending on the item, but the appropriate temperature range for most items to which the cold chain is applied is above -30°C and is in the low temperature range of 10°C or lower, 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 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) under the Warehousing Business Act, and can be stored within the appropriate temperature range by appropriately selecting from cooling devices commonly used in everyday living environments, such as cooling and heating devices that use Peltier elements, cooling and heating 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 discolorable color memory property applied to the present invention in the range of -25 to 15°C, the temperature management indicator of the present invention can function effectively for temperature management within the appropriate temperature range of an article that requires temperature management or its storage container. When a temperature management indicator in which the first thermosensitive discolorable color memory material is in a colored state is placed in a temperature environment exceeding the appropriate temperature range, the first thermosensitive discolorable 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 discolorable 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. Furthermore, since the temperature management of the article or its storage container can be performed strictly, 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 discolorable 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, a warehouse or cooling device classified as Class F1 or Class C1 - 3, specifically, the first thermosensitive discolorable color memory material does not easily color by a cooling device generally used in daily living environments. That is, in order to color the first thermosensitive discolorable color memory material, a warehouse or 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 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), Class F4 (-50°C or lower temperature range) based on the Warehouse Business Act, and examples thereof include cooling devices 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 in a colored state using a warehouse or cooling equipment classified as F2 to 4 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 equipment classified as F1 or C1 to 3 under the Warehousing Business Act, which are used for storing items or their storage containers that require temperature control.

[0052] Therefore, 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 Class C4 based on the Warehousing Business Law by setting the complete color development temperature t1 of the first thermochromic color memory material to -30°C or lower, and the first thermochromic color memory material can be colored, and the color of the first thermochromic color memory material in the colored state can be visually recognized (initial state). Furthermore, since the initial state can be maintained in a temperature environment below the complete decolorization temperature t4 of the first thermochromic color memory material, the temperature control indicator can be maintained in the initial state by using a cooling device commonly used in daily living environments, specifically a warehouse or cooling device classified as Class F1 or Class C1 to Class C3 based on the Warehousing Business Law. 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 perform temperature management of an article or its storage container having an appropriate temperature range in the low temperature range. When the temperature management indicator in the initial state is placed in a temperature environment exceeding the appropriate temperature range, the first thermochromic color-memory material in the colored state decolorizes, and the color of the thermochromic color-memory material in the decolorized state becomes visible (state 1). Therefore, since the color change occurs when the temperature management indicator changes from the initial state to state 1, it is possible to detect that the temperature management indicator has deviated from the temperature environment exceeding the appropriate temperature range. Even if the temperature control indicator in state 1 is stored again in the warehouse or cooling device in which the article or its storage container was stored, the first thermochromic color-memory material does not change color and remains in a decolorized state. This is because the temperature t1 of the first thermochromic color-memory material of the temperature control indicator of the present invention is in the ultra-low temperature range (below -30°C), and cooling devices commonly used in daily 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, and it is possible to irreversibly determine that it has deviated from the temperature environment beyond the appropriate temperature range.

[0053] In addition, in a temperature control indicator in which the first thermochromic color-memory material is in a decolorized state, the first thermochromic color-memory material is maintained in the decolorized state unless it is cooled to a temperature below the complete color-developing temperature t1, so that, for example, in a room temperature (25°C) environment, the first thermochromic color-memory material is in the decolorized state. In addition, since the complete color-developing temperature t1 of the first thermochromic color-memory material is below -30°C, it is difficult to cause the first thermochromic color-memory material to develop color using a cooling device commonly used in everyday living environments. In other words, in a room temperature environment, the color exhibited by the first thermochromic color memory material in its colored state is not visible, and only by cooling to an ultra-low temperature range can the color exhibited by 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 color-discoloring 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 color-discoloring temperature t4 is within the above temperature range, the temperature control indicator of the present invention can effectively function in an article or its storage container having 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 becomes unnecessary thereafter. Therefore, by not placing the warehouse or cooling device capable of initializing the temperature control indicator adjacent to the warehouse or cooling device for controlling the temperature of the item or storage container that requires temperature control, it becomes easier to prevent tampering by cooling the temperature control indicator, which has deviated from the appropriate temperature range and the first thermochromic color memory material has become decolorized, back to the 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 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, and the temperature of the items or their storage containers is controlled by this. This is preferable because it makes it easier to prevent tampering by cooling the temperature control indicator, which has fallen into a temperature environment that exceeds the appropriate temperature range and whose first thermochromic color memory material has become discolored, back to its initial state.

[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. By having the complete color development temperature t1 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 decolorized due to deviation from a temperature environment exceeding the appropriate temperature range to its initial state using a cooling device commonly used in daily living environments, making it easier to irreversibly determine that the temperature control indicator has deviated from the appropriate temperature range and more easily 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 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 hysteresis width (ΔH) of the first thermochromic color memory material is preferably 20 to 100°C, the complete color development temperature t1 is -40°C or less, and the complete discoloration temperature t4 is preferably in the range of -25 to 15°C, and the hysteresis width (ΔH) is preferably 30 to 100°C. This makes it easier to maintain each state before and after discoloration, and makes it easier to irreversibly determine that the temperature environment has deviated from 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 hysteresis width (ΔH) of the first thermochromic color memory material is 20 to 100°C, the complete color development temperature t1 is -50°C or less, and the complete discoloration temperature t4 is in the range of -25 to 15°C, and the hysteresis width (ΔH) is preferably 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 thermosensitive color-changing color-memory material, like the first thermosensitive color-changing color-memory material described above, has a color-changing temperature in the low temperature range, and is a thermosensitive color-changing color-memory microcapsule pigment encapsulating a thermosensitive color-changing color-memory composition consisting of at least components (a), (b), and (c), or a thermosensitive color-changing color-memory resin particle in which the thermosensitive color-changing color-memory composition is dispersed in a thermoplastic resin or a thermosetting resin. The 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 temperature-sensitive color-changing and color-memory material, that is, t 4′ <satisfies t4, and further, with respect to 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 the article or its storage container that requires temperature management, 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] The temperature management indicator provided with the second temperature-sensitive color-changing and color-memory material has, when the temperature is less than t 4′ <, a color in which the colors by each temperature-sensitive color-changing and color-memory material in the coloring state are mixed colors 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 temperature-sensitive color-changing and color-memory material in the coloring state decolorizes, and the color by the first temperature-sensitive color-changing and 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 temperature-sensitive color-changing and color-memory material in the coloring state decolorizes, and the colors in which each temperature-sensitive color-changing and color-memory material is in the decolorized state are visually recognized (state 3) is configured. And since it is difficult for the temperature management indicator once placed in the specific temperature range or once placed in a temperature environment exceeding the appropriate temperature range to return to the initial state, it can be irreversibly detected that it has been placed in the specific temperature range or has deviated from the temperature environment exceeding the appropriate temperature range.

[0061] The complete coloring temperature t of the second temperature-sensitive color-changing and color-memory material 1′Since the temperature is -30°C or lower, 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 develop color in a warehouse or cooling device classified as F1 class or C1 to C3 class based on the Warehousing Business Law, which is used to store items requiring temperature control or their storage containers in an appropriate temperature range. In other words, in order to develop color in the second thermochromic color-memory material, a warehouse or cooling device classified as F2 to C4 class based on the Warehousing Business Law is required. By using such a warehouse or cooling device, it becomes possible to develop color in both the first thermochromic color-memory material and the second thermochromic color-memory material. A temperature control indicator in which a first thermochromic color-memory material and a second thermochromic color-memory material are in a colored state by a warehouse or cooling device classified as F2 to 4 class based on the Warehousing Business Law is a temperature control indicator that is capable of controlling the temperature at which the second thermochromic color-memory material completely loses its color. 4′ Since each thermochromic color-memory material can be maintained in a colored state in a temperature range below 30°C, the temperature control indicator can be maintained in its initial state even when using a warehouse or cooling equipment 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-memorizing materials can be cooled in an ultra-low temperature range using a warehouse or cooling device classified as F2 to 4 under the Warehousing Business Law, and the colors of the thermochromic color-memorizing materials in the colored state can be mixed and visually recognized (initial state). 4′ It can maintain its initial state in a temperature environment below the complete decolorization temperature t 4′Since the range of temperature is -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 has a complete color loss 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 with respect to the difference (Δt4) between the temperature control indicator and the specific temperature range of an item or its storage container that has an appropriate temperature range in the low temperature range, the item or its storage container can have a temperature control function in the specific temperature range. 4′ When the temperature control indicator is placed in a temperature environment below temperature t4, the second thermochromic color memory material in a colored state loses its color, and the color of the first thermochromic color memory material in a 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 is possible to detect 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 decolored 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 (-30°C or lower), and cooling devices commonly used in daily living environments cannot cool the temperature to the temperature required to return 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 it has been placed in a specific temperature range within the appropriate temperature range. When the 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 a colored state loses its color, and the color of each thermochromic color memory material in a decolored state becomes visible (State 3). Even if a temperature control indicator in the initial state is placed in a temperature environment that exceeds the appropriate temperature range, each thermochromic color memory material in a colored state loses its color, and the indicator 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 is possible to detect that the temperature control indicator has deviated from the temperature environment that exceeds the appropriate temperature range. Even if the temperature control indicator in state 3 is stored again in the warehouse or cooling device in which the article or its storage container was stored, each thermochromic color-memorizing material does not develop color and is maintained 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-memorizing composition and the complete color development temperature t 1′ This is because the temperature is in the ultra-low temperature range (-30°C or lower), and cooling devices commonly used in everyday living environments cannot cool the temperature to the temperature required to return 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 temperature has deviated from 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 are distributed or stored within the appropriate temperature range below are classified as items in a specific temperature range (temperature t 4′ This can be used for temperature control when thawing at a temperature above t3 but below t4. When a frozen item 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 it has been placed in the specific temperature range and to determine that the frozen item has been thawed in the specific temperature range.

[0064] In addition, for a temperature control indicator in which both the first temperature-sensitive color-changing and color-memory material and the second temperature-sensitive color-changing and color-memory material are in a decolorized state, the full-color temperature t1 and the full-color temperature t 1′ Unless cooled below this temperature, each temperature-sensitive color-changing and color-memory material is maintained in a decolorized state. For example, in a room temperature (25 °C) environment, each temperature-sensitive color-changing and color-memory material is in a decolorized state. Also, the full-color temperature t1 of the first temperature-sensitive color-changing and color-memory material and the full-color temperature t 1′ is -30 °C or lower, so it is difficult to cause each temperature-sensitive color-changing and color-memory material to develop color using a cooling device commonly used in daily living environments. That is, in a room temperature environment, the colors shown by each temperature-sensitive color-changing and color-memory material in the colored state are not visible. Only by cooling to an ultra-low temperature range can the color of the first temperature-sensitive color-changing and color-memory material in the colored state or the color of the second temperature-sensitive color-changing and color-memory material in the colored state be seen for the first time. 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 temperature-sensitive color-changing and color-memory material develops color in the temperature range below the temperature t1, and the color of the first temperature-sensitive color-changing and color-memory material in the colored state is visible. When the temperature is t 1′ or lower, the second temperature-sensitive color-changing and color-memory material develops color, and a color in which the colors of the temperature-sensitive color-changing and color-memory materials in the colored state are mixed is visible. That is, a difference occurs in the visible color at a specific temperature (a temperature exceeding t 1′ and below the temperature t1). Therefore, it can be used as an anti-counterfeiting medium with an enhanced anti-counterfeiting function. Note that "substantially the same" means that the temperature t1 and the temperature t 1′ are exactly the same temperature. Also, in the present invention, the absolute value (|Δt1|) of the difference (Δt1) between the temperature t1 and the temperature t1 satisfies |Δt1 = (the full-color temperature t1 of the first temperature-sensitive color-changing and color-memory material) - (the full-color temperature t 1′ )| ≦ 3 °C.

[0065] The 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′ By virtue of being within the above temperature range, the temperature control indicator of the present invention can function effectively for articles or their storage containers having an appropriate temperature range in a lower temperature 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, it becomes easier for the temperature control indicator to function effectively in temperature control in a specific temperature range of an article or its storage container whose appropriate temperature range is in the low temperature range.

[0067] In addition, in the case of a temperature control indicator having a second thermochromic color memory material, once it is initialized using a warehouse or cooling device classified as F2 to 4 class under the Warehousing Business Law, the warehouse or cooling device is no longer necessary. Therefore, by not placing the warehouse or cooling device capable of initializing the temperature control indicator adjacent to the warehouse or cooling device for controlling the temperature of the item or storage container that requires temperature control, it becomes easier to prevent tampering by cooling the temperature control indicator, which is placed in a specific temperature range and the second thermochromic color memory material is in a decolorized state, or which is deviated from the temperature environment exceeding the appropriate temperature range and both thermochromic color memory materials are in a decolorized state, back to the initial state. Furthermore, by setting the environment in which the temperature control indicator can be set to its initial state far away from the environment in which the temperature of the items or their storage containers that require temperature control is controlled, and transporting the temperature control indicator that has been set to its initial state in a warehouse or cooling device classified as F2 to 4 under the Warehousing Business Act to a warehouse or cooling device that controls the temperature of the items or their storage containers while maintaining its initial state, and controlling the temperature of the items or their storage containers, this is preferable because it makes it easier to prevent tampering by cooling the temperature control indicator again to its initial state after it has been placed in a specific temperature range and the second thermochromic color memory material has become discolored, or after it has deviated from the appropriate temperature range and both thermochromic color memory materials have become discolored.

[0068] The complete color development temperature t of the second thermochromic color memory material 1′ 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 exceeding the appropriate temperature range and both thermochromic color memory materials have become discolored, to its initial state using a cooling device commonly used in everyday living environments, making it easier to irreversibly determine that the temperature control indicator has been placed in a specific temperature range or has been placed in a temperature environment exceeding the appropriate temperature range, and it also becomes 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 be easily and effectively used for temperature control in 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 development temperature t 1′ is -40℃ or lower, 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′ It is preferable that the difference (Δt4) between the temperature and the temperature change satisfies 5≦Δt4≦40, and furthermore, the hysteresis width (ΔH') is 30 to 100°C. This makes it easier to maintain each state before and after the color change, makes it easier to irreversibly determine that the temperature has been placed in a specific temperature range and that the temperature has deviated from the appropriate temperature range, and further 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 preferable that 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 lower, and the complete color loss 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) satisfies 5≦Δt4≦40, and further 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, and therefore the color seen in the temperature control indicator in the initial state will be the same as the color seen in the temperature control indicator in state 2 where only the first thermochromic color-memory material is in the colored state. The color seen in the initial state is of higher density 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 when the temperature control indicator is in a specific temperature range (temperature t 4′As a result, 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 organic color-forming compound, and it is more preferable that the thermochromic color memory materials exhibit different colors 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 each thermochromic color-memory material is in the color-developing state is different from the color seen in the temperature control indicator in the 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 the 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 complete color development temperature t1, a color development start temperature t2, and a decolorization start temperature t3 of a first thermochromic color memory material, and a complete color development temperature t 1′ , color onset temperature t 2′ , and decolorization start temperature t 3′ Each temperature (t1 and t 1′ , t2 and t 2′ , t3 and t 3′ ) are exactly 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'=[the temperatures (t1, t2, t3) of the first thermochromic color-memory material] - [the temperatures (t 1′ , t 2′ , t 3′ ))|≦3°C.

[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 of the second thermochromic color memory material 2′ , the first thermochromic color memory material's decolorization start temperature t3 and the second thermochromic color memory material's decolorization start temperature t 3′ The color change behavior of the temperature control indicators, which are almost 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 visually recognized as a mixture of the colors of the thermochromic color-memory materials in the color-developing state. This is the temperature t 4′ The initial temperature control indicator is maintained at a temperature of t 4′ When the second thermochromic color memory material is placed in a temperature environment below temperature t4, the second thermochromic color memory material in the colored state disappears, and the temperature t 1′ Within a temperature range exceeding 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 loses its color, and the color disappears at temperatures t1 and t 1′ Within the temperature range exceeding this, the color of each thermochromic color-memory material in its decolorized state is visually recognized (state 3). The temperature control indicators are designed to change the temperature from the initial state in which each thermochromic color-memory material is in a colored state to a specific 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, they exhibit the same color change behavior as described above. When the temperature t1 and the temperature t 1′ are not substantially the same and t1 < t 1′ is satisfied, the temperature control indicator in state 2 exceeds the temperature t 1′ , and only the color due to the first thermosensitive discoloring color memory material in the colored state is visible within the temperature range exceeding t and less than t4. The temperature control indicator in state 3 shows the color of each thermosensitive discoloring color memory material in the faded state within the temperature range exceeding t 1′ . Also, when the temperature t1 and the temperature t 1′ are not substantially the same and t 1′ < t1 is satisfied, the temperature control indicator in state 2 exceeds the temperature t 1′ , and only the color due to the first thermosensitive discoloring color memory material in the colored state is visible within the temperature range exceeding t and less than t4. The temperature control indicator in state 3 shows the color of each thermosensitive discoloring color memory material in the faded state within the temperature range exceeding 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 of the second thermochromic color memory material 2′ are approximately the same, and the decolorization start temperature t3 of the first thermochromic color memory material and the decolorization start temperature t 3′ are not substantially the same, and the decolorization start temperature t3 of the first thermochromic color memory material is 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 lines are the color density-temperature curves of the first thermochromic color-memory material, and the dashed lines are the color density-temperature curves of the second thermochromic color-memory material. The temperature control indicator is the temperature t3 of the first thermochromic color memory material and the temperature t4 of the second thermochromic color memory material 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 when an item that requires temperature control or its storage container is placed in a specific temperature range within the appropriate temperature range.The temperature control device has a temperature control function and can easily detect when the item has been placed 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 of the second thermochromic color memory material 2′ are approximately the same, and the decolorization start temperature t3 of the first thermochromic color memory material and the decolorization start temperature t 3′ are not substantially the same, and the decolorization start temperature t3 of the first thermochromic color memory material is lower than the complete decolorization temperature t 4′ The color change behavior of the temperature control indicator when the temperature change is larger than 100° C. is shown in Fig. 5. In Fig. 5, 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. The temperature control indicator is the temperature t3 of the first thermochromic color memory material and the temperature t4 of the second thermochromic color memory material 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 when an item that requires temperature control or its storage container is placed in a specific temperature range within the appropriate temperature range.The temperature control device has a temperature control function and can easily detect when the item has been placed in a temperature environment that exceeds the appropriate temperature range.

[0077] The temperature control indicator shown in FIG. 2 to FIG. 5 is in a state where the color of each thermochromic color-memory material in a colored state is mixed and the color is visible. The temperature control indicator ... 4′ When the temperature control indicator is placed in a temperature range below t4 (above), the color of the first thermochromic color memory material in a colored state is visible, but in the temperature control indicators shown in Figures 2 to 4, the first thermochromic color memory material starts 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 a completely colored state. Therefore, the change from the color of the first thermochromic color memory material in a 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 a faded state, which is visible when the temperature environment deviates from the appropriate temperature range, may be unclear. 5, in the specific temperature range, the first thermochromic color memory material is in a completely colored state, and the second thermochromic color memory material is in a completely discolored state, so that the color seen in the temperature control indicator in state 2 is the color of the first thermochromic color memory material in a completely colored state. Therefore, there is a clear change from the color seen in the colored state of the first thermochromic color memory material when the temperature control indicator is placed in the specific temperature range to the color seen when the temperature environment exceeds the appropriate temperature range and each thermochromic color memory material is in a discolored state. 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 of the second thermochromic color memory material 2′ are approximately the same, and the decolorization start temperature t3 of the first thermochromic color memory material and the decolorization start temperature t 3′ are not substantially the same, and the decolorization start temperature t3 of the first thermochromic color memory material is lower than the complete decolorization temperature t 4′ Larger is preferred.

[0078] The temperature management indicator of the present invention can be configured to have a reversible thermochromic layer (2) containing a thermochromic color-memorizing material such as a thermochromic color-memorizing microencapsulated pigment or resin particles on a support (3), as shown in Fig. 6. The reversible thermochromic layer (2) can be a first reversible thermochromic layer (reversible thermochromic layer A) (21) containing a first thermochromic color-memorizing material (thermochromic color-memorizing material A). In addition, when the temperature management indicator of the present invention is equipped with 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 a 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. Also, as shown in FIG. 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-memorizing material in combination with a non-thermochromic colorant, an alternating 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-memorizing liquid composition such as ink or paint in which a thermochromic color-memorizing 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 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, fiber, knitted fabric, woven fabric, nonwoven fabric, and other fabrics, synthetic leather, leather, plastic, glass, elastomer, rubber, ceramics, metal, wood, stone, and the like. The support may have an uneven shape, but is preferably flat, sheet-like, or film-like.

[0081] The binder resin is not particularly limited as long as it does not affect the coloring, fading, and discoloration of the thermosensitive color-changing color memory material, and may be a general-purpose resin, for example, an ionomer resin, an isobutylene-maleic anhydride copolymer resin, an acrylonitrile-acrylic styrene copolymer resin, an acrylonitrile-styrene copolymer resin, an acrylonitrile-butadiene-styrene copolymer resin, an acrylonitrile-chlorinated polyethylene-styrene copolymer resin, an ethylene-vinyl chloride copolymer resin, an ethylene-vinyl acetate copolymer resin, an ethylene-vinyl acetate-vinyl chloride graft copolymer resin, a vinylidene chloride resin, a vinyl chloride resin, a chlorinated vinyl chloride resin, a vinyl chloride-vinylidene chloride copolymer resin, a chlorinated polyethylene, a chlorinated polypropylene, a polyamide, a polyethylene terephthalate, a polybutylene terephthalate, a polycarbonate, a polystyrene, a high-impact polystyrene, a polypropylene, a polymethylstyrene, a polyacrylic acid ester, or a polymethyl methacrylate. , epoxy acrylate resins, alkylphenol resins, rosin-modified phenolic resins, rosin-modified alkyd resins, phenolic resin-modified alkyd resins, epoxy resin-modified alkyd resins, styrene-modified alkyd resins, acrylic-modified alkyd resins, aminoalkyd resins, vinyl chloride-vinyl acetate resins, styrene-butadiene resins, epoxy resins, unsaturated polyesters, saturated polyesters, polyurethanes, alkyd resins, natural rubber, polyisobutylene, butyl rubber, polyvinyl alkyl ethers, rosin, rosin esters, rosin derivatives, polyterpenes, oil-soluble phenolic resins, petroleum-based hydrocarbon resins, shellac, cyclized rubbers, vinyl acetate-based emulsion resins, styrene-butadiene-based emulsion resins, acrylic acid ester-based emulsion resins, water-soluble alkyd resins, water-soluble melamine resins, water-soluble urea resins, water-soluble phenolic resins, water-soluble epoxy resins, water-soluble polybutadiene, cellulose acetate, cellulose nitrate, and ethyl cellulose.

[0082] In addition, 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 contacts the object. For example, in a configuration in which a reversible thermochromic layer is provided on a support, as shown in FIG. 9, 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. In addition, when the support has transparency, as shown in FIG. 10, a reversible thermochromic layer (2) can be provided on a transparent support (6), and an adhesive layer (5) can be provided on the surface of the reversible thermochromic layer opposite to the surface on which the support is provided. The temperature control indicator having the adhesive layer and the above configuration can be used by adhering to an article 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 or its storage container that requires temperature control. 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, decoloring, discoloration, etc. of the thermochromic color memory material and can be attached to an article or its storage container that requires temperature control. Examples of the adhesive 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 is not likely to decrease in low or ultra-low temperature ranges, and acrylic resins, rubber resins, silicone resins, and epoxy resins are preferred.

[0084] In addition, when the temperature control indicator shown in Figure 10 is attached to an item or its storage container that requires temperature control, the transparent support functions as a transparent protective layer, so that the reversible thermochromic layer can be made durable without having to provide a transparent protective layer on 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 has transparency, and examples thereof include plastic, glass, elastomer, rubber, etc. in the form of a plane, sheet, film, etc. In addition, the support may be colorless and transparent, or colored and transparent. 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 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. Here, transparency refers to the property of transmitting light with wavelengths in the visible light region (the wavelength region of 380 to 780 nm as defined by 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 adjacent reversible thermochromic layers can be easily visually observed and the color and color change exhibited by the reversible thermochromic layer can be visually observed. The visible light transmittance can be calculated 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 (manufactured by 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, in a configuration in which a reversible thermochromic layer is provided on a support, can be configured such that the support is 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 Fig. 11. By attaching the temperature control indicator of the above configuration to an object such as an item that requires temperature control or its storage container, when the item or its storage container deviates from 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 again, and reattaching it, or replacing it with a new temperature control indicator.

[0086] The tamper-proof member exhibits a tamper-proof function by being configured such that an adhesive layer is provided on the outermost layer of a laminated member. Examples of tamper-evident components that can be used include tamper-evident labels, tapes, or stickers, and an example of such a tamper-evident component is one that has a tamper-evident function in which, when attached to an adherend and then peeled off, the adhesive layer is transferred to the adherend in the form of letters due to intra-layer peeling of the laminated structure. Further examples of tamper-evident components that have tamper-evident properties include a type in which, when peeled off after being attached to an adherend, separation occurs at the interface of the laminated structure, and the layers deform so that no residue is left on the adherend and letters appear on the tamper-evident component; and a type in which a base material made of a fragile material is used so that, when peeled off after being attached to an adherend, the base material is destroyed and a peeling mark remains on the adherend.

[0087] As the temperature control indicator of the present invention, a reversible thermochromic molded body (8) having a configuration containing a thermochromic color memory material in a support can also be used. An example of the reversible thermochromic molded body is 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 is equipped with a second thermochromic color memory material, the reversible thermochromic molded body (8) can 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) 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 a 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. By using the thermochromic color-memorizing material and the non-thermochromic colorant in combination, an alternating color change from color (1) to color (2) can be achieved.

[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 a 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 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 esters, polymethacrylic acid esters, polyamides, copolymers, and the like. Polymerized polyamide, polyamideimide, polyacetal, polyvinyl formal, polyvinyl butyral, polyarylate, polyetherimide, polyetheretherketone, 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-acrylic acid ester-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 the thermosetting resin include epoxy resin, xylene resin, toluene resin, guanamine resin, epoxy acrylate, phenol resin, unsaturated polyester, furan resin, polyimide, poly(p-hydroxybenzoic acid), polyurethane, urea resin, melamine resin, and silicone resin.

[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 transparent 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 resins, epoxy acrylates, phenol resins, unsaturated polyester resins, urea resins, aryl resins, and silicone resins.

[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-memorizing material is contained in a support, as shown in Fig. 13, an adhesive layer (5) can be provided on either surface of a reversible thermochromic molded body (8) and the indicator can be attached to an 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 thermosensitive color-changing color memory material and can be attached to an item or its storage container that requires temperature control. Examples of the adhesive 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 is not likely to decrease in low or ultra-low temperature ranges, and acrylic resins, rubber resins, silicone resins, and epoxy resins are preferred.

[0091] Furthermore, a transparent protective layer can be provided on the reversible thermochromic layer or on 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 temperature-sensitive color-changing color-memory composition contained in the reversible thermochromic molded body from physical impact, and can be provided 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, 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 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. Here, transparency refers to the property of transmitting light with wavelengths in the visible light region (the wavelength region of 380 to 780 nm as defined by 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, it becomes easier to visually recognize the adjacent reversible thermochromic layer or reversible thermochromic molded article, and the color and color change exhibited by the reversible thermochromic layer or reversible thermochromic molded article can be visually recognized. The visible light transmittance can be calculated by providing a transparent protective layer on a transparent substrate that transmits light with wavelengths in the visible light range, measuring the transmittance in the wavelength range from 380 nm to 780 nm using a spectrophotometer (manufactured by Hitachi, Ltd., product name: U-3210), and calculating the midpoint 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, while 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 surfaces are coated with a metal oxide such as titanium oxide, etc. 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] The temperature control indicator comprising the first and second thermochromic color memory materials may have the above-mentioned configuration, or may have a configuration in which, 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 are laminated. In this case, the support constituting the other reversible thermochromic laminate provided on one reversible thermochromic laminate has transparency. In the above configuration, the above-mentioned adhesive layer is provided between one reversible thermochromic laminate and the other reversible thermochromic laminate, and one reversible thermochromic laminate and the other reversible thermochromic laminate are attached via the adhesive layer to form a temperature control indicator. It may also be a structure in which the first reversible thermochromic laminate and the second reversible thermochromic molded body are laminated, or a structure in which the first reversible thermochromic molded body and the second reversible thermochromic laminate are laminated, 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, has transparency. In the above structure, the above-mentioned adhesive layer is provided between the reversible thermochromic laminate and the reversible thermochromic molded body, and the reversible thermochromic laminate and the reversible thermochromic molded body are attached via the adhesive layer to form a temperature management 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, the temperature control indicator is set to an initial state in which the first thermochromic color memory material is in a colored state using a device capable of cooling in an ultralow temperature range, such as an ultralow temperature storage. The temperature control indicator in the initial state continues to maintain the initial state in a temperature environment below the complete decolorization temperature t4 of the thermochromic color memory material. 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 daily living environments, so that a temperature change in the item or its storage container can be detected. In this state, it is possible to detect whether the item or storage container has deviated from a temperature environment that exceeds the appropriate temperature range based on a color change in the temperature control indicator. When the first thermochromic color-memory material becomes a decolorized state and the temperature control indicator laminated on the item or its storage container changes color (state 1), it is possible to detect that the item or its storage container has deviated from a temperature environment that exceeds the appropriate temperature range. In order to return a temperature control indicator in state 1 to its initial state again, it needs to 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 which 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 item or storage container 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, by 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 a 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 generally used in daily 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 in a specific temperature range (temperature t 4′ From the color change of the temperature control indicator, it can be detected whether the item or its storage container has been placed in a temperature range above t3 (temperature t4 or lower) and whether the temperature environment 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 state 2 to the initial state again, the second thermochromic color memory material must reach a complete color-changing temperature t 1′ The second thermochromic color memory material needs to be cooled to a temperature below the full coloring 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 is possible to 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 thermosensitive color-changing 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 left 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 complete color development temperature t1 of the first thermochromic color-memorizing composition and the complete color development temperature t2 of the second thermochromic color-memorizing composition are 1′ However, in cooling devices such as refrigerators and freezers that control the temperature of the above items or storage containers, the complete color-developing temperature t1 and the complete color-developing 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. EXAMPLES

[0096] The following examples are given, but the present invention is not limited thereto. In the examples, "parts" refers to parts by weight.

[0097] Example 1 Preparation of thermosensitive color-changing and color-memory microencapsulated pigments A thermochromic color-memorizing 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 aromatic isocyanate prepolymer as a wall film material and 50 parts of cosolvent, and then emulsified and dispersed in a 6% polyvinyl alcohol aqueous solution. After continuing to stir while heating, 2.5 parts of water-soluble aliphatic modified amine was added, and further stirring was continued to prepare a microcapsule dispersion. A thermochromic color-memorizing 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 thermosensitive color-changing, color-memorizing ink was prepared by uniformly dispersing 40 parts of the above-mentioned microcapsule pigment, 50 parts of ethylene-vinyl acetate copolymer resin emulsion, 1 part of leveling agent, 1 part of defoaming agent, 0.5 parts of viscosity modifier, and 7.5 parts of water. A solid print was then made on high-quality paper, and the ink was dried and cured to form a reversible thermocolor changing layer. Next, a 16 μm-thick transparent PET film having an adhesive layer was attached onto the reversible thermochromic layer via the adhesive layer and laminated to prepare a measurement sample.

[0099] Discoloration temperature measurement The above-mentioned measurement sample was immersed in a glass container filled with ethanol, the glass container was placed in an ultra-low temperature aluminum block thermostatic bath Cryoporter (manufactured by Synix Co., Ltd., product name: CS-80C), and the temperature-sensing part of a general-purpose semi-solid / liquid temperature sensor (manufactured by Anritsu Instruments Co., Ltd., product name: BS-21E-010) connected to a digital thermometer (manufactured by Anritsu Instruments Co., Ltd., product name: HFT-50) was placed in the glass container. Next, the temperature of the measurement sample immersed in ethanol was changed between room temperature (25°C) and -90°C in 1°C increments, and the color change of the thermochromic color-memory composition was visually observed. The temperature at which the thermosensitive color-changing, color-memory composition changed color was measured with a digital thermometer to measure the complete color-developing temperature t1, the color-developing start temperature t2, the color-fading start temperature t3, and the complete color-fading temperature t4, and the hysteresis width [ΔH=(intermediate temperature between t3 and t4)-(intermediate temperature between t1 and t2)]. The thermosensitive color-changing color-memory composition of Example 1 had a complete color-developing temperature t1: -55°C, a color-developing start temperature t2: -45°C, a discoloration start temperature t3: -10°C, a complete discoloration temperature t4: -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 consisting of 30 parts of the above-mentioned microcapsule pigment, 62 parts of a urethane-based 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 a white synthetic paper as a support (3), and printed in a solid pattern using a 120-mesh screen. The ink was 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 distribution and storage of fresh fish (the appropriate temperature range is -7°C or below, and it is necessary to determine whether the temperature has exceeded the appropriate range) The above temperature control indicator was placed in an ultra-low temperature storage unit (classified as F4 class under the Warehousing Business Act) set at -55°C, and the temperature control indicator was cooled to cause the thermochromic, color-memory material to change color; the blue temperature control indicator was then visible (initial state). Next, while keeping the temperature control indicator in its initial state, it was transferred to a freezer (classified as Class C1 under the Warehousing Business Act) set at -15°C where fresh fish is stored, and stacked on top of a storage container containing fresh fish.Since the temperature inside the freezer is 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 visibly observed. When the storage container was placed in a temperature environment of -6°C or higher, the thermochromic color-memory material lost its color, the temperature control indicator changed color, and only the white color of the support was 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 layered on a storage container for fresh fish changes color from its initial state, it cannot easily be returned 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. In order to return the temperature control indicator to its initial state, it needs to be cooled to -55°C or lower, but it was difficult to return it to its initial state in freezers commonly used in everyday living environments. In addition, by placing the environment in which the temperature control indicator is returned to its initial state by causing the thermosensitive color-changing color-memory material to change color and the environment in which the temperature of fresh fish is controlled far away from each other, and transporting the temperature control indicator that has been returned to its initial state by the ultra-low temperature stocker while maintaining its initial state to an environment without an ultra-low temperature stocker to control 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. 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 1°C, and temperature control was possible. In addition, in everyday living environments, the above-mentioned temperature control indicator only shows the white color of the support, but when cooled to below -55°C, the thermosensitive color-changing color memory material changes color to 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 microencapsulated pigments A thermochromic color-memorizing 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 aromatic isocyanate prepolymer as a wall film material and 50 parts of cosolvent, and then emulsified and dispersed in a 6% polyvinyl alcohol aqueous solution. After continuing to stir while heating, 2.5 parts of water-soluble aliphatic modified amine was added, and further stirring was continued to prepare a microcapsule dispersion. A thermochromic color-memorizing microcapsule pigment with an average particle size of 5.2 μm was obtained from the above microcapsule dispersion by centrifugation.

[0103] Preparation of samples for measuring discoloration temperature A measurement sample was 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 color fade temperature t4 of the thermosensitive color-changing 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 thermosensitive color-changing color-memory composition of Example 2 had a complete color-developing temperature t1: -45°C, a color-developing start temperature t2: -40°C, a discoloration start temperature t3: -8°C, a complete discoloration temperature t4: -5°C, and a 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 printed in a solid pattern on a white synthetic paper used as a support (3) using a 120 mesh screen, and then dried and cured to form a non-thermochromic layer (4). Next, a thermochromic color-memorizing ink consisting of 30 parts of the above-mentioned microcapsule pigment as a thermochromic color-memorizing material, 62 parts of a urethane-based 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 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.

[0106] Temperature control during distribution and storage of frozen foods (to 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 storage unit (classified as F3 class under the Warehousing Business Act) set to -45°C, and the temperature control indicator was cooled to cause the thermochromic color-memory material to develop color.The temperature control indicator then appeared purple, a mixture of the pink color from the non-thermochromic layer and the blue color from the reversible thermochromic layer (initial state). 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 at -10°C where frozen foods are stored, and stacked on 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 visibly observed. 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, with only the pink color due to the non-thermochromic layer being visible (state 1). Furthermore, even when the packaging container was placed back in the freezer set to -10°C, the temperature control indicator could not be restored to its initial state, and only the pink color was visible. Therefore, once the temperature control indicator layered on a packaging container containing frozen food 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 fallen into a temperature environment that exceeds the appropriate temperature range. In order to return the temperature control indicator to its initial state, it needs to be cooled to -45°C or lower, but it was difficult to return it to its initial state in freezers commonly used in everyday living environments. In addition, by placing the environment in which the temperature control indicator is returned to its initial state by causing the thermochromic color-memory material to change color and the environment in which the temperature of frozen foods is controlled far away from each other, and transporting the temperature control indicator that has been returned to its initial state by the ultra-low temperature stocker while maintaining its initial state to an environment without an ultra-low temperature stocker to control 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. 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 0°C<ΔT≦1°C, allowing for even stricter temperature control. In addition, in the above-mentioned temperature control indicator, only the pink color due to the non-thermochromic layer is visible in everyday living environments, but when cooled to below -45°C, the thermochromic color memory material develops color, and the pink color due to the non-thermochromic layer and the blue color due to the reversible thermochromic layer mix to become purple, so that it can be used as an anti-counterfeiting medium with anti-counterfeiting functions.

[0107] Example 3 Preparation of thermosensitive color-changing and color-memory microencapsulated pigments A thermochromic color-memorizing 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 aromatic isocyanate prepolymer as a wall film material and 50 parts of cosolvent, and then emulsified and dispersed in a 6% polyvinyl alcohol aqueous solution. After continuing to stir while heating, 2.5 parts of water-soluble aliphatic modified amine was added, and further stirring was continued to prepare a microcapsule dispersion. A thermochromic color-memorizing 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 A measurement sample was 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 color fade temperature t4 of the thermosensitive color-changing 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 thermosensitive color-changing color-memory composition of Example 3 had a complete color-developing temperature t1: -37°C, a color-developing start temperature t2: -30°C, a discoloration start temperature t3: 3°C, a complete discoloration temperature t4: 8°C, and a 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-memorizing ink consisting of 30 parts of the above-mentioned microcapsule pigment, 62 parts of a urethane-based 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 a 25 μm-thick white transparent polyester film used as a support (3). The ink was then solid-printed using a 120-mesh screen and dried and cured to form a reversible thermochromic layer (2). Next, a 16 μm thick transparent PET film having an adhesive layer was attached onto the reversible thermochromic layer via the adhesive layer to provide 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 provided to provide an adhesive layer (5), thereby producing a temperature control indicator.

[0111] Temperature control during distribution and storage of vegetables (the appropriate temperature range is between 0℃ and 5℃, 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 storage unit (classified as F2 class under the Warehousing Business Act) set at -37°C, and the temperature control indicator was cooled to cause the thermochromic color-memory material to change color; a magenta-colored temperature control indicator was then visible (initial state). Next, while maintaining the temperature control indicator in its initial state, it was moved to a refrigerator (classified as C3 class under the Warehousing Business Act) set at 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, the temperature control indicator changed color, and only the white color of the support was visible (state 1). Furthermore, even when the packaging container was returned to the refrigerator set at 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 a 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 fallen into a temperature environment that exceeds the appropriate temperature range. In order to return the temperature control indicator to its initial state, it needs to be cooled to -37°C or lower, but it was difficult to return it to its initial state in a refrigerator commonly used in everyday living environments. In addition, by placing the environment in which the temperature control indicator is set to its initial state by causing the thermochromic color-memory material to change color and the environment in which the temperature of vegetables is controlled at a distance from each other, and transporting the temperature control indicator set to its initial state by the ultra-low temperature stocker while maintaining its initial state to an environment without an ultra-low temperature stocker to control 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. 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 3°C, and strict temperature control was possible. In addition, while the above-mentioned temperature control indicator only shows the white color of the support in everyday living environments, when cooled to below -37°C, the thermosensitive color-changing 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 microencapsulated pigments A thermochromic color-memorizing 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 49 parts of cyclohexylmethyl caprate and 1 part of 4-benzyloxyphenylethyl palmitate as component (C) was added to a mixed solution consisting of 30 parts of aromatic isocyanate prepolymer as a wall film material and 50 parts of cosolvent, and then emulsified and dispersed in a 6% polyvinyl alcohol aqueous solution. After continuing to stir while heating, 2.5 parts of water-soluble aliphatic modified amine was added and further stirring was continued to prepare a microcapsule dispersion. A thermochromic color-memorizing microcapsule pigment having an average particle size of 3.9 μm was obtained from the above microcapsule dispersion by centrifugation.

[0113] Preparation of samples for measuring discoloration temperature A measurement sample was 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 color fade temperature t4 of the thermosensitive color-changing 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 thermosensitive color-changing color-memory composition of Example 4 had a complete color-developing temperature t1: -45°C, a color-developing start temperature t2: -30°C, a discoloration start temperature t3: -16°C, a complete discoloration temperature t4: -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-memorizing 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 surface opposite to the adhesive surface of an 80 μm-thick tamper-evident label made of a white polypropylene film (manufactured by Lintec Corporation, product name: TE80W PAT1 8K) as a thermochromic, color-memorizing material, using a 120-mesh screen to perform solid printing, followed by drying and curing to provide a reversible thermochromic layer (2). Next, a 16 μm thick transparent PET film with 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 with tamper-proof function.

[0116] Temperature control during distribution and storage of bread dough (the appropriate temperature range is between -20℃ and -10℃, 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 storage unit (classified as F3 class under the Warehousing Business Act) set to -45°C, and the temperature control indicator was cooled to cause the thermochromic, color-memory material to change color; the blue temperature control indicator was then visible (initial state). Next, while keeping the temperature control indicator in its initial state, it was transferred to a freezer (classified as Class C1 under the Warehousing Business Act) set at -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 visibly observed. When the storage container was placed in a temperature environment of -10°C or higher, the thermochromic color-memory material lost its color, the temperature control indicator changed color, and only the white color of the support was 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 a storage container for storing bread dough changes color from its initial state, it cannot easily be returned 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. In order to return the temperature control indicator to its initial state, it needs to be cooled to -45°C or lower, but it was difficult to return it to its initial state in a freezer commonly used in everyday living environments. In addition, by placing the environment in which the temperature control indicator is brought to its initial state by causing the thermosensitive color-changing color-memory material to change color and the environment in which the temperature of the bread dough is controlled far away from each other, and by transporting the temperature control indicator brought to its initial state by the ultra-low temperature stocker while maintaining its initial state to an environment without an ultra-low temperature stocker and controlling the temperature of the bread dough there, 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. In addition, when the temperature control indicator was peeled off from the storage container to replace it in order to prevent a record of the dough being placed in a temperature environment that exceeded the appropriate temperature range, the base material of the tamper-proof label was destroyed and a peeled-off mark remained on the storage container. Therefore, the above-mentioned temperature control indicator had a function of preventing tampering due to replacement. 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 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 white color of the support, but when cooled to below -45°C, the thermosensitive color-changing color memory material changes color to 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 microencapsulated pigments A thermochromic color-memorizing 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 aromatic isocyanate prepolymer as a wall film material and 50 parts of cosolvent, and then emulsified and dispersed in a 6% polyvinyl alcohol aqueous solution. After continuing to stir while heating, 2.5 parts of water-soluble aliphatic modified amine was added, and further stirring was continued to prepare a microcapsule dispersion. A thermochromic color-memorizing 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 A measurement sample was 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 color fade temperature t4 of the thermosensitive color-changing 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 thermosensitive color-changing color-memory composition of Example 5 had a complete color-developing temperature t1: -36°C, a color-developing start temperature t2: -32°C, a discoloration start temperature t3: 4°C, a complete discoloration temperature t4: 8°C, and a ΔH of 40°C, and reversibly changed from blue to colorless with temperature change.

[0120] Fabrication of temperature control indicator As a thermochromic color-memorizing 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-memorizing molding resin composition. Next, the above resin composition was used to mold into a plate shape at a cylinder temperature of 180° C. in an injection molding machine to prepare a temperature control indicator (support containing a thermosensitive color-changing, color-memorizing composition).

[0121] Temperature control during distribution and storage of vegetables (the appropriate temperature range is between 0℃ and 5℃, 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 storage unit (classified as F2 class under the Warehousing Business Act) set at -36°C, and the temperature control indicator was cooled to cause the thermochromic, color-memory material to change color; the blue temperature control indicator was then visible (initial state). Next, while keeping the temperature control indicator in its initial state, it was moved to a refrigerator (classified as C3 class under the Warehousing Business Act) set at 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 visibly observed. When the packaging container was placed in a temperature environment of 8°C or higher, the thermochromic color-memory material lost its color, the temperature control indicator changed color, and only the packaging container on which the temperature control indicator was layered was visible (state 1). Furthermore, even when the packaging container was returned to the refrigerator set at 3°C, the temperature control indicator could not be restored to its initial state, and only the packaging container was visible. Therefore, once the temperature control indicator attached to a 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 fallen into a temperature environment that exceeds the appropriate temperature range. In order to return the temperature control indicator to its initial state, it needs to be cooled to -36°C or lower, but it was difficult to return it to its initial state in a refrigerator commonly used in everyday living environments. In addition, by placing the environment in which the temperature control indicator is set to its initial state by causing the thermochromic color-memory material to change color and the environment in which the temperature of vegetables is controlled far away from each other, and transporting the temperature control indicator set to its initial state by the ultra-low temperature stocker while maintaining its initial state to an environment without an ultra-low temperature stocker to control 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. 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 3°C, and strict temperature control was possible. In addition, while the above-mentioned temperature control indicator only shows the color of the packaging container in everyday living environments, when cooled to below -36°C, the thermosensitive color-changing color-memory material changes color and turns blue, making it possible to use it as an anti-counterfeiting medium that has the function of preventing counterfeiting.

[0122] Example 6 Fabrication of temperature control indicator (see Figure 14) A thermochromic, color-memorizing ink consisting 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 uniformly dispersed on a white synthetic paper as a support (3), and printed in a solid pattern using a 120-mesh screen. The ink was 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.

[0123] Temperature control during vaccine distribution and storage (ensuring that the proper temperature range is 5°C or less and determining whether the temperature environment has exceeded the proper temperature range) The above temperature control indicator was placed in an ultra-low temperature storage unit (classified as F2 class under the Warehousing Business Act) set at -37°C, and the temperature control indicator was cooled to cause the thermochromic color-memory material to change color; a magenta-colored temperature control indicator was then visible (initial state). Next, while keeping the temperature control indicator in its initial state, it was transferred to a freezer (classified as F1 class under the Warehousing Business Act) set at -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, the temperature control indicator changed color, and only the white color of the support was 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 be returned 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. In order to return the temperature control indicator to its initial state, it needs to be cooled to -37°C or below, but it was difficult to return it to its initial state in freezers commonly used in everyday living environments. In addition, by placing the environment in which the temperature control indicator is returned to its initial state by causing the thermochromic color-memory material to change color and the environment in which the vaccine's temperature is controlled at a distance from each other, and transporting the temperature control indicator that has been returned to its initial state by the 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. 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 3°C, and strict temperature control was possible. In addition, while the above-mentioned temperature control indicator only shows the white color of the support in everyday living environments, when cooled to below -37°C, the thermosensitive color-changing 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-memorizing ink consisting of 15 parts of the microcapsule pigment of Example 3 as the first thermochromic color-memorizing material, 15 parts of the microcapsule pigment of Example 4 as the second thermochromic color-memorizing 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 printed in a solid pattern on a 25 μm-thick white transparent polyester film used 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 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-mentioned temperature control indicator was placed in an ultra-low temperature storage unit (classified as F3 class under the Warehouse Business Act) set at -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, a mixture of the magenta color from the first thermochromic color memory material and the blue color from the second thermochromic color memory material, was visible (initial state). Next, while maintaining the temperature control indicator in the initial state, the indicator is transferred to a freezer (classified as C1 class under the Warehousing Business Law) set at -18°C where meat products are stored, and is attached to a packaging container containing the meat products. The temperature in the freezer reaches the complete color-discoloring 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) of -10°C or higher and lower than 8°C, the second thermochromic color-memory material lost its color, the temperature control indicator changed color, and only the magenta color of the first thermochromic color-memory material in its colored state was 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 at -18°C, the temperature control indicator could not return to state 2 or the 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 thus providing a temperature control function in a 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 a temperature environment that exceeds the appropriate temperature range. In order to return the temperature control indicator to its initial state, it needs to be cooled to -45°C or lower, but it was difficult to return it to its initial state in freezers commonly used in everyday living environments. In addition, the environment in which the temperature control indicator is brought to its initial state by causing each thermochromic color-memory material to change color and the environment in which the temperature of meat products is controlled are located far apart, and the temperature control indicator that has been brought to its initial state by the ultra-low temperature stocker is transported to an environment without an ultra-low temperature stocker while maintaining its initial state, and the temperature of meat products is controlled there. This makes it 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 state 3. In addition, 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 develops a magenta color, so it could be used as an anti-counterfeiting medium with an anti-counterfeiting function. Furthermore, when cooled to below -45°C, the second thermochromic color memory material develops a purple color, which is 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, so it could also be used as an anti-counterfeiting medium with an even better anti-counterfeiting function.

[0126] Comparative Example 1 Preparation of thermosensitive color-changing and color-memory microencapsulated pigments A thermochromic color-memorizing 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 aromatic isocyanate prepolymer as a wall film material and 50 parts of cosolvent, and then emulsified and dispersed in a 6% polyvinyl alcohol aqueous solution. After continuing to stir while heating, 2.5 parts of water-soluble aliphatic modified amine was added, and further stirring was continued to prepare a microcapsule dispersion. A thermochromic color-memorizing 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 thermosensitive color-changing, color-memorizing ink was prepared by uniformly dispersing 40 parts of the above-mentioned microcapsule pigment, 50 parts of ethylene-vinyl acetate copolymer resin emulsion, 1 part of leveling agent, 1 part of defoaming agent, 0.5 parts of viscosity modifier, and 7.5 parts of water. A solid print was then made on high-quality paper, and the ink was dried and cured to form a reversible thermocolor changing layer. Next, a 16 μm-thick transparent PET film having an adhesive layer was attached onto the reversible thermochromic layer via the adhesive layer and laminated to prepare a measurement sample.

[0128] Discoloration temperature measurement The above measurement sample was set in the measurement section of a color difference meter (Tokyo Denshoku Co., Ltd., product name: TC-3600), and the temperature of the sample section was raised and lowered at a rate of 2°C per minute, and the lightness value was measured as the color density at each temperature, and a color density-temperature curve was created. From the color density-temperature curve, the complete color development temperature t1, color development start temperature t2, decolorization start temperature t3, and complete decolorization temperature t4 were measured, and the hysteresis width [ΔH = (intermediate temperature between t3 and t4) - (intermediate temperature between t1 and t2)] was calculated. The thermosensitive color-changing color-memory composition of Comparative Example 1 had a complete color-developing temperature t1 of 6°C, a color-developing start temperature t2 of 12°C, a discoloration start temperature t3 of 36°C, a complete discoloration temperature t4 of 46°C, and a 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 consisting of 30 parts of the above-mentioned microcapsule pigment, 62 parts of a urethane-based 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 a white synthetic paper as a support (3), and printed in a solid pattern using a 120-mesh screen. The ink was 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 distribution and storage of fresh fish (the appropriate temperature range is -7°C or below, and it is necessary to determine whether the temperature has exceeded the appropriate range) The above temperature control indicator was placed in an ultra-low temperature storage unit (classified as F4 class 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 keeping the temperature control indicator in its initial state, it was transferred to a freezer (classified as Class C1 under the Warehousing Business Act) set at -15°C where fresh fish is stored, and stacked on top of a storage container containing fresh fish.Since the temperature inside the freezer is 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 visibly observed. 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 exceeded 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, the temperature control indicator changed color, and only the white color of the support was visible (State 1). When the storage container was returned to the freezer set at -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 laminated on the storage container for fresh fish maintains its initial state even when placed in a specific temperature environment exceeding the appropriate temperature range, and the temperature control indicator that has changed from the initial state to state 1 can easily return to its initial state, making it impossible to irreversibly determine that the fresh fish has left a 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 since 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 at 180°C in an extruder to obtain a thermochromic, color-memory molding resin composition. Next, the resin composition was used to obtain a petal-shaped molded body by injection molding using a flower-shaped mold. The molded bodies were stacked together to produce an artificial flower (ornament). When this artificial flower was cooled to below -55℃, the thermochromic, color-memory microencapsulated pigment developed its color, and the blue color from the microencapsulated pigment and the yellow color from the non-thermochromic colorant were mixed to produce a green color. At temperatures below the complete decolorization temperature t4, the microencapsulated pigment maintained its color and the artificial flower remained green. When the artificial flower was then placed in an environment with a temperature of -6°C or higher, the microencapsulated pigment disappeared and the yellow color of the non-thermochromic colorant became visible. When the artificial flower was cooled again to -55°C or lower, the green color became visible.

[0132] Application example 2 A thermochromic, color-memorizing ink consisting of 30 parts of the thermochromic, color-memorizing microcapsule pigment of Example 1, 62 parts of a urethane-based 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 printed solidly on 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 onto the reversible thermochromic layer via the adhesive layer to provide a transparent protective layer, and further, an adhesive layer made of an acrylic resin was applied to the surface of the support opposite to the surface on which the reversible thermochromic layer was provided, to produce 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 to which the laminate was attached was cooled to -55°C or lower, the thermochromic color-memory microencapsulated pigment developed a color, and the laminate turned blue. The laminate maintained its color development at temperatures below the complete decolorization temperature t4, and remained blue. 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 showed a blue color. Generally, ice cream contains air and starts to melt at around -5°C. Once melted, the air in the ice cream escapes, causing a poor texture and impairing the quality. Therefore, when serving ice cream, care must be taken to prevent the ice cream from melting too much. As described above, unless the disher is placed in a temperature environment of -6°C or higher, the microcapsule pigment continues to maintain its colored state and the laminate shows blue, and at -6°C or higher, the microcapsule pigment loses color and the laminate shows 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 teaching tool for serving ice cream with care so that it does not melt too much and impair its quality.

[0134] Application example 3 A thermochromic, color-memorizing ink consisting of 30 parts of the thermochromic, color-memorizing microcapsule pigment of Example 4, 62 parts of urethane-based emulsion resin, 2 parts of thickener, 0.5 parts of leveling agent, 0.5 parts of defoaming agent, and 5 parts of crosslinking agent was printed solid on a white synthetic paper support using a 120-mesh screen, and then dried and cured to provide a reversible thermochromic layer, thereby obtaining an anti-counterfeiting medium. In the medium for preventing counterfeiting, 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 medium for preventing counterfeiting was cooled to -45°C or lower, the microcapsule pigment was in a colored state, and the blue color was visible, so the medium had a counterfeiting prevention function. Furthermore, the medium for preventing counterfeiting maintained a state in which the blue color was visible in a temperature range of less than -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 printed solid on 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 provide a second reversible thermochromic layer (reversible thermochromic layer B), thereby obtaining an anti-counterfeiting medium. In the counterfeit prevention medium, each of the thermochromic color-memorizing microcapsule pigments was in a decolorized state under a daily living environment (for example, 25°C), and the white color due to the support was visible. When the counterfeit prevention medium was cooled to a temperature above -55°C and below -37°C, one of the microcapsule pigments (microcapsule pigment B) developed color and magenta was visible, so the medium had a counterfeit prevention function. Furthermore, when the counterfeit prevention medium was cooled to below -55°C, the other microcapsule pigment (microcapsule pigment A) developed color and purple, which was a mixture of the blue color due to the colored microcapsule pigment A and the magenta color due to the colored microcapsule pigment B, was visible, so the counterfeit prevention medium had a superior function as a counterfeit prevention medium. Furthermore, the counterfeit prevention medium maintained a state in which purple was visible in a temperature range 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: the color development start temperature of the thermochromic color-memory composition or the first thermochromic color-memory material t3: the color-discoloring start temperature of the thermochromic color-memory composition or the first thermochromic color-memory material 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 decolorization start temperature of the second thermosensitive 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-memorizing material and a second thermochromic color-memorizing material 3 Support 4. Non-thermochromic layer 5 Adhesive layer 6. Transparent support 7 Tamper-proof components with adhesive layer 8. Reversible thermochromic moldings 81 A first reversible thermochromic molded body containing a first thermochromic color memory material in a support 81' A first reversible thermochromic molded body comprising 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 comprising a second thermochromic color memory material in a transparent support. 83 Reversible thermochromic molded body containing a first thermochromic color-memorizing material and a second thermochromic color-memorizing material in a support 9 Transparent protective layer

Claims

1. A thermosensitive color-changing 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 temperature from the colored state, the composition exhibits a decolorization start temperature t ３ When the temperature reaches t ３ Higher complete bleaching temperature t ４ In the above temperature range, the color is completely decolorized. In the process of decreasing the temperature from the decolorized state, the color development starting temperature t ２ When the temperature reaches t ２ Lower full color temperature t １ The color density-temperature curve shows a hysteresis width (ΔH) of 8 to 100°C and changes color at the temperature t １ is −30° C. or lower, and the complete decolorization temperature t ４ The thermosensitive color-changing color-memorizing composition has a color-memorizing effect in the range 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-memorizing composition according to claim 1, wherein X is a hydrogen atom, a methyl group, or a cyclohexyl group.

3. The R ２ 3. The thermosensitive color-changing color-memorizing composition according to claim 1, wherein is a straight-chain or branched alkyl group having 3 to 11 carbon atoms.

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

5. A thermosensitive color-changing, color-memorizing liquid composition comprising the thermosensitive color-changing, 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 according to claim 4.

7. 5. A thermochromic, color-memorizing molding resin composition comprising the thermochromic, color-memorizing 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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