JP7645757B2 - Temperature control indicators and their uses - Google Patents

Description

The present invention relates to a temperature control indicator and a method for using the same. More specifically, the present invention relates to a temperature control indicator that can control the temperature of items that need to be stored within an appropriate temperature range by changing the color of a thermochromic, color-memorizing material, and a method for using the same.

Conventionally, there has been disclosed a counterfeit prevention medium capable of detecting counterfeits by a color change of a reversible thermochromic layer caused by a temperature increase or decrease (see, for example, Patent Document 1).
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, making it difficult to return one of the thermochromic color-memory compositions to its pre-color change state in which it is colored, and thus functions as a temperature control indicator that can irreversibly determine whether or not a specified temperature range has been exceeded.

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 appropriate temperature range is low, to be distributed over a wide area without deteriorating in quality by maintaining the appropriate temperature range during the distribution process from production to transportation to consumption. In the cold chain, it is necessary to manage the temperature so that it is possible to determine whether the goods have been kept in a temperature environment outside the appropriate temperature range during the distribution process without ever departing from the appropriate temperature range. By using a material that changes color when it deviates from a specified temperature range, it is possible to easily detect whether the goods have deviated from the appropriate temperature range. Although the above-mentioned counterfeit prevention medium functions as a temperature management indicator that can irreversibly determine whether the goods have deviated from the normal temperature range using a thermochromic color-memorizing material, when used for goods that have an appropriate temperature range in the low temperature range and have a narrower appropriate temperature range, it is difficult for the thermochromic color-memorizing material to selectively memorize and retain the color, making it difficult to irreversibly determine whether the goods have deviated from the appropriate temperature range.

JP 2017-170664 A

The present invention aims to provide a temperature control indicator and a method for using the same that can irreversibly determine whether or not fresh foods, frozen foods, medicines, and other items or their storage containers, which have a narrow optimum temperature range in the low temperature range, have been stored without ever deviating from the optimum temperature range during distribution and storage, by the color change of a thermochromic, color-memorizing material.

〔式中、Ｒ_１は、下記式（＊）で示される基、又は、シクロアルキル基を示し、Ｒ_２は、炭素数１～１３の直鎖又は分岐のアルキル基を示す〕

（式中、Ｘは、水素原子、又は、炭素数１～３の直鎖若しくは分岐のアルキル基を示す）
さらには、前記Ｒ_１が、Ｘが水素原子若しくはメチル基である基、又は、シクロヘキシル基であること、前記Ｒ_２が、炭素数３～１１の直鎖又は分岐のアルキル基であること、前記発色状態の感温変色性色彩記憶性材料の完全発色温度ｔ_１が－３０℃以下であること、前記消色状態の感温変色性色彩記憶性材料の完全消色温度ｔ_４が４０℃以上であることを要件とする。
さらには、前記第一の可逆熱変色体及び第二の可逆熱変色体に備えられる各感温変色性色彩記憶性材料は、発色状態で互いに異なる色を呈すること、前記第一の可逆熱変色体と第二の可逆熱変色体を並設してなること、前記第一の可逆熱変色体上に前記第二の可逆熱変色体を積層してなること、前記第二の可逆熱変色体が透明性を有してなること、前記第一の可逆熱変色体又は第二の可逆熱変色体の少なくとも一方が、支持体上に感温変色性色彩記憶性材料を含有してなる可逆熱変色層を設けてなる可逆熱変色性積層体であること、前記可逆熱変色体の、対象物と接する面に粘着層を設けてなること、前記支持体が、対象物に貼着後剥がすと剥がしたことが判別できる、粘着層を設けた改ざん防止用部材であることを要件とする。
さらには、前記温度管理インジケーターを、対象物に設けて使用することを特徴とする温度管理インジケーターの使用方法を要件とする。 The present invention provides a temperature management indicator comprising a first reversible thermochromic body having a thermochromic color memory material and a second reversible thermochromic body having a thermochromic color memory material, the thermochromic color memory material being a thermochromic color memory microcapsule pigment encapsulating a thermochromic color memory composition comprising at least (a) an electron donating organic compound, (b) an electron accepting compound, and (c) a reaction medium for controlling the color reaction of the components (a) and (b), or a thermochromic color memory resin particle having the thermochromic color memory composition dispersed in a thermoplastic resin or a thermosetting resin, the thermochromic color memory material exhibiting a hysteresis characteristic in a color density-temperature curve and exhibiting alternation between a colored state and a decolored state, and in the process of increasing temperature from a colored state, decoloration begins when a decolorization initiation temperature _t3 is reached, and the complete decolorization temperature _t4 is higher than the temperature t3. The thermosensitive color- _memory material is in a completely decolorized state in a temperature range of _t4 or more, and in the process of decreasing temperature from the decolorized state, when the color development start temperature _t2 is reached, color development begins, and in a temperature range of t1 or less that is lower than _t2 , the thermosensitive color-memory material is in a completely colored state, exhibiting a hysteresis characteristic, and discoloration occurs with a hysteresis width (ΔH) of 8 to 100°C in terms of the color density-temperature curve, and one side of the thermosensitive color-memory material is in a colored state, and the other side is in a decolorized state, the completely decolorized temperature _t4 of the thermosensitive color-memory material in the decolorized state is higher than the completely decolorized temperature _t4 of the thermosensitive color-memory material in the colored state, and the completely colored temperature _t1 of the thermosensitive color-memory material in the decolorized state is higher than the completely colored temperature t2 of the thermosensitive color-memory material in the colored state. The temperature control indicator is characterized in that the temperature (c) of the thermochromic color-memory material in the colored state is greater than ₁ , the component (c) of the thermochromic color-memory material in the colored state is a compound represented by the following formula (C), the complete color-discoloring temperature _t4 is in the range of -25°C or more and 15°C or less, and the complete color-discoloring temperature _t1 of the thermochromic color-memory material in the color-discolored state is greater than -30°C and 10°C or less.

[wherein R ₁ represents a group represented by the following formula (*) or a cycloalkyl group, and R ₂ represents a linear or branched alkyl group having 1 to 13 carbon atoms]

(wherein X represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms).
Further requirements are that R ₁ is a group in which X is a hydrogen atom or a methyl group, or a cyclohexyl group, that R ₂ is a linear or branched alkyl group having 3 to 11 carbon atoms, that the thermochromic color-memory material in a colored state has a complete color-developing temperature t ₁ of −30° C. or lower, and that the thermochromic color-memory material in a decolored state has a complete decolorizing temperature t ₄ of 40° C. or higher.
Furthermore, the requirements are that the thermochromic color memory materials provided in the first reversible thermochromic body and the second reversible thermochromic body exhibit different colors from each other in a colored state, that the first reversible thermochromic body and the second reversible thermochromic body are arranged side by side, that the second reversible thermochromic body is laminated on the first reversible thermochromic body, that the second reversible thermochromic body is transparent, that at least one of the first reversible thermochromic body or the second reversible thermochromic body is a reversible thermochromic laminate comprising a reversible thermochromic layer containing a thermochromic color memory material provided on a support, that an adhesive layer is provided on the surface of the reversible thermochromic body that comes into contact with the object, and that the support is a tamper-proof member provided with an adhesive layer that allows it to be determined that the support has been peeled off after being attached to the object.
Furthermore, the present invention also provides a method for using the temperature control indicator, which is characterized in that the temperature control indicator is attached to an object.

The present invention provides a temperature control indicator and a method for using the same, which can detect whether or not fresh food, frozen food, medicine, or other items or storage containers with narrow optimum temperature ranges in the low temperature range have been stored without ever deviating from the optimum temperature range during distribution and storage, by the color change of a thermochromic color-memorizing material, and which is irreversible and therefore difficult to restore to its original color once it deviates from the optimum temperature range.

1 is a graph illustrating the hysteresis characteristic in the color density-temperature curve of a thermochromic color-memorizing composition applied to the present invention. 4 is a graph illustrating an example of color change behavior of a temperature management indicator in an initial state in the present invention. 10 is a graph illustrating another example of color change behavior of the temperature management indicator in the initial state in the present invention. FIG. 1 is a vertical cross-sectional view illustrating an example of a temperature management indicator of the present invention. FIG. 11 is a vertical cross-sectional view illustrating another example of a temperature management indicator of the present invention. FIG. 5 is an explanatory diagram of a color change of the temperature control indicator of FIG. 4 . FIG. 6 is an explanatory diagram of a color change of the temperature control indicator of FIG. 5 . FIG. 11 is a vertical cross-sectional view illustrating another example of a temperature management indicator of the present invention. FIG. 9 is an explanatory diagram of a color change of the temperature control indicator of FIG. 8 . FIG. 2 is a longitudinal sectional view illustrating an example of a first reversible thermochromic body. FIG. 2 is a longitudinal sectional view illustrating an example of a second reversible thermochromic body. FIG. 11 is a vertical cross-sectional view illustrating another example of a temperature management indicator of the present invention. FIG. 11 is a vertical cross-sectional view illustrating another example of a temperature management indicator of the present invention. FIG. 11 is a vertical cross-sectional view illustrating another example of a temperature management indicator of the present invention. FIG. 11 is a vertical cross-sectional view illustrating another example of a temperature management indicator of the present invention. FIG. 11 is a vertical cross-sectional view illustrating another example of a temperature management indicator of the present invention. FIG. 11 is a vertical cross-sectional view illustrating another example of a temperature management indicator of the present invention. FIG. 11 is a vertical cross-sectional view illustrating another example of a temperature management indicator of the present invention. FIG. 11 is a vertical cross-sectional view illustrating another example of a temperature management indicator of the present invention. FIG. 11 is a vertical cross-sectional view illustrating another example of a temperature management indicator of the present invention. FIG. 11 is a vertical cross-sectional view illustrating another example of a temperature management indicator of the present invention. FIG. 11 is a vertical cross-sectional view illustrating another example of a temperature management indicator of the present invention.

In the present 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 that are commonly used in everyday living environments, such as refrigerators and freezers, specifically a temperature range exceeding -30°C and not exceeding 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 with cooling devices commonly used in everyday living environments, specifically a temperature range of -30°C or lower.

The hysteresis characteristic in the color density-temperature curve of the thermochromic color-memory composition (reversible thermochromic composition having color memory properties) applied to the present invention will be described below.
In 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 start 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 start 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 color change temperature region is the temperature region 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 region between the color development start temperature _t2 and the decolorization start temperature t3, which is the region in which the difference in color density is _large, is the substantial color change temperature region.
Specifically, a thermosensitive color-changing 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 made to be in 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 thermosensitive color-changing 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-discoloring initiation temperature _t3 , the change to the color-discolored state can be initiated, and by heating it to a temperature equal to or higher than the complete color-discoloring temperature _t4 , the composition can be brought to a completely color-discolored state, and this state can be maintained unless the temperature of the thermosensitive color-discoloring color-memory composition is lowered to the color-discoloring initiation temperature _t2 .
In addition, 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 width showing the degree of hysteresis [hereinafter referred to as hysteresis width (ΔH)], and the larger this ΔH is, the easier it is to maintain each state before and after the discoloration. The 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 same as the hysteresis characteristics in the color density-temperature curve of the thermosensitive color-memory composition.

The components (a), (b), and (c) of the thermochromic color-memorizing composition used in the present invention are specifically described below.

Component (A), that is, the electron-donating organic color-forming compound, is the component that determines the color, and is a compound that donates electrons to component (B), which is a color developer, to develop color.
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.

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-N-p-tolylamino)fluoran,
3,6-dimethoxyfluoran,
3,6-di-n-butoxyfluoran,
2-methyl-6-(N-ethyl-N-p-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-N-p-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-N-p-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]xanthene]-3-one,
3',6'-bis[phenyl(3-methylphenyl)amino]spiro[isobenzofuran-1(3H),9'-[9H]xanthene]-3-one,
3',6'-bis[phenyl(3-ethylphenyl)amino]spiro[isobenzofuran-1(3H),9'-[9H]xanthene]-3-one,
2,6-bis(2'-ethyloxyphenyl)-4-(4'-dimethylaminophenyl)pyridine,
2,6-bis(2',4'-diethyloxyphenyl)-4-(4'-dimethylaminophenyl)pyridine,
2-(4'-dimethylaminophenyl)-4-methoxyquinazoline,
4,4'-Ethylenedioxy-bis[2-(4-diethylaminophenyl)quinazoline]
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.

Component (b), that is, 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.

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 acid and derivatives thereof, aromatic carboxylic acids and derivatives thereof, or aliphatic carboxylic acids and derivatives thereof having 2 to 5 carbon atoms 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.

Among the above-mentioned components (b), 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 have a substituent such as an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, a carboxyl group and its ester or amide group, or a halogen atom.

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

Examples of compounds of component (b) are given below.
Examples of the compound 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,
2-heptadecafluorooctylethane 4-hydroxybenzoate,
benzyl 4-hydroxybenzoate,
4-hydroxybenzoic acid benzyl ester,
4-hydroxybenzoic acid-o-methylbenzyl
m-methylbenzyl 4-hydroxybenzoate,
p-methylbenzyl 4-hydroxybenzoate,
p-ethylbenzyl 4-hydroxybenzoate,
p-propylbenzyl 4-hydroxybenzoate,
p-tert-butylbenzyl 4-hydroxybenzoate,
phenylethyl 4-hydroxybenzoate,
4-hydroxybenzoic acid-o-methylphenylethyl ester,
4-hydroxybenzoic acid-m-methylphenylethyl ester,
p-methylphenylethyl 4-hydroxybenzoate,
p-ethylphenylethyl 4-hydroxybenzoate,
p-propylphenylethyl 4-hydroxybenzoate,
An example thereof is p-tert-butylphenylethyl 4-hydroxybenzoate.

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,
Examples include 2,4-dihydroxy-3',4',5'-triethoxybenzophenone.

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)methyl propionate,
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'-hydroxydiphenyl 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'-hydroxydiphenyl 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,
Examples include 1,8-bis(4-hydroxyphenylthio)-3,6-dioxaoctane.

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

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:

Examples of the compound 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"-ethylidynetris{[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"-ethylidynetris[2,6-bis(2-hydroxybenzyl)phenol],
4,4',4"-ethylidynetris[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,
Examples include 2,2-bis[4,4',4'',4''-tetrakis(3,5-dihydroxymethyl-4-hydroxyphenyl)cyclohexyl]propane.

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,
An example is 2-O-(phenethylaminocarbonyl)-lactic acid.

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, etc.

As the component (b), a compound having a phenolic hydroxyl group is preferable because it can more effectively express the thermochromic property, 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.

The component (iii) of the reaction medium that reversibly induces an electron donor-acceptor reaction between the components (i) and (ii) in a specific temperature range will now be described.
The thermochromic color-memorizing materials used in the present invention have different thermochromic properties, i.e., their color density-temperature curves are different from each other, one being in a colored state and the other being in a decolored state. In other words, the component (iii) used in each thermochromic color-memorizing material (thermochromic color-memorizing composition) is also different from each other.

〔式中、Ｒ_１は、下記式（＊）で示される基、又は、シクロアルキル基を示し、Ｒ_２は、炭素数１～１３の直鎖又は分岐のアルキル基を示す〕

（式中、Ｘは、水素原子、又は、炭素数１～３の直鎖若しくは分岐のアルキル基を示す） The thermochromic color-memorizing material in a colored state applied to the present invention exhibits the above-mentioned hysteresis characteristics, has a hysteresis width (ΔH) of 8 to 100° C., and has a complete color-developing temperature _t4 in the range of −25° C. to 15° C. As the component (c) of the thermochromic color-memorizing material in a colored state, an ester compound having a specific structure represented by formula (C) is used.
The ester compound represented by formula (C) will be described.

[wherein R ₁ represents a group represented by the following formula (*) or a cycloalkyl group, and R ₂ represents a linear or branched alkyl group having 1 to 13 carbon atoms]

(wherein X represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms).

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

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. In terms of availability and cost, however, alkylbenzyl alcohol having an alkyl group substituted at the 4-position (para-position) is preferably used.

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

Specific examples of carboxylic acids having 2 to 14 carbon atoms include acetic acid, butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, and myristic acid.

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

With regard to _R1 , it is preferable that X is a hydrogen atom or a methyl group, or a cyclohexyl group, since this tends to give a compound with a larger hysteresis width (ΔH).
_R2 is preferably a linear or branched alkyl group having 3 to 11 carbon atoms, since this makes it easier to obtain a compound whose discoloration temperature is in a lower range.

In formula (C), since it is easy to obtain a compound having a lower discoloration temperature and a larger hysteresis width, it is preferable that R ₁ is a group represented by formula (*) or a cycloalkyl group and R ₂ is a linear or branched alkyl group having 3 to 11 carbon atoms. In the above structure, it is preferable that R ₁ is a group in which X is a hydrogen atom or a methyl group, or a cyclohexyl group.

The component (C) applied to the thermochromic color memory material in the colored state may be an ester compound represented by formula (C) that is used in combination of two or more kinds as appropriate. Also, the component (C) may further contain other conventionally known components (C) such as alcohols, esters, ketones, ethers, and acid amides, which will be described later, other than the compound represented by formula (C).
When the component (c) contains a compound other than formula (C), the blending ratio of the compound other than formula (C) 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 (c).

The thermochromic color memory material in the decolorized state applied to the present invention exhibits the above-mentioned hysteresis characteristics, with a hysteresis width (ΔH) of 8 to 100° C. and a complete color development temperature _t1 in the range of more than −30° C. and not more than 10° C. The component (iii) used in the thermochromic color memory material in the decolorized state is not particularly limited as long as it satisfies the above-mentioned hysteresis width and complete color development temperature _t1 , and examples of the component (iii) include conventionally known alcohols, esters, ketones, ethers, and acid amides.

When a thermosensitive color-changing, color-memorizing composition is encapsulated in a microcapsule for secondary processing, low molecular weight compounds will evaporate out of the capsule when subjected to high heat treatment, so compounds with 10 or more carbon atoms are preferably used to keep the compound stably inside the capsule.

As alcohols, aliphatic monohydric saturated alcohols having 10 or more carbon atoms are effective, such as decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, heptadecyl alcohol, octadecyl alcohol, eicosyl alcohol, and docosyl alcohol.

As the esters, esters having 10 or more carbon atoms other than the compounds represented by formula (C) are effective, and examples thereof include esters obtained from any combination of a monovalent carboxylic acid having an aliphatic and alicyclic or aromatic ring and a monohydric alcohol having an aliphatic and alicyclic or aromatic ring, esters obtained from any combination of a polyvalent carboxylic acid having an aliphatic and alicyclic or aromatic ring and a monohydric alcohol having an aliphatic and alicyclic or aromatic ring, esters obtained from any combination of a monovalent carboxylic acid having an aliphatic and alicyclic or aromatic ring and a monohydric alcohol having an aliphatic and alicyclic or aromatic ring, and esters obtained from any combination of a monovalent carboxylic acid having an aliphatic and alicyclic or aromatic ring and a monohydric alcohol having an aliphatic and alicyclic or aromatic ring. Examples of the esters include esters obtained from any combination of polyhydric alcohols having a ring, such as ethyl caprylate, octyl caprylate, stearyl caprylate, myristyl caprate, docosyl caprate, 2-ethylhexyl laurate, n-decyl laurate, 3-methylbutyl myristate, cetyl myristate, isopropyl palmitate, neopentyl palmitate, nonyl palmitate, cyclohexyl palmitate, n-butyl stearate, 2-methylbutyl stearate, and 3,5,5-trimethyl stearate. Methylhexyl, n-undecyl stearate, pentadecyl stearate, stearyl stearate, cyclohexylmethyl stearate, isopropyl behenate, hexyl behenate, lauryl behenate, behenyl behenate, cetyl benzoate, stearyl 4-tert-butylbenzoate, dimyristyl phthalate, distearyl phthalate, dimyristyl oxalate, dicetyl oxalate, dicetyl malonate, dilauryl succinate, dilauryl glutarate, diundecyl adipate, dilauryl azelate, di-(n) sebacate -nonyl), 1,18-octadecylmethylenedicarboxylate dineopentyl, ethylene glycol dimyristate, propylene glycol dilaurate, propylene glycol distearate, hexylene glycol dipalmitate, 1,5-pentanediol distearate, 1,2,6-hexanetriol trimyristate, 1,4-cyclohexanediol didecyl, 1,4-cyclohexanedimethanol dimyristate, xylene glycol dicaprinate, xylene glycol distearate, etc.

Also effective are ester compounds of saturated fatty acids and branched aliphatic alcohols, and ester compounds of unsaturated fatty acids or branched or substituted saturated fatty acids and branched or aliphatic alcohols having 16 or more carbon atoms, such as 2-ethylhexyl butyrate, 2-ethylhexyl behenate, 2-ethylhexyl myristate, 2-ethylhexyl caprate, 3,5,5-trimethylhexyl laurate, 3,5,5-trimethylhexyl palmitate, 3,5,5-trimethylhexyl stearate, 2-methylbutyl caproate, and 2-methylbutyl caprylate. , 2-methylbutyl caprate, 1-ethylpropyl palmitate, 1-ethylpropyl stearate, 1-ethylpropyl behenate, 1-ethylhexyl laurate, 1-ethylhexyl myristate, 1-ethylhexyl palmitate, 2-methylpentyl caproate, 2-methylpentyl caprylate, 2-methylpentyl caprate, 2-methylpentyl laurate, 2-methylbutyl stearate, 2-methylbutyl stearate, 3-methylbutyl stearate, 1-methylheptyl stearate, 2-methylbutyl behenate, 3-methylbutyl behenate ethyl, 1-methylheptyl stearate, 1-methylheptyl behenate, 1-ethylpentyl caproate, 1-ethylpentyl palmitate, 1-methylpropyl stearate, 1-methyloctyl stearate, 1-methylhexyl stearate, 1,1-dimethylpropyl laurate, 1-methylpentyl caprate, 2-methylhexyl palmitate, 2-methylhexyl stearate, 2-methylhexyl behenate, 3,7-dimethyloctyl laurate, 3,7-dimethyloctyl myristate, 3,7-dimethyloctyl palmitate, stearin Examples include 3,7-dimethyloctyl ester, 3,7-dimethyloctyl behenate, stearyl oleate, behenyl oleate, stearyl linoleate, behenyl linoleate, 3,7-dimethyloctyl erucate, stearyl erucate, isostearyl erucate, cetyl isostearate, stearyl isostearate, 2-methylpentyl 12-hydroxystearate, 2-ethylhexyl 18-bromostearate, isostearyl 2-ketomyristate, 2-ethylhexyl 2-fluoromyristate, cetyl butyrate, stearyl butyrate, and behenyl butyrate.

Also effective are fatty acid ester compounds obtained from an aliphatic monohydric alcohol having an odd number of carbon atoms of 9 or more and an aliphatic carboxylic acid having an even number of carbon atoms, and fatty acid ester compounds having a total of 17 to 23 carbon atoms obtained from n-pentyl alcohol or n-heptyl alcohol and an aliphatic carboxylic acid having an even number of carbon atoms of 10 to 16, such as n-pentadecyl acetate, n-tridecyl butyrate, n-pentadecyl butyrate, n-undecyl caproate, n-tridecyl caproate, n-pentadecyl caproate, n-nonyl caprylate, n-undecyl caprylate, n-tridecyl caprylate, n-pentadecyl caprylate, n-heptyl caprate, n-nonyl caprate, n-undecyl caprate, n-tridecyl caprate, n-pentadecyl caprate, n-pentyl laurate, n-heptyl laurate, n-nonyl laurate, lauric acid n-undecyl, n-tridecyl laurate, n-pentadecyl laurate, n-pentyl myristate, n-heptyl myristate, n-nonyl myristate, n-undecyl myristate, n-tridecyl myristate, n-pentadecyl myristate, n-pentyl palmitate, n-heptyl palmitate, n-nonyl palmitate, n-undecyl palmitate, n-tridecyl palmitate, Examples include n-pentadecyl palmitate, n-nonyl stearate, n-undecyl stearate, n-tridecyl stearate, n-pentadecyl stearate, n-nonyl eicosanoate, n-undelci eicosanoate, n-tridecyl eicosanoate, n-pentadecyl eicosanoate, n-nonyl behenate, n-undecyl behenate, n-tridecyl behenate, and n-pentadecyl behenate.

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

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

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

Examples of acid amides include acetamide, propionic acid amide, butyric acid amide, caproic acid amide, caprylic acid amide, capric acid amide, lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, oleic acid amide, erucic acid amide, benzamide, caproic acid anilide, caprylic acid anilide, capric acid anilide, lauric acid anilide, myristic acid anilide, palmitic acid anilide, stearic acid anilide, behenic acid anilide, oleic acid anilide, erucic acid anilide, caproic acid N-methylamide, caprylic acid N-methylamide, capric acid N-methylamide, Phosphoric acid N-methylamide, lauric acid N-methylamide, myristic acid N-methylamide, palmitic acid N-methylamide, stearic acid N-methylamide, behenic acid N-methylamide, oleic acid N-methylamide, erucic acid N-methylamide, lauric acid N-ethylamide, myristic acid N-ethylamide, palmitic acid N-ethylamide, stearic acid N-ethylamide, oleic acid N-ethylamide, lauric acid N-butylamide, myristic acid N-butylamide, palmitic acid N-butylamide, stearic acid N-butylamide, oleic acid N-butylamide, lauric acid N-octylamide Amides, myristic acid N-octylamide, palmitic acid N-octylamide, stearic acid N-octylamide, oleic acid N-octylamide, lauric acid N-dodecylamide, myristic acid N-dodecylamide, palmitic acid N-dodecylamide, stearic acid N-dodecylamide, oleic acid N-dodecylamide, dilauric acid amide, dimyristic acid amide, dipalmitic acid amide, distearic acid amide, dioleic acid amide, trilauric acid amide, trimyristic acid amide, tripalmitic acid amide, tristearic acid amide, trioleic acid amide, succinic acid amide, adipic acid Examples of the amide include glutaric acid amide, malonic acid amide, azelaic acid amide, maleic acid amide, succinic acid N-methylamide, adipic acid N-methylamide, glutaric acid N-methylamide, malonic acid N-methylamide, azelaic acid N-methylamide, succinic acid N-ethylamide, adipic acid N-ethylamide, glutaric acid N-ethylamide, malonic acid N-ethylamide, azelaic acid N-ethylamide, succinic acid N-butylamide, adipic acid N-butylamide, glutaric acid N-butylamide, malonic acid N-butylamide, adipic acid N-octylamide, and adipic acid N-dodecylamide.

〔式中、Ｒ_１は水素原子又はメチル基を示し、ｍは０～２の整数を示し、Ｘ_１及びＸ_２のいずれか一方は－（ＣＨ_２）_ｎＯＣＯＲ_２又は（ＣＨ_２）_ｎＣＯＯＲ_２、他方は水素原子を示し、ｎは０～２の整数を示し、Ｒ_２は炭素数４以上のアルキル基又はアルケニル基を示し、Ｙ_１及びＹ_２はそれぞれ独立して、水素原子、炭素数１～４のアルキル基、メトキシ基、ハロゲン原子のいずれかを示し、ｒ及びｐはそれぞれ独立して、１～３の整数を示す〕 The component (iii) of the thermochromic color-memorizing material in the decolorized state may be a compound represented by the following formula (1).

[In the formula, _R1 represents a hydrogen atom or a methyl group, m represents an integer of 0 to 2, one of _X1 and _X2 is -( _CH2 ) _nOCOR2 or ( _CH2 ) _nCOOR2 , _and the other represents a hydrogen atom, _n represents an integer of 0 to 2, _R2 represents an alkyl group or an alkenyl group having 4 or more carbon atoms, _Y1 and _Y2 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, or a halogen atom, and r and p each independently represent an integer of 1 to 3]

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

（式中、Ｒは炭素数８以上のアルキル基又はアルケニル基を示し、好ましくは炭素数１０～２４のアルキル基であり、より好ましくは炭素数１２～２２のアルキル基である） Among the compounds represented by formula (1), a compound represented by the following formula (2) is more preferable.

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

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

（式中、Ｒは炭素数８以上のアルキル基又はアルケニル基を示し、ｍ及びｎはそれぞれ独立して、１～３の整数を示し、Ｘ及びＹはそれぞれ独立して、水素原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、ハロゲン原子のいずれかを示す） Furthermore, the component (iii) may be a compound represented by the following formula (3).

(In the formula, R represents an alkyl group or alkenyl group having 8 or more carbon atoms, m and n each independently represent an integer from 1 to 3, and X and Y each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom.)

Examples of the compound represented by formula (3) include diphenylmethyl octanoate, diphenylmethyl nonanoate, diphenylmethyl decanoate, diphenylmethyl undecanoate, diphenylmethyl dodecanoate, diphenylmethyl tridecanoate, diphenylmethyl tetradecanoate, diphenylmethyl pentadecanoate, diphenylmethyl hexadecanoate, diphenylmethyl heptadecanoate, and diphenylmethyl octadecanoate.

（式中、Ｘは水素原子、炭素数１～４のアルキル基、メトキシ基、ハロゲン原子のいずれかを示し、ｍは１～３の整数を示し、ｎは１～２０の整数を示す） Furthermore, the component (iii) may be a compound represented by the following formula (4).

(In the formula, X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, or a halogen atom, m represents an integer of 1 to 3, and n represents an integer of 1 to 20.)

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

（式中、Ｒは炭素数１～２１のアルキル基又はアルケニル基を示し、ｎは１～３の整数を示す） Furthermore, the component (iii) may be a compound represented by the following formula (5).

(In the formula, R represents an alkyl group or alkenyl group having 1 to 21 carbon atoms, and n represents an integer of 1 to 3.)

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

（式中、Ｘは水素原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、ハロゲン原子のいずれかを示し、ｍは１～３の整数を示し、ｎは１～２０の整数を示す） Furthermore, the component (iii) may be a compound represented by the following formula (6).

(In the formula, X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom; m represents an integer of 1 to 3; and n represents an integer of 1 to 20.)

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

（式中、Ｒは炭素数４～２２のアルキル基、シクロアルキルアルキル基、シクロアルキル基、炭素数４～２２のアルケニル基のいずれかを示し、Ｘは水素原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、ハロゲン原子のいずれかを示し、ｎは０又は１を示す） Furthermore, the component (iii) may be a compound represented by the following formula (7).

(In the formula, R represents any one of an alkyl group having 4 to 22 carbon atoms, a cycloalkylalkyl group, a cycloalkyl group, and an alkenyl group having 4 to 22 carbon atoms; X represents any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom; and n represents 0 or 1.)

Examples of the compound represented by formula (7) include decyl 4-phenylbenzoate, lauryl 4-phenylbenzoate, myristyl 4-phenylbenzoate, cyclohexylethyl 4-phenylbenzoate, octyl 4-biphenylacetate, nonyl 4-biphenylacetate, decyl 4-biphenylacetate, lauryl 4-biphenylacetate, myristyl 4-biphenylacetate, tridecyl 4-biphenylacetate, pentadecyl 4-biphenylacetate, cetyl 4-biphenylacetate, cyclopentyl 4-biphenylacetate, cyclohexylmethyl 4-biphenylacetate, hexyl 4-biphenylacetate, and cyclohexylmethyl 4-biphenylacetate.

（式中、Ｒは炭素数３～１８のアルキル基又は炭素数３～１８の脂肪族アシル基を示し、Ｘは水素原子、炭素数１～３のアルキル基、炭素数１又は２のアルコキシ基、ハロゲン原子のいずれかを示し、Ｙは水素原子又はメチル基を示し、Ｚは水素原子、炭素数１～４のアルキル基、炭素数１又は２のアルコキシ基、ハロゲン原子のいずれかを示す） Furthermore, the component (iii) may be a compound represented by the following formula (8).

(In the formula, R represents an alkyl group having 3 to 18 carbon atoms or an aliphatic acyl group having 3 to 18 carbon atoms; X represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 or 2 carbon atoms, or a halogen atom; Y represents a hydrogen atom or a methyl group; and Z represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 or 2 carbon atoms, or a halogen atom.)

Examples of compounds represented by formula (8) include phenoxyethyl 4-butoxybenzoate, phenoxyethyl 4-pentyloxybenzoate, phenoxyethyl 4-tetradecyloxybenzoate, esters of phenoxyethyl 4-hydroxybenzoate and dodecanoic acid, and dodecyl ether of phenoxyethyl vanillate.

（式中、Ｒは炭素数４～２２のアルキル基、炭素数４～２２のアルケニル基、シクロアルキルアルキル基、シクロアルキル基のいずれかを示し、Ｘは水素原子、アルキル基、アルコキシ基、ハロゲン原子のいずれかを示し、Ｙは水素原子、アルキル基、アルコキシ基、ハロゲン原子のいずれかを示し、ｎは０又は１を示す） Furthermore, the component (iii) may be a compound represented by the following formula (9).

(In the formula, R represents any one of an alkyl group having 4 to 22 carbon atoms, an alkenyl group having 4 to 22 carbon atoms, a cycloalkylalkyl group, and a cycloalkyl group; X represents any one of a hydrogen atom, an alkyl group, an alkoxy group, and a halogen atom; Y represents any one of a hydrogen atom, an alkyl group, an alkoxy group, and a halogen atom; and n represents 0 or 1.)

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

（式中、Ｒは炭素数３～１８のアルキル基、炭素数６～１１のシクロアルキルアルキル基、炭素数５～７のシクロアルキル基、炭素数３～１８のアルケニル基のいずれかを示し、Ｘは水素原子、炭素数１～４のアルキル基、炭素数１～３のアルコキシ基、ハロゲン原子のいずれかを示し、Ｙは水素原子、炭素数１～４のアルキル基、メトキシ基、エトキシ基、ハロゲン原子のいずれかを示す） Furthermore, the component (iii) may be a compound represented by the following formula (10).

(In the formula, R represents any one of an alkyl group having 3 to 18 carbon atoms, a cycloalkylalkyl group having 6 to 11 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, and an alkenyl group having 3 to 18 carbon atoms; X represents any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a halogen atom; and Y represents any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, an ethoxy group, and a halogen atom.)

Examples of compounds represented by formula (10) include phenoxyethyl ether of nonyl 4-hydroxybenzoate, phenoxyethyl ether of decyl 4-hydroxybenzoate, phenoxyethyl ether of undecyl 4-hydroxybenzoate, and phenoxyethyl ether of dodecyl vanillate.

（式中、Ｒは炭素数３～８のシクロアルキル基又は炭素数４～９のシクロアルキルアルキル基を示し、ｎは１～３の整数を示す） Furthermore, the component (iii) may be a compound represented by the following formula (11).

(In the formula, R represents a cycloalkyl group having 3 to 8 carbon atoms or a cycloalkylalkyl group having 4 to 9 carbon atoms, and n represents an integer of 1 to 3.)

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

（式中、Ｒは炭素数３～１７のアルキル基、炭素数３～８のシクロアルキル基、炭素数５～８のシクロアルキルアルキル基のいずれかを示し、Ｘは水素原子、炭素数１～５のアルキル基、メトキシ基、エトキシ基、ハロゲン原子のいずれかを示し、ｎは１～３の整数を示す） Furthermore, the component (iii) may be a compound represented by the following formula (12).

(In the formula, R represents any one of an alkyl group having 3 to 17 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and a cycloalkylalkyl group having 5 to 8 carbon atoms; X represents any one of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a methoxy group, an ethoxy group, and a halogen atom; and n represents an integer of 1 to 3.)

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

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

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 conditions of use, and can exert the same action and effect.

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 microcapsule according to the purpose to impart durability or to modify the surface properties for practical use.
During microencapsulation, a non-thermochromic colorant such as a general dye or pigment can be added to bring about an alternating color change from color (1) to color (2).
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.

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 diameter was measured by determining the particle region using an image analysis type 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 diameter of particles equivalent to a sphere of equal volume using this value.
When the particle size of all or most 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 measuring device (manufactured by HORIBA, Ltd., product name: LA-300) based on values measured using the above software or a measuring device using the Coulter method.

The temperature control indicator of the present invention is applied to items requiring temperature control, such as fresh foods, frozen foods, and medicines, to which a cold chain is applied. The appropriate temperature range for these items 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 a cold chain is applied is in the low temperature range above -30°C and below 10°C, and they are distributed and stored in a refrigerated or frozen state. The above-mentioned items or storage containers for which the appropriate temperature range is in the low temperature range are stored in warehouses or cooling devices such as refrigerators and 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. For example, cooling and heating devices that use Peltier elements, cooling and heating devices filled with refrigerants such as cold water or ice chips, refrigerators, freezers, and other cooling devices commonly used in everyday living environments can be appropriately selected according to the appropriate temperature range of the item, allowing storage within the appropriate temperature range.

The temperature control indicator of the present invention uses two types of thermochromic color-memorizing materials. Of the two types of thermochromic color-memorizing materials, the component (C) is a compound represented by the above formula (C), and the thermochromic color-memorizing material having a complete decolorization temperature _t4 in the range of -25°C or more and 15°C or less (hereinafter sometimes referred to as "one thermochromic color-memorizing material") is in a colored state, and the thermochromic color-memorizing material having a complete decolorization temperature _t1 in the range of -30°C or more and 10°C or less (hereinafter sometimes referred to as "the other thermochromic color-memorizing material") is in a decolorized state. When the thermochromic color-memory material in a colored state completely loses color at a complete color-discoloring temperature _t4 , or when the thermochromic color-memory material in a color-discolored state completely develops color at a complete color-developing temperature _t1 , a color change occurs in the temperature control indicator, making it possible to determine whether an item requiring temperature control has deviated from the appropriate temperature range.
Here, the complete discoloration temperature _t4 of the thermochromic color memory material in the colored state is a temperature higher than the upper limit temperature of the appropriate temperature range, and the complete discoloration temperature _t1 of the thermochromic color memory material in the discolored state is a temperature lower than the lower limit temperature of the appropriate temperature range, so that the temperature control indicator of the present invention can effectively function for temperature control of an article within the appropriate temperature range.
In other words, when the complete decolorization temperature _t4 of the thermochromic color-memory material in a colored state and the upper limit temperature _TMAX of the appropriate temperature range of the article satisfy _TMAX < _t4 , it is possible to determine from the color change of the temperature control indicator that the article or its storage container has deviated from a temperature environment higher than the appropriate temperature range. In order to strictly control the temperature, the difference ( _ΔTMAX ) between temperature _t4 and temperature _TMAX [=(complete decolorization temperature _t4 of the thermochromic color-memory material in a colored state)-(upper limit temperature _TMAX of the appropriate temperature range)] is preferably 0< _ΔTMAX ≦3, more preferably 0< _ΔTMAX ≦2, and even more preferably 0< _ΔTMAX ≦1.
Similarly, when the complete color-developing temperature _t1 of the thermochromic color-memory material in the decolorized state and the lower limit temperature _Tmin of the appropriate temperature range of the article satisfy _t1 < _Tmin , it is possible to determine from the color change of the temperature control indicator that the article or its storage container has deviated from a temperature environment lower than the appropriate temperature range. In order to strictly control the temperature, the difference ( _ΔTmin ) between temperature _t1 and temperature _Tmin [= (lower limit temperature _Tmin of the appropriate temperature range) - (complete color-developing temperature _t1 of the thermochromic color-memory material in the decolorized state)] is preferably 0 < _ΔTmin ≦ 3, more preferably 0 < _ΔTmin ≦ 2, and even more preferably 0 < ΔTmin _≦ 1.

The complete decolorization temperature _t4 of the thermochromic color memory material in the decolorized state is higher than the complete decolorization temperature _t4 of the thermochromic color memory material in the colored state, and the complete color development temperature _t1 of the thermochromic color memory material in the decolorized state is higher than the complete color development temperature _t1 of the thermochromic color memory material in the colored state. As a result, if the temperature control indicator deviates from the appropriate temperature range for the article even once, it becomes difficult for one of the initial thermochromic color memory materials to return to the temperature control indicator before decoloration in the colored state, and therefore it becomes possible to irreversibly determine by the temperature control indicator whether the article requiring temperature control or its storage container has been stored without ever deviating from the appropriate temperature range.

The temperature management indicator of the present invention can determine whether an item or its storage container has deviated from the appropriate temperature range by the fact that the thermochromic color-memory material in a colored state becomes decolorized in a temperature range equal to or higher than _the complete color-discoloring temperature _t4 , or by the fact that the thermochromic color-memory material in a decolorized state becomes colored in a temperature range equal to the complete color-discoloring temperature t1, and the upper limit temperature of the appropriate temperature range corresponds to the complete color-discoloring temperature _t4 of the thermochromic color-memory material in a colored state, and the lower limit temperature of the appropriate temperature range corresponds to the complete color-discoloring temperature _t1 of the thermochromic color-memory material in a decolorized state.
Here, when one type of thermochromic color-memory material is used as a temperature control indicator, it is necessary to make the complete decolorization temperature _t4 correspond to the upper limit temperature of the appropriate temperature range and the complete color development temperature _t1 correspond to the lower limit temperature of the appropriate temperature range, but since the complete decolorization temperature _t4 and the complete color development temperature _t1 are determined by the type of component (iii) used in the thermochromic color-memory material, it may be difficult to make both the temperature _t4 and the temperature _t1 correspond to the upper limit temperature and the lower limit temperature of the appropriate temperature range. In other words, depending on the appropriate temperature range of the article, it may be difficult to perform temperature control using a temperature control indicator using a thermochromic color-memory material.
In the temperature control indicator of the present invention, the complete decolorization temperature _t4 and the complete color development temperature _t1 are also determined by the type of component (c) of each thermochromic color memory material, but by using two types of thermochromic color memory materials, it is not necessary to make the temperatures _t4 and _t1 of each thermochromic color memory material correspond to the upper limit and lower limit temperatures of the appropriate temperature range, respectively. In other words, it is sufficient to make the complete decolorization temperature _t4 of the thermochromic color memory material in the colored state correspond to the upper limit temperature of the appropriate temperature range, and the complete color development temperature _t1 of the thermochromic color memory material in the decolored state correspond to the lower limit temperature of the appropriate temperature range, and it becomes easy to perform temperature control by the temperature control indicator using the thermochromic color memory material, regardless of the appropriate temperature range of the article.
Furthermore, by changing the type of component (c) used in each thermochromic color-memory material, the complete decolorization temperature _t4 of the thermochromic color-memory material in the colored state and the complete color-developing temperature _t1 of the thermochromic color-memory material in the decolorized state can be adjusted to any temperature, making it easy to control the temperature using the temperature control indicator of the present invention even for items with a narrow appropriate temperature range.

In the initial state of the temperature management indicator of the present invention, one of the thermochromic color-memory materials (thermochromic color-memory material A) is in a colored state and the other thermochromic color-memory material (thermochromic color-memory material B) is in a decolored state, and within the appropriate temperature range of the item requiring temperature management, only the color of the thermochromic color-memory material in the colored state can be seen.
An example of the color change behavior of the temperature management indicator in the initial state is shown in FIG. 2, and another example is shown in FIG. 3. In FIG. 2 and FIG. 3, the vertical axis represents color density, and the horizontal axis represents temperature, and the change in color density due to temperature change proceeds along the arrow. The solid line is the color density-temperature curve of the thermochromic color memory material in the colored state, and the dashed line is the color density-temperature curve of the thermochromic color memory material in the decolored state. Here, t ₁ , t ₂ , t ₃ , and t ₄ respectively represent the complete color development temperature, color development start temperature, decolorization start temperature, and complete decolorization temperature of the thermochromic color memory material in the colored state, and t ₁ ', t ₂ ', t ₃ ', and t ₄ ' respectively represent the complete color development temperature, color development start temperature, decolorization start temperature, and complete decolorization temperature of the thermochromic color memory material in the decolored state. Hereinafter, _the complete color development temperature _t1 , color development onset temperature _t2 , decolorization onset temperature t3, and complete decolorization temperature _t4 of the thermochromic color memory material in the decolorized state may be referred to as "complete color development temperature _t1 ',""color development onset temperature _t2 ',""decolorization onset temperature _t3 '," and "complete decolorization temperature _t4 '," respectively.
a is a point in a temperature control indicator in an initial state that represents the concentration shown by the thermochromic color memory material in a colored state at a certain temperature t within the appropriate temperature range, and b is a point in a temperature control indicator in an initial state that represents the concentration shown by the thermochromic color memory material in a decolorized state at temperature t.

The color change behavior when the temperature control indicator in the initial state is placed in a temperature environment higher than the appropriate temperature range (a temperature range exceeding temperature _t1 ' and lower than temperature _t4 ) will be described with reference to FIG.
When the temperature control indicator in the initial state is placed in a temperature environment higher than the appropriate temperature range (temperature range above temperature _t4 ), the thermochromic color memory material in the colored state will lose its color (arrow 1), and each thermochromic color memory material will be in a decolored state (state 1). In order to return the thermochromic color memory material to the colored state from this state, cooling is required. However, when the indicator is placed in a specific temperature environment lower than the appropriate temperature range (temperature range above temperature _t1 and below temperature _t1 '), the other thermochromic color memory material (the thermochromic color memory material in the decolored state in the initial state) will develop a color (arrow 2), and only the other thermochromic color memory material will develop a color (state 2). When the indicator is placed in a temperature range below temperature _t1 , one of the thermochromic color memory materials will develop a color (arrow 3), and each thermochromic color memory material will develop a color (state 3).

Also, the color change behavior when the temperature control indicator in the initial state is placed in a temperature environment lower than the appropriate temperature range (a temperature range exceeding temperature _t1 ' and lower than temperature _t4 ) will be described with reference to FIG.
When the temperature control indicator in the initial state is placed in a temperature environment lower than the appropriate temperature range (temperature range below temperature _t1 '), the thermochromic color memory material in the decolorized state develops color (arrow 1'), and each thermochromic color memory material becomes in a colored state (state 3'). In order to return the thermochromic color memory material to the decolorized state from this state, heating is required, but when the indicator is placed in a specific temperature environment higher than the appropriate temperature range (temperature range above temperature _t4 and below temperature _t4 '), one of the thermochromic color memory materials (the thermochromic color memory material in the colored state in the initial state) decolors (arrow 2'), and the other thermochromic color memory material (the thermochromic color memory material in the decolorized state in the initial state) is in a colored state (state 2'). When placed in a temperature range above temperature t ₄ ', the other thermochromic color memory material loses its color (arrow 3'), and both thermochromic color memory materials enter a decolored state (state 1').
As described above, if the temperature control indicator of the present invention is placed even once from its initial state in a temperature environment higher than the appropriate temperature range for the item, or in a temperature environment lower than the appropriate temperature range, it becomes difficult for one of the thermosensitive color-changing color-memory materials to return to its initial colored state, pre-color change temperature control indicator, making it possible to irreversibly determine whether an item requiring temperature control or its storage container has been stored without ever deviating from the appropriate temperature range.

The temperature management indicator of the present invention can determine that an article has left a temperature environment higher than the appropriate temperature range by causing both thermochromic color-memory materials to become decolorized, and that an article has left a temperature environment lower than the appropriate temperature range by causing both thermochromic color-memory materials to become colored.In addition, by maintaining only the other thermochromic color-memory material (the thermochromic color-memory material that is initially decolorized) in a colored state, it can determine that an article has left a temperature environment higher than the appropriate temperature range and a temperature environment lower than the appropriate temperature range.
This is because the complete discoloration temperature _t4 (complete discoloration temperature _t4 ') of the thermochromic color memory material in the discolored state is higher than the complete discoloration temperature _t4 of the thermochromic color memory material in the colored state, and the complete color development temperature _t1 (complete color development temperature _t1 ') of the thermochromic color memory material in the discolored state is higher than the complete color development temperature _t1 of the thermochromic color memory material in the colored state.
Since temperature _t4 ' is greater than temperature _t4 , when the initial state deviates to a temperature environment lower than the appropriate temperature range and the state (state 3') in which both thermochromic color-memory materials are colored deviates to a temperature environment higher than the appropriate temperature range, only the other thermochromic color-memory material develops color in a specific temperature environment (temperature range equal to or greater than temperature _t4 and less than temperature _t4 '). This state is only expressed when the initial state deviates to a temperature environment lower than the appropriate temperature range and then deviates to a temperature environment higher than the appropriate temperature range, so it is possible to distinguish between deviating to a temperature environment higher than the appropriate temperature range and a temperature environment lower than the appropriate temperature range.
Since it becomes easier to determine whether the temperature control indicator has deviated from the appropriate temperature range into a higher or lower temperature environment, the difference (Δt ₄ ) between temperatures t ₄ ' and t ₄ [= (completely bleached temperature t ₄ ') - (completely bleached temperature t ₄ )] is preferably Δt ₄ ≧ 5, and more preferably Δt ₄ ≧ 10. When Δt ₄ satisfies the above range, in the process of heating the thermochromic color memory materials from a state in which both are colored (state 3'), when one thermochromic color memory material (a thermochromic color memory material in an initial colored state) is bleached at temperature t ₄ , the other thermochromic color memory material is more likely to be maintained in a completely colored state.

Similarly, because temperature _t1 ' is greater than temperature _t1 , when the temperature environment deviates from the initial state to a temperature environment higher than the appropriate temperature range and deviates from a state (state 1) in which both thermochromic color-memory materials are decolorized to a temperature environment lower than the appropriate temperature range, only the other thermochromic color-memory material develops color in a specific temperature environment (a temperature range exceeding temperature _t1 and equal to or lower than temperature _t1 '). This state is only manifested when the temperature environment deviates from the initial state to a temperature environment higher than the appropriate temperature range and then to a temperature environment lower than the appropriate temperature range, so it is possible to distinguish between deviations from a temperature environment higher than the appropriate temperature range and a temperature environment lower than the appropriate temperature range.
Since it becomes easier to determine whether the temperature control indicator has deviated from the appropriate temperature range into a higher or lower temperature environment, the difference (Δt ₁ ) between temperature t ₁ ' and temperature t ₁ [= (complete color-developing temperature t ₁ ') - (complete color-developing temperature t ₁ )] is preferably Δt ₁ ≧ 5, and more preferably Δt ₁ ≧ 10. When Δt ₁ satisfies the above range, in the process of cooling each of the thermochromic color-memory materials from a state in which both are decolorized (state 1), when the other thermochromic color-memory material develops color at temperature t ₁ ', one of the thermochromic color-memory materials is more likely to be maintained in a completely decolorized state.

Since it becomes easy to distinguish whether the temperature control indicator has deviated to a temperature environment higher than or lower than the appropriate temperature range, it is preferable that the decolorization start temperature _t3 (decolorization start temperature _t3 ') of the thermochromic color memory material in the decolorized state is higher than the complete decolorization temperature _t4 of the thermochromic color memory material in the colored state ( _t3 '> _t4 ). In this way, in the process of heating the thermochromic color memory materials from the state in which both are colored (state 3'), when one thermochromic color memory material (a thermochromic color memory material in a colored state in the initial state) is completely decolored at temperature _t4 , the other thermochromic color memory material (a thermochromic color memory material in a decolored state in the initial state) is easily maintained in a completely colored state. Therefore, it becomes easy to clearly distinguish whether the article has deviated to a temperature environment lower than or higher than the appropriate temperature range.
Since the other thermosensitive color-changing color memory material is more likely to be maintained in a fully colored state, the difference between temperatures t ₃ ' and t ₄ , (t ₃ '-t ₄ ) [= (color-discoloring starting temperature t ₃ ')-(complete color-discoloring temperature t ₄ )] is preferably (t ₃ '-t ₄ )≧1, more preferably (t ₃ '-t ₄ )≧3, and even more preferably (t ₃ '-t ₄ )≧5.

Since it becomes easier to determine whether the temperature control indicator has deviated from the appropriate temperature range to a temperature environment higher or lower than the appropriate temperature range, it is preferable that the complete color development temperature _t1 (complete color development temperature _t1 ') of the thermochromic color memory material in the decolorized state is higher than the color development start temperature _t2 of the thermochromic color memory material in the colored state ( _t1 '> _t2 ). This makes it easier to maintain one of the thermochromic color memory materials (the thermochromic color memory material in the colored state in the initial state) in a completely decolorized state when the other thermochromic color memory material (the thermochromic color memory material in the decolorized state in the initial state) completely develops color at temperature t1 _' in the process of cooling from the decolorized state (state 1) of both thermochromic color memory materials. Therefore, it becomes easier to clearly determine whether the article has deviated from the appropriate temperature range to a temperature environment higher or lower than the appropriate temperature range.
Furthermore, since one of the thermosensitive color-changing color memory materials is more likely to be maintained in a completely decolorized state, it is preferable that the difference between temperature t ₁ ' and temperature t ₂ (t ₁ '-t ₂ ) [= (complete color-developing temperature t ₁ ')-(color-developing initiation temperature t ₂ )] is (t ₁ '-t ₂ )≧1, more preferably (t ₁ '-t ₂ )≧3, and even more preferably (t ₁ '-t ₂ )≧5.

Since it becomes easy to determine whether the temperature control indicator has deviated from the appropriate temperature range to a temperature environment higher or lower than the appropriate temperature range, it is preferable that the complete decolorization temperature t ₄ (complete decolorization temperature t ₄ ') of the decolorized thermochromic color memory material is 40°C or higher (t ₄ '≧40). This makes it difficult for the other thermochromic color memory material in a colored state (the thermochromic color memory material in an initial decolorized state) to decolorize in an everyday living environment (for example, normal temperature range), and in the process of heating from the state in which both thermochromic color memory materials are colored (state 3'), the other thermochromic color memory material is easily maintained in a completely colored state. Therefore, it is easy to determine whether the article has deviated from the appropriate temperature range to a temperature environment lower or higher than the appropriate temperature range. The normal temperature is based on 20±15° C. as specified in JIS Z 8703, and the normal temperature range is a temperature range of 5° C. or higher and 35° C. or lower.
The complete decolorization temperature _t4 ' is more preferably 50° C. or higher, and even more preferably 60° C. or higher. When the temperature _t4 ' satisfies the above range, the other thermochromic color memory material in the colored state becomes more difficult to decolor in an everyday living environment, and becomes more likely to maintain the completely colored state during the process of heating from state 3'.

Since it becomes easier to distinguish whether the temperature control indicator is in a higher or lower temperature environment than the appropriate temperature range, it is preferable that the complete color development temperature _t1 of the thermochromic color memory material in the colored state is −30° C. or lower (t1 _≦ −30).
The temperature range of -30°C or less is a temperature range that is difficult to reach with cooling tools that are generally used in daily living environments, and when the complete color development temperature _t1 is -30°C or less, the thermochromic color memory material in the decolorized state is difficult to develop color in cooling tools that are generally used in daily living environments, and in the process of cooling from the state (state 1) in which both thermochromic color memory materials are decolorized, one of the thermochromic color memory materials (the thermochromic color memory material in the colored state in the initial state) is more likely to be maintained in the decolorized state. Therefore, only the other thermochromic color memory material (the thermochromic color memory material in the decolorized state in the initial state) is in a completely colored state, and it is easy to distinguish whether the article has deviated from the appropriate temperature range to a temperature environment higher or lower.
The complete color development temperature _t1 is more preferably −40° C. or lower, and even more preferably −50° C. or lower. When the complete color development temperature _t1 satisfies the above range, one of the thermochromic color-memory materials in the decolorized state is less likely to develop color in a cooling device commonly used in everyday living environments, and only the other thermochromic color-memory material is more likely to be maintained in a completely colored state.

In the temperature control indicator of the present invention, it is preferable that the decolorization start temperature _t3 of the thermochromic color memory material in the colored state is higher than the colorization start temperature _t2 (colorization start temperature _t2 ') of the thermochromic color memory material in the decolored state ( _t3 > _t2 '). This makes it easier for the temperature control indicator in the initial state to maintain the completely colored state of the thermochromic color memory material in the colored state and the completely decolored state of the thermochromic color memory material in the decolored state at a certain temperature within the appropriate temperature range, and makes it easier to visually recognize only the color of one of the thermochromic color memory materials. Therefore, when the temperature control indicator deviates from the appropriate temperature range and a color change occurs, the color change of the temperature control indicator from the initial state is clear, and it is easy to determine whether or not the appropriate temperature range has been deviated.

In each thermochromic color memory material applied to the present invention, it is preferable that the decolorization start temperature _t3 is higher than the color development start temperature _t2 ', the decolorization start temperature _t3 ' is higher than the complete decolorization temperature _t4 , and the complete color development temperature _t1 ' is higher than the color development start temperature _t2 . It is also preferable that the complete decolorization temperature _t4 ' is 40°C or higher, and the complete color development temperature _t1 is -30°C or lower.

The temperature management indicator of the present invention is composed of a first reversible thermochromic body having a thermosensitive color-memorizing material and a second reversible thermochromic body having a thermosensitive color-memorizing material. Here, the configuration of the temperature management indicator (10) may be, for example, a configuration in which the first reversible thermochromic body (20) and the second reversible thermochromic body (30) are arranged side by side, as shown in Figures 4 and 5, or a configuration in which the second reversible thermochromic body (30) is laminated on the first reversible thermochromic body (20). When the temperature management indicator has a laminated configuration, it is preferable that the size of the second reversible thermochromic body is smaller than that of the first reversible thermochromic body.
An example of the color change when two reversible thermochromic bodies are arranged side by side will be described with reference to FIG. 6, and an example of the color change when they are layered will be described with reference to FIG.

6 and 7, in the initial state of the temperature control indicator, one of the thermochromic color memory materials is in a colored state, so that at a certain temperature t within the appropriate temperature range, only the color of the thermochromic color memory material in the colored state is visible (state a). When the temperature control indicator is placed in a temperature environment higher than the appropriate temperature range (temperature range of temperature _t4 or higher), the colors shown by each thermochromic color memory material in the decolored state are visible (state b). When the temperature control indicator is placed in a specific temperature environment lower than the appropriate temperature range (temperature range exceeding temperature _t1 and lower than temperature _t1 '), the color shown by the other thermochromic color memory material (the thermochromic color memory material in the decolored state in the initial state) in the colored state is visible (state c). Furthermore, when placed in a temperature range lower than temperature _t1 , the colors shown by each thermochromic color memory material in the colored state are visible (state d).
Similarly, when the temperature control indicator in state a is placed in a temperature environment lower than the appropriate temperature range (temperature range below temperature _t1 '), the colors shown by each thermochromic color memory material in the colored state are visually recognized (state d'). When it is placed in a specific temperature environment higher than the appropriate temperature range (temperature range above temperature _t4 and below temperature _t4 '), the color shown by the other thermochromic color memory material (the thermochromic color memory material in the decolored state in the initial state) in the colored state is visually recognized (state c'). Furthermore, when it is placed in a temperature range above temperature _t4 ', the colors shown by each thermochromic color memory material in the decolored state are visually recognized (state b').
In other words, if the temperature control indicator of the present invention deviates from the appropriate temperature range even once from its initial state, it becomes difficult to return it to the initial pre-color change temperature control indicator state in which one of the thermosensitive color-changing color memory materials is in a colored state, making it possible to irreversibly determine whether an item requiring temperature control or its storage container has been stored without ever deviating from the appropriate temperature range.

When the temperature management indicator has a configuration in which a second reversible thermochromic body is laminated on a first reversible thermochromic body, the second reversible thermochromic body may be transparent, for example, as shown in Fig. 8. In this case, the first reversible thermochromic body and the second reversible thermochromic body may be of the same size.
An example of the color change of the temperature control indicator in this case will be described with reference to FIG.

In the initial state of the temperature control indicator, one of the thermochromic color memory materials is in a colored state and the other thermochromic color memory material is in a decolored state, so that at a certain temperature t within the appropriate temperature range, a mixture of the color shown by the thermochromic color memory material in the colored state and the color shown by the thermochromic color memory material in the decolored state is visible (state a). When the temperature control indicator is placed in a temperature environment higher than the appropriate temperature range (temperature range equal to or higher than temperature _t4 ), a mixture of the colors shown by the thermochromic color memory materials in the decolored state is visible (state b). When the thermochromic color memory material is placed in a specific temperature environment lower than the appropriate temperature range (a temperature range above temperature _t1 and below temperature _t1 '), a color obtained by mixing the color shown in the colored state of the other thermochromic color memory material (the thermochromic color memory material in the decolored state in the initial state) and the color shown in the decolored state of the one thermochromic color memory material (the thermochromic color memory material in the colored state in the initial state) is visible (state c).When the thermochromic color memory material is placed in a temperature range below temperature _t1 , a color obtained by mixing the colors shown in the colored states of the thermochromic color memory materials is visible (state d).
Similarly, when the temperature control indicator in state a is placed in a temperature environment lower than the appropriate temperature range (temperature range below temperature _t1 '), a color obtained by mixing the colors shown by each thermochromic color memory material in the colored state is visible (state d'). When it is placed in a specific temperature environment higher than the appropriate temperature range (temperature range above temperature _t4 and below temperature _t4 '), a color obtained by mixing the color shown by the other thermochromic color memory material (the thermochromic color memory material in the colored state in the initial state) and the color shown by the one thermochromic color memory material (the thermochromic color memory material in the colored state in the initial state) in the decolored state is visible (state c'). Furthermore, when it is placed in a temperature range above _t4 ', a color obtained by mixing the colors shown by each thermochromic color memory material in the decolored state is visible (state b').
In other words, if the above-mentioned temperature control indicator deviates from the appropriate temperature range even once from its initial state, it becomes difficult to return it to the initial pre-color change temperature control indicator in which one of the thermosensitive color-changing color memory materials is in a colored state, making it possible to irreversibly determine whether an item requiring temperature control or its storage container has been stored without ever deviating from the appropriate temperature range.
Furthermore, in the temperature control indicator having the above configuration, since the second reversible thermochromic body has transparency, the first reversible thermochromic body can be seen through the second reversible thermochromic body, and a mixture of the colors shown by the thermochromic color memory materials can be seen. Therefore, the color change shown by the temperature control indicator can be made diverse, and it is easy to determine whether the temperature control indicator has deviated from the appropriate temperature range, so it is preferable that the second reversible thermochromic body has transparency.

It is preferable that the thermochromic color-memory materials used in the present invention exhibit different colors in the colored state, that is, the components (a) of the thermochromic color-memory materials are different from each other.
In this case, the color seen in the colored state of one thermosensitive color-changing color memory material is different from the color seen in the colored state of the other thermosensitive color-changing color memory material, making it easy to determine whether the temperature control indicator in its initial state has deviated from the appropriate temperature range.
In particular, in a configuration in which a temperature control indicator is formed by laminating a transparent second reversible thermochromic body on a first reversible thermochromic body, when each thermochromic color memory material is in a colored state, a mixture of the colors exhibited by each thermochromic color memory material in a colored state is visible, and therefore the color visible when only one of the initial thermochromic color memory materials is in a colored state, the color visible when both thermochromic color memory materials are in a colored state, and the color visible when only the other thermochromic color memory material is in a colored state are all different, making it easy and clear to determine whether the temperature control indicator has deviated from its initial state to a temperature environment lower than the appropriate temperature range, a temperature environment higher than the appropriate temperature range, or a temperature environment lower than and higher than the appropriate temperature range.

The hysteresis width (ΔH) of each thermosensitive color-changing color-memory material is 8 to 100°C, 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. By having the hysteresis width (ΔH) within the above range, it becomes easier for the temperature control indicator to function effectively in temperature control of items whose appropriate temperature range is in the low temperature range.

The thermochromic color-memorizing material in the colored state applicable to the present invention has a complete decolorization temperature _t4 in the range of -25° C. or more and 15° C. or less (-25≦ _t4 ≦15), and the thermochromic color-memorizing material in the decolorized state has a complete color-developing temperature _t1 (complete color-developing temperature _t1 ') in the range of more than -30° C. and 10° C. or less [-30< _t1 ( _t1 ')≦10]. This allows the temperature control indicator of the present invention to function effectively in temperature control of articles having an appropriate temperature range in the low temperature region.
Since the temperature control indicator of the present invention can be effectively used in articles having a lower appropriate temperature range, the complete decolorization temperature _t4 of the thermochromic color memory material in the colored state is preferably in the range of -25°C or more and 10°C or less (-25≦t4 _≦ 10), and more preferably in the range of -25°C or more and 5°C or less (-25≦t4 _≦ 5). The complete decolorization temperature _t1 ( _t1 ') of the thermochromic color memory material in the decolored state is preferably in the range of more than -30°C and 5°C or less [-30< _t1 ( _t1 ')≦5], and more preferably in the range of more than -30°C and 0°C or less [-30< _t1 ( _t1 ')≦0].

As shown in FIG. 10, the first reversible thermochromic body (20) may be a reversible thermochromic laminate (first reversible thermochromic laminate (20')) having a structure in which a reversible thermochromic layer (first reversible thermochromic layer (202)) containing a thermochromic color-memorizing material such as a thermochromic color-memorizing microcapsule pigment or resin particles is provided on a support (201). Alternatively, a reversible thermochromic molded body (first reversible thermochromic molded body (20")) containing a thermochromic color-memorizing material in a support may be used.

As shown in FIG. 11, the second reversible thermochromic body (30) may be a reversible thermochromic laminate (second reversible thermochromic laminate (30')) having a structure in which a reversible thermochromic layer (second reversible thermochromic layer (302)) containing a thermochromic color-memorizing material such as a thermochromic color-memorizing microcapsule pigment or resin particles is provided on a support (301). Alternatively, a reversible thermochromic molded body (second reversible thermochromic molded body (30")) containing a thermochromic color-memorizing material in a support may be used.

The first reversible thermochromic body and the second reversible thermochromic body may both be transparent, in which case the thermochromic color memory material is blended in an amount that does not impair the transparency of the reversible thermochromic body.

The configuration of the temperature control indicator (10) is not particularly limited, and may be, for example, a configuration in which a first reversible thermochromic laminate (20') and a second reversible thermochromic laminate (30') are arranged side by side or stacked as shown in FIG. 12. Also, for example, a configuration in which a first reversible thermochromic molded body (20") and a second reversible thermochromic molded body (30") are arranged side by side or stacked as shown in FIG. 13. Also, a configuration in which a first reversible thermochromic laminate and a second reversible thermochromic molded body are arranged side by side or stacked, or a configuration in which a first reversible thermochromic molded body and a second reversible thermochromic laminate are arranged side by side or stacked, may be used.

A reversible thermochromic laminate having a reversible thermochromic layer on a support can be obtained by printing or applying 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, using 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.

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. The form of the support may be uneven, but a flat, sheet, or film form is preferred.
When the reversibly thermochromic laminate has transparency, a transparent support is used. The transparent support is not particularly limited as long as it is colorless and transparent or colored and transparent, and allows the pattern, character, etc. of the adjacent object to be visually recognized, and when the object is a reversibly thermochromic body, the pattern, character, color change, etc. of the reversibly thermochromic body to be visually recognized.
Examples of the transparent support include plastic, glass, elastomer, and rubber.
The support is preferably made of plastic because of its excellent handleability. In addition, considering that the temperature control indicator of the present invention is used in a low temperature range or an ultra-low temperature range, the support is preferably one that is not easily embrittled in the low temperature range or an ultra-low temperature range, and plastics made of polyethylene, polyethylene terephthalate, and acrylonitrile-butadiene-styrene copolymer resin are suitable.

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

In the reversible thermochromic laminate, a non-thermochromic colorant such as a general dye or pigment can be used in combination to bring about an alternating color change from color (1) to color (2). Specific examples include a configuration in which a non-thermochromic layer containing a non-thermochromic colorant is provided between the support and the reversible thermochromic layer, and a configuration in which a non-thermochromic colorant is contained in the reversible thermochromic layer. When the reversible thermochromic laminate is transparent, the non-thermochromic colorant is blended in an amount that does not impair transparency.

A reversible thermochromic molded body containing a thermochromic color-memorizing material in a support can be obtained by molding a thermochromic color-memorizing molding resin composition, which is a molding resin selected from thermoplastic resins or thermosetting resins, by melt-blending the above-mentioned thermochromic color-memorizing material into the molding resin, using a general-purpose molding method such as injection molding, extrusion molding, blow molding, or cast molding.

Examples of molding resins that form the support 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, poly polyamide, copolymer polyamide, polyamideimide, polyacetal, polyvinyl formal, polyvinyl butyral, polyarylate, polyetherimide, polyether ether ketone, polycarbonate, polyphenylene ether, polyphenylene sulfide, polysulfone, fluororesin, ionomer resin, ethylene-propylene copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl alcohol copolymer resin, ethylene-acrylic acid ester copolymer resin, ethylene-methacrylic acid ester copolymer resin, ethylene-vinyl chloride copolymer resin, vinyl chloride-propylene copolymer resin, vinyl chloride-vinylidene chloride copolymer resin, styrene-butadiene copolymer resin, acrylonitrile-vinylidene chloride copolymer resin, acrylonitrile-styrene copolymer resin, acrylonitrile-ethylene-styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, acrylonitrile-chlorinated polyethylene-styrene copolymer resin, acrylonitrile-acrylic acid ester-styrene copolymer resin, ethylene-vinyl acetate resin-vinyl chloride graft copolymer resin, methyl methacrylate-butadiene thermoplastic resins such as styrene-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.

When the reversible thermochromic molded article has transparency, a molding resin that forms a transparent support is used. Examples of molding resins that form a transparent support 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 resins, methacrylic acid ester resins, polyvinyl butyral, polyarylate, polyetherimide, polycarbonate, polysulfone, ionomer resins, ethylene-propylene copolymer resins, ethylene-vinyl acetate copolymer resins, ethylene-vinyl alcohol copolymer resins, ethylene-acrylic acid ester copolymer resins, ethylene-methacrylic acid ester copolymer resins, acrylonitrile-styrene copolymer resins, and cycloolefin copolymers;
Examples of the thermosetting resin include epoxy resin, epoxy acrylate, phenol resin, unsaturated polyester resin, urea resin, aryl resin, silicone resin, and other thermosetting resins.

In the reversibly thermochromic molded product, a non-thermochromic colorant such as a general dye or pigment can be used in combination to bring about an alternating color change from color (1) to color (2). A specific example is a configuration in which a non-thermochromic colorant is contained in the support. Note that, when the reversibly thermochromic molded product has transparency, the non-thermochromic colorant is blended in such a range that does not impair transparency.

A transparent protective layer can be provided on the reversible thermochromic layer of the reversible thermochromic laminate 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 thermochromic color memory material 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 resin emulsion, or by attaching plastic, elastomer, rubber, etc. in the form of a flat surface, sheet, film, etc.
Considering that the temperature control indicator of the present invention is used in a low temperature range or an ultra-low temperature range, it is preferable that the transparent protective layer is not easily embrittled in the low temperature range or the ultra-low temperature range, and it is suitable that the transparent protective layer is composed of a resin such as polyethylene, polyethylene terephthalate, or acrylonitrile-butadiene-styrene copolymer resin.
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.

Examples of the light stabilizer include an ultraviolet absorber, an antioxidant, an antiaging agent, a singlet oxygen quencher, a superoxide anion quencher, an ozone quencher, a visible light absorber, and an infrared absorber.
Examples of the transparent metallic luster pigment include pigments having a core material such as natural mica, synthetic mica, glass pieces, alumina, and transparent film pieces whose surfaces are coated with a metal oxide such as titanium oxide.
By providing a layer in which these light stabilizers or transparent metallic luster pigments are fixed in a dispersed state, light resistance can be imparted.

By providing an adhesive layer on the surface of the reversible thermochromic body that comes into contact with the object, the reversible thermochromic body can be easily adhered to the object.
In the configuration in which the second reversible thermochromic body is laminated on the first reversible thermochromic body, for example, as shown in Fig. 14, an adhesive layer [first adhesive layer (203)] is provided on the surface of the first reversible thermochromic body opposite to the surface on which the second reversible thermochromic body is provided [surface in contact with the object (item or its storage container, etc.)], and the first reversible thermochromic body is attached to the object, and the second reversible thermochromic body is laminated on the first reversible thermochromic body, so that it can be used as a temperature management indicator. In addition, for example, as shown in Fig. 15, an adhesive layer [second adhesive layer (303)] is provided on the surface of the second reversible thermochromic body in contact with the object (first reversible thermochromic body), and the second reversible thermochromic body is attached to the first reversible thermochromic body and laminated on the object.
Furthermore, by providing a first adhesive layer on the surface of the first reversible thermochromic body opposite to the surface on which the second reversible thermochromic body is provided, and by providing a second adhesive layer on the surface of the second reversible thermochromic body that contacts the first reversible thermochromic body, the first reversible thermochromic body can be attached to an object such as an article or its storage container, and the second reversible thermochromic body can be attached to the first reversible thermochromic body for use.
When the reversible thermochromic body is a reversibly thermochromic laminate, the adhesive layer can be provided on the surface of the support opposite to the surface on which the reversible thermochromic layer is provided.
In addition, a first adhesive layer is provided on the surface of the first reversible thermochromic body that contacts the object (such as an article or its storage container), and a second adhesive layer is provided on the surface of the second reversible thermochromic body that contacts the object (such as an article or its storage container), and by attaching both the first reversible thermochromic body and the second reversible thermochromic body to the object, the first reversible thermochromic body and the second reversible thermochromic body can be used as a temperature control indicator in which the first reversible thermochromic body and the second reversible thermochromic body are arranged side by side.

The adhesive layer is not particularly limited as long as it does not affect the coloring, decoloring, color change, etc. of the thermochromic color memory material provided in the reversible thermochromic body and can be attached to an object. When the reversible thermochromic body is transparent, the pattern, letters, etc. of the adjacent object can be visually recognized, and when the object is a reversible thermochromic body, the pattern, letters, color change, etc. of the reversible thermochromic body can be visually recognized.
Examples of adhesives used in the adhesive layer include acrylic resins, urethane resins, styrene-butadiene copolymer resins, ethylene-vinyl acetate copolymer resins, vinyl ether 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 is one that is less likely to lose its adhesiveness in low or ultra-low temperature ranges, and acrylic resins, rubber resins, silicone resins, and epoxy resins are preferred.
The adhesive layer may be provided with a release layer in order to improve the convenience during use and the processability of the reversible thermochromic body provided with the adhesive layer.

In addition, when the reversible thermochromic body is a reversible thermochromic laminate and the support has transparency, the reversible thermochromic layer can be provided on the transparent support, and an adhesive layer can be provided on the surface of the reversible thermochromic layer opposite the transparent support. When the reversible thermochromic laminate of the above configuration is attached, the transparent support is the outermost layer, so it functions as a protective layer for the reversible thermochromic layer, and durability can be imparted to the reversible thermochromic layer without providing a transparent protective layer on the reversible thermochromic layer.

The first reversible thermochromic laminate and the second reversible thermochromic laminate can use a tamper-prevention member as a support. For example, as shown in FIG. 16, the support of the first reversible thermochromic laminate [20 (20')] can be a tamper-prevention member (204) provided with an adhesive layer. By attaching the first reversible thermochromic body of the above-mentioned configuration to an object and laminating the second reversible thermochromic body on the first reversible thermochromic body, when an article or its storage container deviates from a temperature environment outside the appropriate temperature range, it is possible to prevent tampering such as peeling off the first reversible thermochromic body, cooling or heating it again and reattaching it, or replacing it with a new temperature control indicator.
The support of the second reversible thermochromic laminate may be a tamper-proof member provided with an adhesive layer. By laminating or adhering a temperature control indicator in which the second reversible thermochromic body of the above configuration is attached to the first reversible thermochromic body, it is possible to prevent tampering such as peeling off the second reversible thermochromic body, cooling or heating it again, and reattaching it, or replacing it with a new temperature control indicator, when the article or its storage container is placed in a temperature environment outside the appropriate temperature range.
Furthermore, the support of the first reversible thermochromic body and the support of the second reversible thermochromic body can be made into a tamper-proof member provided with an adhesive layer. By adhering the first reversible thermochromic body having the above-mentioned configuration to an object and adhering the second reversible thermochromic body having the above-mentioned configuration to the first reversible thermochromic body, tampering can be further prevented.
As shown in Fig. 17, the support of the transparent second reversible thermochromic laminate [31 (31')] can be a transparent tamper-proof member (314) provided with an adhesive layer. By laminating or adhering a temperature control indicator in which the second reversible thermochromic body of the above configuration is attached to the first reversible thermochromic body, it is possible to prevent tampering such as peeling off the second reversible thermochromic body, cooling or heating it again, and reattaching it, or replacing it with a new temperature control indicator, when the article or its storage container deviates from the temperature environment outside the appropriate temperature range.

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. For example, an example of a tamper-evident component having a tamper-evident function is one in which, when attached to an object and then peeled off, the adhesive layer is transferred to the object in the form of characters due to intra-layer peeling of the laminated structure.
Further examples of tamper-evident components include those that, when attached to an object and then peeled off, separate at the interface of the laminated structure, causing deformation of the layers so that no residue is left on the object and letters appear on the tamper-evident component; and those that use a base material made of a fragile material so that, when attached to an object and then peeled off, the base material is destroyed and a peeling mark remains on the adherend.

In the present invention, transparency refers to the property of transmitting light having a wavelength in the visible light region (a wavelength region of 380 to 780 nm as defined by JIS B 7079).
When the first or second reversible thermochromic body is transparent, the light transmittance in the visible light region (visible light transmittance) is preferably 5% or more, more preferably 10% or more, and even more preferably 20% or more. When the visible light transmittance satisfies the above range, the patterns, characters, color changes, etc. of adjacent reversible thermochromic bodies, or the patterns, characters, etc. of adjacent objects can be clearly and easily recognized.
The light transmittance (visible light transmittance) of the transparent protective layer in the visible light region is preferably 5% or more, more preferably 10% or more, and even more preferably 20% or more. When the visible light transmittance satisfies the above range, the pattern, character, color change, etc. of the adjacent reversible thermochromic layer or reversible thermochromic molded body can be clearly and easily recognized.
The visible light transmittance can be measured, for example, using a spectrophotometer (manufactured by Hitachi, Ltd., product name: U-3210). A reversible thermochromic body or a transparent protective layer is provided on a transparent substrate that transmits light with wavelengths in the visible light region, and the visible light transmittance is measured in the wavelength region from 380 nm to 780 nm using the spectrophotometer. The visible light transmittance can be calculated as the intermediate value between the maximum and minimum values.

The temperature control indicator of the present invention can be used, for example, as follows.
First, the component (C) is a compound represented by the above formula (C), and a reversible thermochromic body provided with a thermochromic color memory material (one thermochromic color memory material) having a complete decolorization temperature _t4 in the range of -25°C or more and 15°C or less is used as a first reversible thermochromic body, and in order to bring the thermochromic color memory material into a colored state, the first reversible thermochromic body is cooled at a temperature equal to or lower than the complete color development temperature _t1 to maintain the colored state. Also, a reversible thermochromic body provided with a thermochromic color memory material (the other thermochromic color memory material) having a complete color development temperature _t1 ^' in the range of more than -30°C and 10°C or less is used as a second reversible thermochromic body, and in order to bring the thermochromic color memory material into a decolored state, the second reversible thermochromic body is heated at a temperature equal to or higher than the complete decolorization temperature _t4 ' to maintain the decolored state.
Next, the cooling of the first reversible thermochromic body and the heating of the second reversible thermochromic body are stopped, and the first reversible thermochromic body and the second reversible thermochromic body are arranged side by side on an article or a storage container in a temperature environment within the appropriate temperature range to form a temperature control indicator. Alternatively, the second reversible thermochromic body is laminated on the first reversible thermochromic body in a temperature environment within the appropriate temperature range to form a temperature control indicator, which is then laminated on the article or the storage container. In this initial state of the temperature control indicator, one of the thermochromic color memory materials is in a colored state and the other thermochromic color memory material is in a decolored state, and the temperature change of the article or its storage container that requires temperature control can be detected. From this state, the color of the temperature control indicator changes, making it possible to irreversibly determine that the article or its storage container has deviated from the appropriate temperature range.
Here, if the temperature control indicator is mistakenly placed in a temperature environment higher than the appropriate temperature range before use and both reversible thermochromic bodies become decolorized, the first reversible thermochromic body is removed from the temperature control indicator and cooled again to a temperature equal to or lower than temperature _t1 to maintain the colored state. Next, the cooling of the first reversible thermochromic body is stopped, and the first reversible thermochromic body and the second reversible thermochromic body are placed side by side again in a temperature environment within the appropriate temperature range, or the second reversible thermochromic body is layered on the first reversible thermochromic body, thereby returning the temperature control indicator to its initial state.
In addition, if the temperature control indicator is mistakenly placed in a temperature environment lower than the appropriate temperature range before use and both reversible thermochromic bodies become colored, the second reversible thermochromic body is removed from the temperature control indicator and heated again at a temperature equal to or higher than _t4 ' to maintain the decolorized state. Next, heating of the second reversible thermochromic body is stopped, and the first reversible thermochromic body and the second reversible thermochromic body are placed side by side again in a temperature environment within the appropriate temperature range, or the second reversible thermochromic body is layered on the first reversible thermochromic body, thereby returning the temperature control indicator to its initial state.
In addition, the first reversible thermochromic body may be a reversible thermochromic body provided with a thermochromic color memory material (the other thermochromic color memory material) having a complete color development temperature t ₁ ^' in the range of more than -30 ° C. and not more than 10 ° C., and the second reversible thermochromic body may be a reversible thermochromic body provided with a thermochromic color memory material (one thermochromic color memory material) having a complete decolorization temperature t ₄ in the range of -25 ° C. or more and 15 ° C. or less. In this case, the first reversible thermochromic body in the decolorized state and the second reversible thermochromic body in the colored state are arranged side by side, or the second reversible thermochromic body in the colored state is laminated on the first reversible thermochromic body in the decolorized state to form a temperature control indicator, which can be used in the same manner as described above.

The following examples are provided, but the present invention is not limited to these. Note that the parts in the examples refer to parts by weight.

Example 1
Preparation of thermochromic color-memorizing material A (thermochromic color-memorizing microcapsule pigment A) 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) were uniformly heated and dissolved in a mixture 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 stirring while heating, 2.5 parts of water-soluble aliphatic modified amine were added, and stirring was continued to prepare a microcapsule dispersion. Microcapsule pigment A was obtained from the above microcapsule dispersion by centrifugation.
Microencapsulated pigment A had an average particle diameter of 4.6 μm, a complete color development temperature t ₁ : −55° C., a color development initiation temperature t ₂ : −45° C., a decolorization initiation temperature t ₃ : −10° C., a complete decolorization temperature t ₄ : −6° C., and a ΔH of 42° C., and reversibly changed from blue to colorless with temperature change.

Preparation of thermochromic color-memorizing material B (thermochromic color-memorizing microcapsule pigment B) As the (a) component, 2 parts of 6-(N-ethyl-N-isoamylamino)-1,2-benzofluoran, as the (b) component, 5 parts of 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 10 parts of 1,1-bis(4-hydroxyphenyl)n-decane, as the (c) component, 50 parts of 4-benzyloxyphenylethyl caprate, were uniformly heated and dissolved, and then added to a mixed solution consisting of 30 parts of aromatic isocyanate prepolymer as a wall film material and 50 parts of cosolvent, and emulsified and dispersed in an 8% polyvinyl alcohol aqueous solution, and stirred while heating, and then 2.5 parts of water-soluble aliphatic modified amine were added, and further stirring was continued to prepare a microcapsule dispersion. From the above microcapsule dispersion, microcapsule pigment B was obtained by centrifugation.
Microcapsule pigment B had an average particle diameter of 2.0 μm, complete color development temperature t ₁ ': -21°C, color development onset temperature t ₂ ': -13°C, decolorization onset temperature t ₃ ': 38°C, complete decolorization temperature t ₄ ': 60°C, and ΔH: 66°C, and reversibly changed from magenta to colorless with temperature change.

Preparation of temperature control indicator (see Figure 12)
On a white polyester film having a thickness of 25 μm as a support (201), the above-mentioned microcapsule pigment A 30 parts, urethane emulsion 62 parts, thickener 2 parts, leveling agent 0.5 parts, defoamer 0.5 parts, and crosslinking agent 5 parts were uniformly dispersed to form a thermosensitive color-memorizing ink, which was printed solidly using a 120 mesh screen plate, and dried and cured to provide a first reversible thermochromic layer (202), thereby obtaining a first reversible thermochromic body (20) [first reversible thermochromic laminate (20')]. Next, the first reversible thermochromic body was cut to produce a perfect circle-shaped first reversible thermochromic body having a diameter of 5 cm, in which the reversible thermochromic layer was visible over the entire surface.
On a white polyester film having a thickness of 25 μm as a support (301), the above-mentioned microcapsule pigment B 30 parts, urethane emulsion 62 parts, thickener 2 parts, leveling agent 0.5 parts, defoamer 0.5 parts, and crosslinking agent 5 parts were uniformly dispersed, and the thermosensitive color-memorizing ink was solid-printed using a 120 mesh screen plate, and dried and cured to provide a second reversible thermochromic layer (302), thereby obtaining a second reversible thermochromic body (30) [second reversible thermochromic laminate (30')]. Next, the second reversible thermochromic body was cut to produce a second reversible thermochromic body having a diameter of 3 cm and a perfect circle in which the reversible thermochromic layer was visible over the entire surface.
The first reversible thermochromic body was cooled to -55°C or lower to maintain the colored state, and the second reversible thermochromic body was heated to 60°C or higher to maintain the decolorized state and stored. Next, the cooling of the first reversible thermochromic body and the heating of the second reversible thermochromic body were stopped, and the second reversible thermochromic body was layered on the first reversible thermochromic body in a temperature environment of -12°C to produce a temperature control indicator (10).

Temperature control during distribution and storage of fresh fish (determining whether the temperature has deviated from the appropriate range of -20°C or higher and -7°C or lower)
When the temperature control indicator was layered on a storage container for fresh fish whose appropriate temperature range was -20°C or higher and -7°C or lower in a temperature environment of -12°C, the blue color of the first reversible thermochromic material was visually recognized in a donut shape (initial state).

When the storage container was placed in a temperature environment of -6°C or higher, the thermosensitive color-memory material A provided in the first reversible thermochromic body disappeared, the temperature control indicator changed color, and a white color was visually recognized as a perfect circle due to the support of the first reversible thermochromic body and the support of the second reversible thermochromic body (state 1).
When the temperature control indicator in State 1 was placed in a temperature environment exceeding -55°C and below -21°C, the thermochromic color memory material B provided in the second reversible thermochromic body developed color, and the magenta color of the second reversible thermochromic body was visible as a perfect circle (State 2).
When the temperature control indicator in state 2 was placed in a temperature environment of -55°C or below, the thermosensitive color-changing color memory material A provided in the first reversible thermochromic body developed color, and the magenta color from the second reversible thermochromic body was visually recognized as a perfect circle, and the blue color from the first reversible thermochromic body was visually recognized as a donut shape surrounding the magenta circle (state 3).

Furthermore, when the storage container was placed in a temperature environment below -21°C, the thermosensitive color-memory material B provided in the second reversible thermochromic body developed color, causing the temperature control indicator to change color, and the magenta color caused by the second reversible thermochromic body was visually recognized as a perfect circle, while the blue color caused by the first reversible thermochromic body was visually recognized as a donut shape surrounding the magenta circle (state 3').
When the temperature control indicator in state 3' was placed in a temperature environment of -6°C or higher and less than 60°C, the thermosensitive color-memory material A provided in the first reversible thermochromic body disappeared, and the magenta color of the second reversible thermochromic body was visible in a perfect circle (state 2').
When the temperature control indicator in state 2' was placed in a temperature environment of 60°C or higher, the thermosensitive color-memory material B provided in the second reversible thermochromic body disappeared, and a white color was visually recognized as a perfect circle due to the support of the first reversible thermochromic body and the support of the second reversible thermochromic body (state 1').

When a storage container containing fresh fish is placed in a temperature environment outside the appropriate temperature range, the temperature control indicator changes color, and since it is difficult to return the temperature control indicator to its original colored state before the color change in one of the thermosensitive color-changing color-memory materials (thermosensitive color-changing color-memory material A), it is possible to irreversibly determine that the storage container has deviated from the appropriate temperature range. Here, since temperature _t3 is greater than temperature _t2 ', it is easy to determine that the storage container has deviated from the appropriate temperature range.
In addition, when the storage container was deviated from the appropriate temperature range to a higher or lower temperature environment, only the other thermochromic color memory material (thermochromic color memory material B) maintained a colored state in a specific temperature environment, so that it was possible to irreversibly determine whether the storage container had deviated from the appropriate temperature range to a higher or lower temperature environment, respectively. Here, since temperature t ₄ ' was 60°C, which was in a temperature range higher than the normal temperature range, temperature t ₁ was -55°C, which was in an ultra-low temperature range, and further, Δt ₄ (t ₄ '-t ₄ ): 66°C, Δt ₁ (t ₁ '-t ₁ ): 34°C, (t ₃ '-t ₄ ): 44°C, (t ₁ '-t ₂ ): 24°C, it was easy to determine whether the storage container had deviated from the appropriate temperature range to a higher or lower temperature environment, respectively.
Furthermore, since the difference (ΔT _MAX ) between temperature _t4 and the upper limit temperature T _MAX of the appropriate temperature range for the storage container satisfies 0<ΔT _MAX ≦1, and the difference (ΔT _min ) between temperature _t1 ' and the lower limit temperature T _min of the appropriate temperature range for the storage container satisfies 0<ΔT _min ≦1, it was possible to control the temperature of the fresh fish even more strictly.

Example 2
Preparation of temperature control indicator (see Figure 12)
On a white synthetic paper as a support (201), a thermosensitive color-changing color-memorizing ink, which is a mixture of 30 parts of the microcapsule pigment A of Example 1, 62 parts of a urethane emulsion, 2 parts of a thickener, 0.5 parts of a leveling agent, 0.5 parts of an antifoaming agent, and 5 parts of a crosslinking agent, was solid-printed using a 120-mesh screen plate, and the ink was dried and cured to provide a first reversible thermochromic layer (202), thereby obtaining a first reversible thermochromic body (20) [first reversible thermochromic laminate (20')]. Next, the first reversible thermochromic body was cut to produce a semicircular first reversible thermochromic body with a radius of 5 cm, in which the reversible thermochromic layer was visible over the entire surface.
On a white synthetic paper as a support (301), a thermosensitive color-changing color-memorizing ink, which is a mixture of 30 parts of the microcapsule pigment B of Example 1, 62 parts of a urethane emulsion, 2 parts of a thickener, 0.5 parts of a leveling agent, 0.5 parts of an antifoaming agent, and 5 parts of a crosslinking agent, was solid-printed using a 120-mesh screen plate, and the ink was dried and cured to provide a second reversible thermochromic layer (302), thereby obtaining a second reversible thermochromic body (30) [a second reversible thermochromic laminate (30')]. The second reversible thermochromic body was then cut to produce a semicircular second reversible thermochromic body with a radius of 5 cm, in which the reversible thermochromic layer was visible over the entire surface.
The first reversible thermochromic material was cooled to -55°C or lower to maintain the colored state, and the second reversible thermochromic material was heated to 60°C or higher to maintain the decolorized state and stored.

Temperature control during distribution and storage of fresh fish (determining whether the temperature has deviated from the appropriate range of -20°C or higher and -7°C or lower)
In a storage container for storing fresh fish in a temperature environment of -12°C and an appropriate temperature range of -20°C or more and -7°C or less, a first reversible thermochromic body and a second reversible thermochromic body were arranged side by side in a perfect circle having a diameter of 5 cm to form a temperature control indicator (10). A semicircular blue color due to the first reversible thermochromic body was visible on the right half of the temperature control indicator (initial state).

When the storage container was placed in a temperature environment of -6°C or higher, the thermosensitive color-memory material A provided in the first reversible thermochromic body disappeared, the temperature control indicator changed color, and a white color was visually recognized as a perfect circle due to the support of the first reversible thermochromic body and the support of the second reversible thermochromic body (state 1).
When the temperature control indicator in state 1 was placed in a temperature environment exceeding -55°C and below -21°C, the thermochromic color memory material B provided in the second reversible thermochromic body developed color, and a semicircular magenta color from the second reversible thermochromic body was visible on the left half of the temperature control indicator (state 2).
When the temperature control indicator in state 2 was placed in a temperature environment below -55°C, the thermochromic color memory material A provided in the first reversible thermochromic body developed color, and a semicircular magenta color due to the second reversible thermochromic body was visible on the left half of the temperature control indicator, and a semicircular blue color due to the first reversible thermochromic body was visible on the right half (state 3).

In addition, when the storage container was placed in a temperature environment below -21°C, the thermosensitive color-memory material B provided in the second reversible thermochromic body developed color, causing the temperature control indicator to change color, with the left half of the temperature control indicator appearing as a semicircle of magenta due to the second reversible thermochromic body, and the right half appearing as a semicircle of blue due to the first reversible thermochromic body (state 3').
When the temperature control indicator in state 3' was placed in a temperature environment of -6°C or higher and less than 60°C, the thermochromic color memory material A provided in the first reversible thermochromic body disappeared, and a semicircular magenta color caused by the second reversible thermochromic body was visible on the left half of the temperature control indicator (state 2').
When the temperature control indicator in state 2' was placed in a temperature environment of 60°C or higher, the thermosensitive color-memory material B provided in the second reversible thermochromic body disappeared, and a white color was visually recognized as a perfect circle due to the support of the first reversible thermochromic body and the support of the second reversible thermochromic body (state 1').

When a storage container containing fresh fish is placed in a temperature environment outside the appropriate temperature range, the temperature control indicator changes color, and since it is difficult to return the temperature control indicator to its original colored state before the color change in one of the thermosensitive color-changing color-memory materials (thermosensitive color-changing color-memory material A), it is possible to irreversibly determine that the storage container has deviated from the appropriate temperature range. Here, since temperature _t3 is greater than temperature _t2 ', it is easy to determine that the storage container has deviated from the appropriate temperature range.
In addition, when the storage container was deviated from the appropriate temperature range to a higher or lower temperature environment, only the other thermochromic color memory material (thermochromic color memory material B) maintained a colored state in a specific temperature environment, so that it was possible to irreversibly determine whether the storage container had deviated from the appropriate temperature range to a higher or lower temperature environment, respectively. Here, since temperature t ₄ ' was 60°C, which was in a temperature range higher than the normal temperature range, temperature t ₁ was -55°C, which was in an ultra-low temperature range, and further, Δt ₄ (t ₄ '-t ₄ ): 66°C, Δt ₁ (t ₁ '-t ₁ ): 34°C, (t ₃ '-t ₄ ): 44°C, (t ₁ '-t ₂ ): 24°C, it was easy to determine whether the storage container had deviated from the appropriate temperature range to a higher or lower temperature environment, respectively.
Furthermore, since the difference (ΔT _MAX ) between temperature _t4 and the upper limit temperature T _MAX of the appropriate temperature range for the storage container satisfies 0<ΔT _MAX ≦1, and the difference (ΔT _min ) between temperature _t1 ' and the lower limit temperature T _min of the appropriate temperature range for the storage container satisfies 0<ΔT _min ≦1, it was possible to control the temperature of the fresh fish even more strictly.

Example 3
Preparation of thermochromic color-memorizing material A (thermochromic color-memorizing microcapsule pigment A) 2.5 parts of 1,3-dimethyl-6-diethylaminofluoran as component (A), 5 parts of 2,2-bis(4-hydroxyphenyl)hexafluoropropane as component (B), 49 parts of cyclohexylmethyl caprate and 1 part of 4-benzyloxyphenylethyl palmitate as component (C) were uniformly heated and dissolved in a mixture 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 stirring while heating, 2.5 parts of water-soluble aliphatic modified amine were added, and stirring was continued to prepare a microcapsule dispersion. Microcapsule pigment A was obtained from the above microcapsule dispersion by centrifugation.
Microcapsule pigment A had an average particle diameter of 3.9 μm, a complete color development temperature t ₁ : −44° C., a color development start temperature t ₂ : −31° C., a decolorization start temperature t ₃ : −15° C., a complete decolorization temperature t ₄ : −9° C., and ΔH: 25.5° C., and reversibly changed from orange to colorless with temperature change.

Preparation of thermochromic color-memorizing material B (thermochromic color-memorizing microcapsule pigment B) A thermochromic color-memorizing composition consisting of 1 part of 3,3-bis(2-ethoxy-4-diethylaminophenyl)-4-azaphthalide as component (A), 4 parts of 2,2-bis(4-hydroxyphenyl)hexafluoropropane and 4 parts of 1,1-bis(4-hydroxyphenyl)n-decane as component (B), and 50 parts of bis(4-methoxyphenyl)methyl hexadecanoate as component (C) was uniformly heated and dissolved, and then added to a mixed solution consisting of 30 parts of aromatic isocyanate prepolymer as a wall film material and 50 parts of cosolvent, and emulsified and dispersed in an 8% polyvinyl alcohol aqueous solution. After stirring while heating, 2.5 parts of water-soluble aliphatic modified amine was added, and stirring was continued to prepare a microcapsule dispersion. From the above microcapsule dispersion, microcapsule pigment B was obtained by centrifugation.
Microcapsule pigment B had an average particle diameter of 2.0 μm, a complete color development temperature t ₁ ': -21°C, a color development initiation temperature t ₂ ': -16°C, a decolorization initiation temperature t ₃ ': 41°C, a complete decolorization temperature t ₄ ': 52°C, and ΔH: 65°C, and reversibly changed from blue-green to colorless with temperature change.

Preparation of temperature control indicator (see Figure 18)
A thermosensitive color-memorizing ink, which is a mixture of 30 parts of the microcapsule pigment A, 62 parts of a urethane emulsion, 2 parts of a thickener, 0.5 parts of a leveling agent, 0.5 parts of an antifoaming agent, and 5 parts of a crosslinking agent, was solid-printed on a white synthetic paper substrate (201) using a 120-mesh screen plate, and the ink was dried and cured to provide a first reversible thermochromic layer (202), thereby obtaining a first reversible thermochromic body (20) [first reversible thermochromic laminate (20')]. The first reversible thermochromic body was then cut to produce a square first reversible thermochromic body, 5 cm square, in which the reversible thermochromic layer was visible over the entire surface.
As a transparent support (311), a thermosensitive color-memorizing ink consisting of 30 parts of the above-mentioned microcapsule pigment B, 62 parts of a urethane emulsion, 2 parts of a thickener, 0.5 parts of a leveling agent, 0.5 parts of an antifoaming agent, and 5 parts of a crosslinking agent was solid-printed on a transparent polyester film having a thickness of 25 μm using a 120 mesh screen plate, and dried and cured to provide a second reversible thermochromic layer (302), thereby obtaining a second reversible thermochromic body (31) [a second reversible thermochromic laminate (31') having transparency] having transparency. Next, the second reversible thermochromic body was cut to produce a second reversible thermochromic body having a square shape of 5 cm square, in which the reversible thermochromic layer was visible on the entire surface.
The first reversible thermochromic body was cooled to -44°C or lower to maintain the colored state, and the second reversible thermochromic body was heated to 52°C or higher to maintain the decolored state and stored. Next, the cooling of the first reversible thermochromic body and the heating of the second reversible thermochromic body were stopped, and the second reversible thermochromic body was laminated on the first reversible thermochromic body to produce a temperature control indicator (10). However, the first reversible thermochromic body was accidentally laminated in a temperature environment of 18°C, and the first reversible thermochromic body in the colored state was decolorized. Therefore, the first reversible thermochromic body was removed from the temperature control indicator, and the temperature was cooled again to -44°C or lower to maintain the colored state and stored.
The cooling of the first reversible thermochromic body was stopped, and the second reversible thermochromic body was layered on top of the first reversible thermochromic body in a temperature environment of -18°C, and the desired temperature control indicator was produced.

Temperature control during distribution and storage of bread dough (determining whether the temperature has deviated from the appropriate range of -20°C or higher and -10°C or lower)
When the temperature control indicator was stacked on a storage container for bread dough in a temperature environment of -18°C, whose appropriate temperature range was -20°C or higher and -10°C or lower, the thermosensitive color-memory material B began to change color, and a light brown square color was visually recognized as a mixture of the orange color from the first reversible thermochromic material and the light blue-green color from the second reversible thermochromic material (initial state).

When the storage container was placed in a temperature environment of -9°C or higher, the thermosensitive color-memory material A provided in the first reversible thermochromic body and the thermosensitive color-memory material B provided in the second reversible thermochromic body lost their color, the temperature control indicator changed color, and the white color caused by the support of the first reversible thermochromic body was visually recognized in a square shape (state 1).
When the temperature control indicator in State 1 was placed in a temperature environment exceeding -44°C and below -21°C, the thermochromic color memory material B provided in the second reversible thermochromic body developed color, and a blue-green color caused by the second reversible thermochromic body was visible in a square shape (State 2).
When the temperature control indicator in State 2 was placed in a temperature environment below -44°C, the thermosensitive color-memory material A provided in the first reversible thermochromic body developed color, and a square-shaped brown (dark brown) color was visible, which was a mixture of the orange color from the first reversible thermochromic body and the blue-green color from the second reversible thermochromic body (State 3).

In addition, when the storage container was placed in a temperature environment below -21°C, the thermosensitive color-memory material B provided in the second reversible thermochromic body developed color, causing the temperature control indicator to change color, and a square-shaped brown (dark brown) color was visible, which was a mixture of the orange color of the first reversible thermochromic body and the blue-green color of the second reversible thermochromic body (state 3').
When the temperature control indicator in state 3' was placed in a temperature environment of -9°C or higher and lower than 52°C, the thermochromic color memory material A provided in the first reversible thermochromic body disappeared, and a blue-green color caused by the second reversible thermochromic body was visible in a square shape (state 2').
When the temperature control indicator in state 2' was placed in a temperature environment of 52°C or higher, the thermosensitive color-changing color memory material B provided in the second reversible thermochromic body disappeared, and the white color caused by the support of the first reversible thermochromic body was visible in a square shape (state 1').

When a storage container containing bread dough is placed in a temperature environment outside the appropriate temperature range, the temperature control indicator changes color, and it is difficult to return the temperature control indicator to its original state before the color change, in which one of the thermosensitive color-changing color-memory materials (thermosensitive color-changing color-memory material A) is in a colored state and the other thermosensitive color-changing color-memory material (thermosensitive color-changing color-memory material B) is slightly colored. Therefore, it is possible to irreversibly determine that the storage container has deviated from the appropriate temperature range. Here, since temperature _t3 is greater than temperature _t2 ', it is easy to determine that the storage container has deviated from the appropriate temperature range.
In addition, when the temperature environment deviated from the appropriate temperature range to a higher or lower temperature environment, only the other thermochromic color memory material (thermochromic color memory material B) maintained a colored state in a specific temperature environment, so that it was possible to irreversibly determine whether the storage container had deviated from the appropriate temperature range to a higher or lower temperature environment, respectively. Here, the temperature t ₄ ' was 52°C, which was in a temperature range higher than the normal temperature range, the temperature t ₁ was -44°C, which was in an ultra-low temperature range, and further, Δt ₄ (t ₄ '-t ₄ ): 61°C, Δt ₁ (t ₁ '-t ₁ ): 23°C, (t ₃ '-t ₄ ): 50°C, (t ₁ '-t ₂ ): 10°C, so that it was easy to determine whether the storage container had deviated from the appropriate temperature range to a higher or lower temperature environment, respectively.
Furthermore, since the difference (ΔT _MAX ) between temperature _t4 and the upper limit temperature T _MAX of the appropriate temperature range for the storage container satisfies 0<ΔT _MAX ≦1, and the difference (ΔT _min ) between temperature _t1 ' and the lower limit temperature T _min of the appropriate temperature range for the storage container satisfies 0<ΔT _min ≦1, the temperature of the bread dough could be controlled even more strictly.

Example 4
Preparation of temperature control indicator (see Figure 19)
As a support (211) having transparency, a thermosensitive color-memorizing ink consisting of 30 parts of microcapsule pigment B of Example 3, 62 parts of urethane emulsion, 2 parts of thickener, 0.5 parts of leveling agent, 0.5 parts of defoamer, and 5 parts of crosslinking agent uniformly dispersed on a transparent polyester film having a thickness of 25 μm was solid-printed using a 120 mesh screen plate, and the ink was dried and cured to provide a first reversible thermochromic layer (202), thereby obtaining a first reversible thermochromic body (21) having transparency [a first reversible thermochromic laminate (21') having transparency]. Next, the first reversible thermochromic body was cut to produce a rectangular first reversible thermochromic body having a size of 3 cm x 5 cm, in which the reversible thermochromic layer was visible on the entire surface.
As a transparent support (311), a thermochromic color-memorizing ink consisting of 30 parts of the microcapsule pigment A of Example 3, 62 parts of a urethane emulsion, 2 parts of a thickener, 0.5 parts of a leveling agent, 0.5 parts of an antifoaming agent, and 5 parts of a crosslinking agent was solid-printed on a transparent polyester film having a thickness of 25 μm using a 120 mesh screen plate, and dried and cured to provide a second reversible thermochromic layer (302), thereby obtaining a second reversible thermochromic body (31) [a second reversible thermochromic laminate (31') having transparency]. Next, a second adhesive layer (303) was provided on the surface of the support opposite to the surface on which the second reversible thermochromic layer was provided, and a release layer was further provided on the outer surface of the adhesive layer. Next, the second reversible thermochromic body was cut to prepare a rectangular second reversible thermochromic body of 3 cm x 5 cm, the entire surface of which was visible as a reversible thermochromic layer.
The first reversible thermochromic body was heated to 52° C. or higher to maintain the decolorized state, and the second reversible thermochromic body was cooled to −44° C. or lower to maintain the colored state and stored. Next, the heating of the first reversible thermochromic body and the cooling of the second reversible thermochromic body were stopped, and the release layer of the second reversible thermochromic body was removed and the second reversible thermochromic body was attached to the first reversible thermochromic body in a temperature environment of −15.5° C. to produce a temperature control indicator (10).

Temperature control during distribution and storage of bread dough (determining whether the temperature has deviated from the appropriate range of -20°C or higher and -10°C or lower)
When the temperature control indicator was layered on a storage container containing bread dough whose appropriate temperature range was -20°C or higher and -10°C or lower in a temperature environment of -15.5°C, the orange color of the second reversible thermochromic body was visually recognized in a rectangular shape (initial state).

When the storage container was placed in a temperature environment of -9°C or higher, the thermosensitive color-changing color-memory material A provided in the second reversible thermochromic body lost its color, the temperature control indicator changed color, and the color due to the storage container was visible (state 1).
When the temperature control indicator in State 1 was placed in a temperature environment exceeding -44°C and below -21°C, the thermochromic color memory material B provided in the first reversible thermochromic body developed color, and a rectangular bluish-green color caused by the first reversible thermochromic body was visible (State 2).
When the temperature control indicator in State 2 was placed in a temperature environment below -44°C, the thermosensitive color-memory material A provided in the second reversible thermochromic body developed color, and a rectangular brown color was visible, which was a mixture of the blue-green color from the first reversible thermochromic body and the orange color from the second reversible thermochromic body (State 3).

In addition, when the storage container was placed in a temperature environment below -21°C, the thermosensitive color-memory material B provided in the first reversible thermochromic body developed color, causing the temperature control indicator to change color, and a rectangular brown color was visually recognized as a mixture of the blue-green color of the first reversible thermochromic body and the orange color of the second reversible thermochromic body (state 3').
When the temperature control indicator in state 3' was placed in a temperature environment of -9°C or higher and lower than 52°C, the thermosensitive color-memory material A provided in the second reversible thermochromic body disappeared, and a rectangular bluish-green color caused by the first reversible thermochromic body was visible (state 2').
When the temperature control indicator in state 2' was placed in a temperature environment of 52°C or higher, the thermochromic color memory material B provided in the first reversible thermochromic body lost its color, and the color due to the storage container was visible (state 1').

When the storage container containing the bread dough is placed in a temperature environment outside the appropriate temperature range, the temperature control indicator changes color, and since it is difficult to return the temperature control indicator to its original state before the color change when one of the thermosensitive color-changing color-memory materials (thermosensitive color-changing color-memory material A) is in a colored state, it is possible to irreversibly determine that the storage container has deviated from the appropriate temperature range. Here, since temperature _t3 is higher than temperature _t2 ', it is easy to determine that the storage container has deviated from the appropriate temperature range.
In addition, when the temperature environment deviated to a higher or lower temperature environment than the appropriate temperature range, only the other thermochromic color memory material (thermochromic color memory material B) maintained a colored state in a specific temperature environment, so that it was possible to irreversibly determine whether the storage container had deviated to a higher or lower temperature environment than the appropriate temperature range. Here, the temperature t ₄ ' was 52°C, which was in a higher temperature range than the normal temperature range, the temperature t ₁ was -44°C, which was in an ultra-low temperature range, and further, Δt ₄ (t ₄ '-t ₄ ): 61°C, Δt ₁ (t ₁ '-t ₁ ): 23°C, (t ₃ '-t ₄ ): 50°C, (t ₁ '-t ₂ ): 10°C, so that it was easy to determine whether the storage container had deviated to a higher or lower temperature environment than the appropriate temperature range.
Furthermore, since the difference (ΔT _MAX ) between temperature _t4 and the upper limit temperature T _MAX of the appropriate temperature range for the storage container satisfies 0<ΔT _MAX ≦1, and the difference (ΔT _min ) between temperature _t1 ' and the lower limit temperature T _min of the appropriate temperature range for the storage container satisfies 0<ΔT _min ≦1, the temperature of the bread dough could be controlled even more strictly.

Example 5
Preparation of thermochromic color-memorizing material A (thermochromic color-memorizing microcapsule pigment A) 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) were uniformly heated and dissolved in a mixture 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 stirring while heating, 2.5 parts of water-soluble aliphatic modified amine were added, and stirring was continued to prepare a microcapsule dispersion. Microcapsule pigment A was obtained from the above microcapsule dispersion by centrifugation.
Microcapsule pigment A had an average particle diameter of 4.9 μm, a complete color development temperature t ₁ : −36° C., a color development initiation temperature t ₂ : −32° C., a decolorization initiation temperature t ₃ : 4° C., a complete decolorization temperature t ₄ : 8° C., and a ΔH of 40° C., and reversibly changed from blue to colorless with temperature change.

Preparation of thermochromic color-memorizing material B (thermochromic color-memorizing microcapsule pigment B) A thermochromic color-memorizing composition consisting of 2 parts of 6-(N-ethyl-N-isoamylamino)-1,2-benzofluoran as component (A), 5 parts of 2,2-bis(4-hydroxyphenyl)hexafluoropropane as component (B), and 50 parts of a diester of 1,4-bis(2-hydroxyethoxy)benzene and caproic acid as component (C) was uniformly heated and dissolved, and then added to a mixed solution consisting of 20 parts of aromatic isocyanate prepolymer as a wall film material and 40 parts of a cosolvent, and emulsified and dispersed in a 15% gelatin aqueous solution. After stirring while heating, 2 parts of a water-soluble aliphatic modified amine were added, and further stirring was continued to prepare a microcapsule dispersion. From the above microcapsule dispersion, microcapsule pigment B was obtained by centrifugation.
Microcapsule pigment B had an average particle diameter of 5.0 μm, a complete color development temperature t ₁ ': -3°C, a color development initiation temperature t ₂ ': 3°C, a decolorization initiation temperature t ₃ ': 58°C, a complete decolorization temperature t ₄ ': 80°C, and a ΔH of 69°C, and reversibly changed from magenta to colorless with temperature change.

Preparation of temperature control indicator (see Figure 20)
10 parts of the above microcapsule pigment A, 1 part of dispersant, and 89 parts of polypropylene homopolymer were melt-mixed at 180°C in an extruder to obtain reversible thermochromic pellets. The reversible thermochromic pellets were molded into a plate shape of 3 cm in length, 5 cm in width, and 0.5 cm in height in an injection molding machine at a cylinder temperature of 180°C to obtain a first reversible thermochromic body (21) [first reversible thermochromic molded body (21″) having transparency].
10 parts of the above microcapsule pigment B, 1 part of dispersant, and 89 parts of polypropylene homopolymer were melt-mixed at 180°C in an extruder to obtain reversible thermochromic pellets. The reversible thermochromic pellets were molded into a plate shape of 3 cm in length, 5 cm in width, and 0.5 cm in height in an injection molding machine at a cylinder temperature of 180°C to obtain a second reversible thermochromic body (31) [second reversible thermochromic molded body (31″)] having transparency.
The first reversible thermochromic body was cooled to -36°C or lower to maintain the colored state, and the second reversible thermochromic body was heated to 80°C or higher to maintain the decolorized state and stored. Next, the cooling of the first reversible thermochromic body and the heating of the second reversible thermochromic body were stopped, and the second reversible thermochromic body was layered on the first reversible thermochromic body in a temperature environment of 3.5°C to produce a temperature control indicator (10).

Temperature control during distribution and storage of vegetables (determining whether the temperature has deviated from the appropriate range of 0°C or higher and 5°C or lower)
When the temperature control indicator was stacked on a storage container containing vegetables whose appropriate temperature range was between 0°C and 5°C in a 3.5°C temperature environment, a rectangular blue color caused by the first reversible thermochromic material was visible (initial state).

When the storage container was placed in a temperature environment of 8°C or higher, the thermosensitive color-changing color-memory material A provided in the first reversible thermochromic body disappeared, the temperature control indicator changed color, and the color due to the storage container was visible (state 1).
When the temperature control indicator in State 1 was placed in a temperature environment exceeding -36°C and below -3°C, the thermochromic color memory material B provided in the second reversible thermochromic body developed color, and the magenta color of the second reversible thermochromic body was visible in a rectangular shape (State 2).
When the temperature control indicator in State 2 was placed in a temperature environment below -36°C, the thermosensitive color-memory material A provided in the first reversible thermochromic body developed color, and a rectangular purple color was visible, which was a mixture of the blue color from the first reversible thermochromic body and the magenta color from the second reversible thermochromic body (State 3).

In addition, when the storage container was placed in a temperature environment below -3°C, the thermosensitive color-memory material B provided in the second reversible thermochromic body developed color, causing the temperature control indicator to change color, and a rectangular purple color was visible, which was a mixture of the blue color from the first reversible thermochromic body and the magenta color from the second reversible thermochromic body (state 3').
When the temperature control indicator in state 3' was placed in a temperature environment of 8°C or higher and less than 80°C, the thermosensitive color-memory material A provided in the first reversible thermochromic body disappeared, and the magenta color caused by the second reversible thermochromic body was visible in a rectangular shape (state 2').
When the temperature control indicator in state 2' was placed in a temperature environment of 80°C or higher, the thermochromic color memory material B provided in the second reversible thermochromic body lost its color, and the color due to the storage container was visible (state 1').

When a storage container containing vegetables is placed in a temperature environment outside the appropriate temperature range, the temperature control indicator changes color, and since it is difficult to return the temperature control indicator to its original colored state before the color change in one of the thermosensitive color-changing color-memory materials (thermosensitive color-changing color-memory material A), it is possible to irreversibly determine that the storage container has deviated from the appropriate temperature range. Here, since temperature _t3 is greater than temperature _t2 ', it is easy to determine that the storage container has deviated from the appropriate temperature range.
In addition, when the storage container was deviated from the appropriate temperature range to a higher or lower temperature environment, only the other thermochromic color memory material (thermochromic color memory material B) maintained a colored state in a specific temperature environment, so that it was possible to irreversibly determine whether the storage container had deviated from the appropriate temperature range to a higher or lower temperature environment, respectively. Here, since temperature t ₄ ' was 80°C, which was in a temperature range higher than the normal temperature range, temperature t ₁ was -36°C, which was in an ultra-low temperature range, and further, Δt ₄ (t ₄ '-t ₄ ): 72°C, Δt ₁ (t ₁ '-t ₁ ): 33°C, (t ₃ '-t ₄ ): 50°C, (t ₁ '-t ₂ ): 29°C, it was easy to determine whether the storage container had deviated from the appropriate temperature range to a higher or lower temperature environment, respectively.
Furthermore, the difference (ΔT _MAX ) between temperature _t4 and the upper limit temperature T _MAX of the appropriate temperature range for the storage container satisfies 0 < ΔT _MAX ≦ 3, and the difference (ΔT _min ) between temperature _t1 ' and the lower limit temperature T _min of the appropriate temperature range for the storage container satisfies 0 < ΔT _min ≦ 3, so strict temperature control of the vegetables was possible.

Example 6
Preparation of thermochromic color-memorizing material A (thermochromic color-memorizing microcapsule pigment A) 1 part of 2-di-n-butylamino-8-di-n-pentylamino-4-methylspiro[5H-[1]benzopyrano[2,3-d]pyrimidine-5,1'(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) were uniformly heated and dissolved in a thermochromic color-memorizing composition, which was then poured into a mixed solution 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. The mixture was stirred while being heated, and then 2.5 parts of a water-soluble aliphatic modified amine was added, and the mixture was further stirred to prepare a microcapsule dispersion. From the above microcapsule dispersion, a microcapsule pigment A was obtained by centrifugal separation.
Microcapsule pigment A had an average particle diameter of 5.5 μm, a complete color development temperature t ₁ : −37° C., a color development initiation temperature t ₂ : −31° C., a decolorization initiation temperature t ₃ : 4° C., a complete decolorization temperature t ₄ : 9° C., and ΔH: 40.5° C., and reversibly changed from pink to colorless with temperature change.

Preparation of thermochromic color-memorizing material B (thermochromic color-memorizing microcapsule pigment B) A thermochromic color-memorizing composition consisting of 2 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 a diester of 4-phenylphenol ethylene glycol ether and lauric acid as component (C) was uniformly heated and dissolved, and then added to a mixed solution consisting of 20 parts of aromatic isocyanate prepolymer as a wall film material and 40 parts of a cosolvent, and emulsified and dispersed in a 15% gelatin aqueous solution. After stirring while heating, 2 parts of a water-soluble aliphatic modified amine were added, and further stirring was continued to prepare a microcapsule dispersion. From the above microcapsule dispersion, microcapsule pigment B was obtained by centrifugation.
Microcapsule pigment B had an average particle diameter of 2.5 μm, a complete color development temperature t ₁ ': 1°C, a color development initiation temperature t ₂ ': 6°C, a discoloration initiation temperature t ₃ ': 39°C, a complete discoloration temperature t ₄ ': 48°C, and ΔH: 40°C, and reversibly changed from blue to colorless with temperature change.

Preparation of temperature control indicator (see Figure 21)
A non-thermochromic ink consisting of 0.5 parts of a yellow 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 solid-printed on a 25 μm-thick white polyester film used as a support (201) using a 120-mesh screen, and then dried and cured to provide a non-thermochromic layer (401). Further, on the non-thermochromic layer, 30 parts of the above-mentioned microcapsule pigment B, 62 parts of urethane emulsion, 2 parts of thickener, 0.5 parts of leveling agent, 0.5 parts of defoaming agent, and 5 parts of crosslinking agent were uniformly dispersed to perform solid printing using a 120 mesh screen plate, and the ink was dried and cured to provide a first reversible thermochromic layer (202), thereby obtaining a first reversible thermochromic body (20) [first reversible thermochromic laminate (20')]. Next, a first adhesive layer (203) was provided on the surface of the support opposite to the surface on which the non-thermochromic layer and the first reversible thermochromic layer were provided, and a release layer was further provided on the outer surface of the adhesive layer. Next, the first reversible thermochromic body was cut to produce a rectangular first reversible thermochromic body of 3 cm x 5 cm in which the reversible thermochromic layer was visible on the entire surface.
As a transparent support (311), a thermosensitive color-memorizing ink was printed on a transparent polyester film having a thickness of 25 μm by uniformly dispersing 30 parts of the above-mentioned microcapsule pigment A, 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, using a 120-mesh screen plate, and the ink was dried and cured to provide a second reversible thermochromic layer (302), thereby obtaining a second reversible thermochromic body (31) [a second reversible thermochromic laminate (31') having transparency]. Next, a second adhesive layer (303) was provided on the surface of the support opposite to the surface on which the second reversible thermochromic layer was provided, and a release layer was further provided on the outer surface of the adhesive layer. Next, the second reversible thermochromic body was cut to produce a rectangular second reversible thermochromic body of 3 cm x 5 cm.
The first reversible thermochromic body was heated to 48° C. or higher to maintain the decolorized state, and the second reversible thermochromic body was cooled to −37° C. or lower to maintain the colored state and stored. Next, the heating of the first reversible thermochromic body and the cooling of the second reversible thermochromic body were stopped, and the release layer of the second reversible thermochromic body was removed in a temperature environment of 5° C., and the second reversible thermochromic body was attached to the first reversible thermochromic body to produce a temperature control indicator (10).

Temperature control during pharmaceutical distribution and storage (determining whether the temperature has deviated from the appropriate range of 2°C or higher and 8°C or lower)
When the release layer of the first reversible thermochromic material is removed and a temperature control indicator is attached to a storage container containing pharmaceuticals with an appropriate temperature range of 2°C or higher and 8°C or lower in a temperature environment of 5°C, thermochromic color memory material A begins to fade and thermochromic color memory material B begins to develop color, so that a rectangular ochre color is visible, which is a mixture of the light blue color due to the first reversible thermochromic layer of the first reversible thermochromic material, the yellow color due to the non-thermochromic layer, and the light pink color due to the second reversible thermochromic material (initial state).

When the storage container was placed in a temperature environment of 9°C or higher, the thermosensitive color-memory material A provided in the second reversible thermochromic body and the thermosensitive color-memory material B provided in the first reversible thermochromic body lost their color, the temperature control indicator changed color, and a rectangular shape of yellow color due to the non-thermochromic layer of the first reversible thermochromic body was visible (state 1).
When the temperature control indicator in State 1 was placed in a temperature environment exceeding -37°C and below 1°C, the thermosensitive color-memory material B provided in the first reversible thermochromic body developed color, and a rectangular green color was visible which was a mixture of the blue color from the first reversible thermochromic layer of the first reversible thermochromic body and the yellow color from the non-thermochromic layer (State 2).
When the temperature control indicator in State 2 was placed in a temperature environment below -37°C, the thermosensitive color-memory material A provided in the second reversible thermochromic body developed color, and a rectangular brown color was visually recognized as a mixture of the blue color from the first reversible thermochromic layer of the first reversible thermochromic body, the yellow color from the non-thermochromic layer, and the pink color from the second reversible thermochromic body (State 3).

In addition, when the storage container was placed in a temperature environment below 1°C, the thermosensitive color-memory material B provided in the first reversible thermochromic body developed color, causing the temperature control indicator to change color, and a rectangular brown color was visually recognized as a mixture of the blue color from the first reversible thermochromic layer of the first reversible thermochromic body, the yellow color from the non-thermochromic layer, and the pink color from the second reversible thermochromic body (state 3').
When the temperature control indicator in state 3' was placed in a temperature environment of 9°C or higher and lower than 48°C, the thermosensitive color-memory material A provided in the second reversible thermochromic body lost its color, and a rectangular green color was visible which was a mixture of the blue color from the first reversible thermochromic layer of the first reversible thermochromic body and the yellow color from the non-thermochromic layer (state 2').
When the temperature control indicator in state 2' was placed in a temperature environment of 48°C or higher, the thermosensitive color-memory material B provided in the first reversible thermochromic body disappeared, and the yellow color due to the non-thermochromic layer of the first reversible thermochromic body was visible in a rectangular shape (state 1').

When a storage container containing a pharmaceutical is placed in a temperature environment outside the appropriate temperature range, the temperature control indicator changes color, and thereafter, one of the thermosensitive color-changing color-memory materials (thermosensitive color-changing color-memory material A) is slightly discolored and the other thermosensitive color-changing color-memory material (thermosensitive color-changing color-memory material B) is slightly colored.Since it is difficult to return the temperature control indicator to its original state before the color change, it is possible to irreversibly determine that the storage container has deviated from the appropriate temperature range.
In addition, when the storage container was deviated from the appropriate temperature range to a higher or lower temperature environment, only the other thermochromic color memory material (thermochromic color memory material B) maintained a colored state in a specific temperature environment, so that it was possible to irreversibly determine whether the storage container had deviated from the appropriate temperature range to a higher or lower temperature environment, respectively. Here, the temperature t ₄ ' was 48°C, which was in a higher temperature range than the normal temperature range, the temperature t ₁ was -37°C, which was in an ultra-low temperature range, and further, Δt ₄ (t ₄ '-t ₄ ): 39°C, Δt ₁ (t ₁ '-t ₁ ): 38°C, (t ₃ '-t ₄ ): 30°C, (t ₁ '-t ₂ ): 32°C, so that it was easy to determine whether the storage container had deviated from the appropriate temperature range to a higher or lower temperature environment, respectively.
Furthermore, since the difference (ΔT _MAX ) between temperature _t4 and the upper limit temperature T _MAX of the appropriate temperature range for the storage container satisfies 0 < ΔT _MAX ≦ 1, and the difference (ΔT _min ) between temperature _t1 ' and the lower limit temperature T _min of the appropriate temperature range for the storage container satisfies 0 < ΔT _min ≦ 1, it was possible to perform even stricter temperature control of the pharmaceutical.

Example 7
Preparation of thermochromic color-memorizing material A (thermochromic color-memorizing microcapsule pigment A) As the (a) component, 9-ethyl-(3-methylbutyl)amino-spiro[12H-benzo[a]xanthen-12,1'(3'H)-isobenzofuran]-3'-one 3 parts, as the (b) component, 2,2-bis(4-hydroxyphenyl)hexafluoropropane 5 parts, as the (c) component, cyclohexylmethyl laurate 50 parts were uniformly heated and dissolved in a thermochromic color-memorizing composition, which was then poured into 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 were added, and further stirring was continued to prepare a microcapsule dispersion. From the above microcapsule dispersion, microcapsule pigment A was obtained by centrifugation.
Microencapsulated pigment A had an average particle diameter of 5.5 μm, a complete color development temperature t ₁ : −37° C., a color development start temperature t ₂ : −30° C., a decolorization start temperature t ₃ : 3° C., a complete decolorization temperature t ₄ : 8° C., and a ΔH of 39° C., and reversibly changed from magenta to colorless with temperature change.

Preparation of thermochromic color-memorizing material B (thermochromic color-memorizing microcapsule pigment B) As the (a) component, 4.5 parts of 2-(2-chloroanilino)-6-di-n-butylaminofluoran, as the (b) component, 5 parts of 1,1-bis(4-hydroxyphenyl)n-decane, 5 parts of 2,2-bis(4-hydroxyphenyl)hexafluoropropane, as the (c) component, 50 parts of 4-methylbenzyl palmitate, were uniformly heated and dissolved in a mixture of 35 parts of aromatic isocyanate prepolymer as a wall film material and 40 parts of cosolvent, and then emulsified and dispersed in an 8% polyvinyl alcohol aqueous solution. After stirring while heating, 2.5 parts of water-soluble aliphatic modified amine were added, and further stirring was continued to prepare a microcapsule dispersion. From the above microcapsule dispersion, microcapsule pigment B was obtained by centrifugation.
Microcapsule pigment B had an average particle diameter of 2.4 μm, a complete color development temperature t ₁ ': -3°C, a color development initiation temperature t ₂ ': 6°C, a decolorization initiation temperature t ₃ ': 37°C, a complete decolorization temperature t ₄ ': 45°C, and a ΔH of 39.5°C, and reversibly changed from black to colorless with temperature change.

Fabrication of a temperature control indicator with tamper-proof function (see FIG. 22)
As a tamper-evident member (support) (204) provided with an adhesive layer, a tamper-evident label having a thickness of 80 μm and made of a white polypropylene film [manufactured by Lintec Corporation, product name: TE80W PAT1 8K] was solid-printed on the entire surface of the tamper-evident label using a 120-mesh screen plate, on the surface opposite to the adhesive layer, with a thermosensitive color-changing color-memorizing ink obtained by uniformly dispersing 30 parts of the above-mentioned microcapsule pigment A, 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, and then dried and cured to provide a reversible thermochromic layer (202), thereby obtaining a first reversible thermochromic body (20) [first reversible thermochromic laminate (20')].
As a transparent support (311), a thermosensitive color-memorizing ink, which is a mixture of 30 parts of the microcapsule pigment B, 62 parts of a urethane emulsion, 2 parts of a thickener, 0.5 parts of a leveling agent, 0.5 parts of an antifoaming agent, and 5 parts of a crosslinking agent, was solid-printed on a transparent polyester film having a thickness of 25 μm using a 120 mesh screen plate, and the ink was dried and cured to provide a second reversible thermochromic layer (302), thereby obtaining a second reversible thermochromic body (31) [a second reversible thermochromic laminate (31') having transparency]. Next, a second adhesive layer (303) was provided on the surface of the support opposite to the surface on which the second reversible thermochromic layer was provided, and a release layer was provided on the outer surface of the adhesive layer. Next, the second reversible thermochromic body was cut to the same size as the first reversible thermochromic body to prepare a rectangular second reversible thermochromic body with a reversible thermochromic layer visible over the entire surface.
The first reversible thermochromic body was cooled to -37°C or lower to maintain the colored state, and the second reversible thermochromic body was heated to 45°C or higher to maintain the decolorized state and stored. Next, the cooling of the first reversible thermochromic body and the heating of the second reversible thermochromic body were stopped, and in a temperature environment of 2°C, the release layer of the second reversible thermochromic body was removed and the second reversible thermochromic body was attached to the first reversible thermochromic body to produce a temperature control indicator (10).

Temperature control during distribution and storage of vegetables (determining whether the temperature has deviated from the appropriate range of 0°C or higher and 5°C or lower)
When the release sheet of the anti-tampering label is removed and a temperature control indicator is attached to a storage container containing vegetables in a temperature environment of 2°C and whose appropriate temperature range is between 0°C and 5°C, the temperature-sensitive color-changing color memory material B begins to change color, and a rectangular reddish-brown color is visible, which is a mixture of the magenta color of the first reversible thermochromic material and the light black color of the second reversible thermochromic material (initial state).

When the storage container was placed in a temperature environment of 8°C or higher, the thermosensitive color-changing color memory material A provided in the first reversible thermochromic body and the thermosensitive color-memory material B provided in the second reversible thermochromic body disappeared, the temperature control indicator changed color, and the white color caused by the support was visible in a rectangular shape (state 1).
When the temperature control indicator in State 1 was placed in a temperature environment exceeding -37°C and below -3°C, the thermosensitive color-memory material B provided in the second reversible thermochromic body developed color, and the black color caused by the second reversible thermochromic body was visible in a rectangular shape (State 2).
When the temperature control indicator in State 2 was placed in a temperature environment below -37°C, the thermosensitive color-memory material A provided in the first reversible thermochromic body developed color, and a rectangular brown color was visually recognized as a mixture of the magenta color from the first reversible thermochromic body and the black color from the second reversible thermochromic body (State 3).

In addition, when the storage container was placed in a temperature environment below -3°C, the thermosensitive color-memory material B provided in the second reversible thermochromic body developed color, causing the temperature control indicator to change color, and a rectangular brown color was visually recognized as a mixture of the magenta color from the first reversible thermochromic body and the black color from the second reversible thermochromic body (state 3').
When the temperature control indicator in state 3' was placed in a temperature environment of 8°C or higher and less than 45°C, the thermosensitive color-memory material A provided in the first reversible thermochromic body disappeared, and a rectangular shape of black color was visible due to the second reversible thermochromic body (state 2').
When the temperature control indicator in state 2' was placed in a temperature environment of 45°C or higher, the thermosensitive color-changing color memory material B provided in the second reversible thermochromic body disappeared, and the white color caused by the support was visible in a rectangular shape (state 1').

When a storage container containing vegetables is placed in a temperature environment outside the appropriate temperature range, the temperature control indicator changes color, and thereafter, one of the thermosensitive color-changing color-memory materials (thermosensitive color-changing color-memory material A) is in an initial colored state while the other thermosensitive color-changing color-memory material (thermosensitive color-changing color-memory material B) is slightly colored.Since it is difficult to return the temperature control indicator to its original state before the color change, it is possible to irreversibly determine that the storage container has deviated from the appropriate temperature range.
In addition, when the storage container was deviated from the appropriate temperature range to a higher or lower temperature environment, only the other thermochromic color memory material (thermochromic color memory material B) maintained a colored state in a specific temperature environment, so that it was possible to irreversibly determine that the storage container had deviated from the appropriate temperature range to a higher or lower temperature environment, respectively. Here, the temperature t ₄ ' was 45°C, which was in a higher temperature range than the normal temperature range, the temperature t ₁ was -37°C, which was in an ultra-low temperature range, and further, Δt ₄ (t ₄ '-t ₄ ): 37°C, Δt ₁ (t ₁ '-t ₁ ): 34°C, (t ₃ '-t ₄ ): 29°C, (t ₁ '-t ₂ ): 27°C, so that it was easy to determine that the storage container had deviated from the appropriate temperature range to a higher or lower temperature environment, respectively.
Furthermore, the difference (ΔT _MAX ) between temperature _t4 and the upper limit temperature T _MAX of the appropriate temperature range for the storage container satisfies 0 < ΔT _MAX ≦ 3, and the difference (ΔT _min ) between temperature _t1 ' and the lower limit temperature T _min of the appropriate temperature range for the storage container satisfies 0 < ΔT _min ≦ 3, so strict temperature control of the vegetables was possible.
When the temperature control indicator was peeled off from the storage container in an attempt to replace the first reversible thermochromic body with a first reversible thermochromic body in a different color state so as to prevent the vegetables from leaving a history of deviation from the appropriate temperature range, the surface substrate of the tamper-proof label of the first reversible thermochromic body was destroyed and a peeled-off mark remained on the storage container. Thus, the temperature control indicator had a function of preventing tampering such as replacement or reattachment.

Application example 1
Preparation of anti-counterfeiting medium On a white polyester film as a support, 30 parts of the microcapsule pigment A of Example 1, 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 were uniformly dispersed to form a thermosensitive color-memorizing ink, which was printed solidly using a 120-mesh screen plate, and dried and cured to provide a first reversible thermochromic layer, thereby obtaining a first reversible thermochromic body (first reversible thermochromic laminate). Next, the first reversible thermochromic body was cut to produce a rectangular first reversible thermochromic body of 3 cm x 5 cm, in which the reversible thermochromic layer was visible on the entire surface.
As a support having transparency, a 25 μm thick transparent polyester film was used, and a thermosensitive color-memorizing ink was uniformly dispersed with 30 parts of microcapsule pigment B of Example 1, 62 parts of urethane emulsion, 2 parts of thickener, 0.5 parts of leveling agent, 0.5 parts of defoamer, and 5 parts of crosslinking agent. The ink was solid-printed using a 120 mesh screen plate, and dried and cured to provide a second reversible thermochromic layer, thereby obtaining a second reversible thermochromic body having transparency (a second reversible thermochromic laminate having transparency). Next, a second adhesive layer was provided on the surface of the support opposite to the surface on which the second reversible thermochromic layer was provided, and a release layer was further provided on the outer surface of the adhesive layer. Next, the second reversible thermochromic body was cut to produce a rectangular second reversible thermochromic body of 3 cm x 5 cm in which the reversible thermochromic layer was visible on the entire surface.
The first reversible thermochromic body was cooled to -55°C or lower to maintain the colored state, and the second reversible thermochromic body was heated to 60°C or higher to maintain the decolorized state and stored. Next, the cooling of the first reversible thermochromic body and the heating of the second reversible thermochromic body were stopped, and in a temperature environment of -12°C, the release layer of the second reversible thermochromic body was removed and the second reversible thermochromic body was attached to the first reversible thermochromic body to produce an anti-counterfeiting medium.

In the counterfeit prevention medium, a rectangular blue color due to the first reversible thermochromic material was visible in a temperature environment of −12° C. (initial state).
When the counterfeit prevention medium was placed in a temperature environment of -6°C or higher, the thermosensitive color-changing color memory material A provided in the first reversible thermochromic body disappeared, and the white color caused by the support of the first reversible thermochromic body was visually recognized in a rectangular shape (state 1).
When the counterfeit prevention medium in State 1 was placed in a temperature environment exceeding -55°C and below -21°C, the thermochromic color memory material B provided in the second reversible thermochromic body developed color, and the magenta color produced by the second reversible thermochromic body was visible in a rectangular shape (State 2).
Next, when placed in a temperature environment below -55°C, the thermosensitive color-memory material A provided in the first reversible thermochromic body developed color, and a rectangular purple color was visible, which was a mixture of the blue color from the first reversible thermochromic body and the magenta color from the second reversible thermochromic body (state 3).
In addition, when the anti-counterfeiting medium was placed in a temperature environment below -21°C, the thermosensitive color-memory material B provided in the second reversible thermochromic body developed color, and a rectangular purple color was visible, which was a mixture of the blue color from the first reversible thermochromic body and the magenta color from the second reversible thermochromic body (state 3').
When the counterfeit prevention medium in state 3' was placed in a temperature environment of -6°C or higher and lower than 60°C, the thermochromic color memory material A provided in the first reversible thermochromic body disappeared, and the magenta color caused by the second reversible thermochromic body was visible in a rectangular shape (state 2').
Next, when placed in a temperature environment of 60°C or higher, the thermosensitive color-changing color memory material B provided in the second reversible thermochromic body disappeared, and the white color caused by the support of the first reversible thermochromic body was visible in a rectangular shape (state 1').
Therefore, the above-mentioned anti-counterfeiting medium changes color when it deviates from a specific temperature range (a temperature environment above -21°C and below -6°C), and thereafter, it has an anti-counterfeiting function because it is difficult to return the anti-counterfeiting medium to its original pre-discoloration state in which one of the thermochromic color-memory materials (thermochromic color-memory material A) is in a colored state.

_t1 Complete color development temperature of the thermochromic color memory material in the colored state _t2 Color development start temperature of the thermochromic color memory material in the colored state _t3 Color loss start temperature of the thermochromic color memory material in the colored state _t4 Complete loss temperature of the thermochromic color memory material in the colored state _t1 ' Complete color development temperature of the thermochromic color memory material in the loss state _t2 ' Color development start temperature of the thermochromic color memory material in the loss state _t3 ' Color loss start temperature of the thermochromic color memory material in the loss state _t4 ' Complete loss temperature of the thermochromic color memory material in the loss state ΔH Hysteresis width 10 Temperature management indicator 20 First reversible thermochromic body 20' First reversible thermochromic laminate 20'' First reversible thermochromic molded body 201 Support 202 First reversible thermochromic layer 203 First adhesive layer 204 Tamper-proof member provided with adhesive layer 21 First reversible thermochromic body having transparency 21' First reversible thermochromic laminate having transparency 21" Second reversible thermochromic molded body having transparency 211 Support having transparency 30 Second reversible thermochromic body 30' Second reversible thermochromic laminate 30" Second reversible thermochromic molded body 301 Support 302 Second reversible thermochromic layer 303 Second adhesive layer 31 Second reversible thermochromic body having transparency 31' Second reversible thermochromic laminate having transparency 31" Second reversible thermochromic molded body having transparency 311 Support having transparency 314 Transparent tamper-proof member provided with adhesive layer 401 Non-thermochromic layer

Claims (13)

A temperature control indicator comprising a first reversible thermochromic body having a thermochromic color memory material and a second reversible thermochromic body having a thermochromic color memory material, the thermochromic color memory material being a thermochromic color memory microcapsule pigment encapsulating a thermochromic color memory composition comprising at least (a) an electron donating organic compound, (b) an electron accepting compound, and (c) a reaction medium for controlling the color reaction of the components (a) and (b), or a thermochromic color memory resin particle having the thermochromic color memory composition dispersed in a thermoplastic resin or a thermosetting resin, the thermochromic color memory material exhibiting a hysteresis characteristic in a color density-temperature curve and exhibiting alternation between a colored state and a decolored state, and in the process of increasing temperature from the colored state, decoloration begins when a decolorization initiation temperature _t3 is reached, and continues until a complete decolorization temperature t4, which is higher than the temperature _t3, is reached. The thermosensitive color- _memory material is in a completely decolorized state in a temperature range of _t4 or more, and in the process of decreasing temperature from the decolorized state, when the color development start temperature _t2 is reached, color development begins, and in a temperature range of t1 or less that is lower than _t2 , the thermosensitive color-memory material is in a completely colored state, exhibiting a hysteresis characteristic, and discoloration occurs with a hysteresis width (ΔH) of 8 to 100°C in terms of the color density-temperature curve, and one side of the thermosensitive color-memory material is in a colored state, and the other side is in a decolorized state, the completely decolorized temperature _t4 of the thermosensitive color-memory material in the decolorized state is higher than the completely decolorized temperature _t4 of the thermosensitive color-memory material in the colored state, and the completely colored temperature _t1 of the thermosensitive color-memory material in the decolorized state is higher than the completely colored temperature t2 of the thermosensitive color-memory material in the colored state. ₁ , the thermochromic color-memory material in the colored state has a component (c) which is a compound represented by the following formula (C), and has a complete discoloration temperature _t4 in the range of -25°C or more and 15°C or less, and the thermochromic color-memory material in the discolored state has a complete discoloration temperature _t1 in the range of more than -30°C and 10°C or less.

[wherein R ₁ represents a group represented by the following formula (*) or a cycloalkyl group, and R ₂ represents a linear or branched alkyl group having 1 to 13 carbon atoms]

(wherein X represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms). 2. The temperature control indicator according to claim 1, wherein _R1 is a group in which X is a hydrogen atom or a methyl group, or a cyclohexyl group. 3. The temperature control indicator according to claim 1, wherein _R2 is a linear or branched alkyl group having 3 to 11 carbon atoms. 4. The temperature management indicator according to claim 1, wherein the complete color development temperature _t1 of the thermochromic color memory material in the colored state is −30° C. or lower. 5. The temperature management indicator according to claim 1, wherein the thermochromic color-memory material in the decolorized state has a complete decolorization temperature _t4 of 40[deg.] C. or higher. The temperature control indicator according to any one of claims 1 to 5, wherein the thermosensitive color-memory materials provided in the first reversible thermochromic body and the second reversible thermochromic body exhibit different colors in the colored state. The temperature control indicator according to any one of claims 1 to 6, comprising the first reversible thermochromic body and the second reversible thermochromic body arranged in parallel. The temperature control indicator according to any one of claims 1 to 6, which is formed by laminating the second reversible thermochromic body on the first reversible thermochromic body. The temperature control indicator according to claim 8, wherein the second reversible thermochromic body has transparency. The temperature management indicator according to any one of claims 1 to 9, wherein at least one of the first reversible thermochromic body and the second reversible thermochromic body is a reversible thermochromic laminate comprising a support and a reversible thermochromic layer containing a thermosensitive color-memorizing material. The temperature control indicator according to any one of claims 1 to 10, in which an adhesive layer is provided on the surface of the reversible thermochromic body that comes into contact with the object. The temperature control indicator according to claim 10, wherein the support is a tamper-proof member having an adhesive layer that makes it possible to tell when the support has been peeled off after being attached to an object. A method of using a temperature control indicator, comprising attaching the temperature control indicator according to any one of claims 1 to 12 to an object.

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