JP2023049995A - Temperature management indicator and method for using the same - Google Patents

Abstract

To provide a temperature management indicator with which, when circulating and preserving articles such as fresh food, frozen food, medicine, etc. having a narrow appropriate temperature range in a low temperature region, it is possible to irreversibly discriminate, by a color change of a thermochromic color memory material, whether or not these articles are kept in storage without ever once deviating from the appropriate temperature range.SOLUTION: Provided is a temperature management indicator (10) comprising a first reversible thermal discoloration substance (20) that includes a thermochromic color memory material, and a second reversible thermal discoloration substance (30) that includes a thermochromic color memory material, the thermochromic color memory materials being discolored exhibiting a 8-100°C hysteresis width. One of the thermochromic color memory materials is in a color-developing state, with ( ) component being a specific compound, and a complete decolorization temperature t4 being in the range from -25°C to 15°C, and the other of the thermochromic color memory materials is in a color-extinguishing state, with a complete decolorization temperature t1 being in the range from over -30°C to 10°C.SELECTED DRAWING: Figure 5

Description

The present invention relates to temperature management indicators and methods of use thereof. More specifically, the present invention relates to a temperature control indicator capable of temperature control of articles, etc. that need to be stored within an appropriate temperature range by means of a color change of a thermochromic color-memory material, and a method of using the same.

Conventionally, an anti-counterfeiting medium has been disclosed in which counterfeiting can be determined by a reversible thermochromic layer changing color due to temperature rise or temperature drop (see, for example, Patent Document 1).
The anti-counterfeiting medium is provided with a reversible thermochromic layer containing each thermochromic color-memory composition, one of which is in a colored state and the other in a colorless state, and which exhibits a large hysteresis characteristic. When it decreases, both of the thermochromic color-memory compositions become colorless or colored, and it becomes difficult to return one of the thermochromic color-memory compositions to the state before discoloration, which is colored. It has a function as a temperature control indicator that can irreversibly determine whether or not the temperature range is exceeded.

In recent years, it has become possible to maintain the proper temperature range for products such as fresh food, frozen food, and pharmaceuticals that have a low proper temperature range during the distribution process of production, transportation, and consumption, and distribute them over a wide area without degrading the quality of the product. A so-called cold chain, a distribution method that enables In the cold chain, it is necessary to manage the temperature so that it can be reliably determined whether or not the product has been kept in a temperature environment outside the appropriate temperature range during the distribution process. By using a material that changes color when out of range, it is possible to easily detect that the article has deviated from the appropriate temperature range. The above anti-counterfeit medium has a function as a temperature control indicator that can irreversibly determine whether or not an article has deviated from the normal temperature range by means of a thermochromic color-memory material. Furthermore, when used for articles with a narrow appropriate temperature range, it is difficult for the thermochromic color-memorizing material to selectively store and retain colors, and the temperature exceeds the appropriate temperature range. It has been difficult to irreversibly determine whether or not it has deviated from the environment.

JP 2017-170664 A

The present invention has an appropriate temperature range in a low temperature range, and an article such as fresh food, frozen food, pharmaceuticals, etc., which has a narrow appropriate temperature range, or a storage container thereof, does not deviate from the appropriate temperature range even once during distribution and storage. To provide a temperature control indicator capable of irreversibly distinguishing whether or not a thermochromic color-memorizing material has been stored without irreversible damage by means of a color change of a thermochromic color-memory material, and to provide a method for using the same.

〔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 is a temperature control indicator comprising a first reversible thermochromic body comprising a thermochromic color-memory material and a second reversible thermochromic body comprising a thermochromic color-memory material. The thermochromic color-memory material comprises (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) the components (a) and (b). A thermochromic color-memory microcapsule pigment encapsulating a thermochromic color-memory composition comprising at least a reaction medium that controls the color reaction of the thermochromic color-memory composition, or heat the thermochromic color-memory composition It is a thermochromic color-memory resin particle dispersed in a plastic resin or thermosetting resin, exhibits hysteresis characteristics with respect to the color density-temperature curve, exhibits tautomorphism between the coloring state and the decoloring state, and changes from the coloring state. In the process of increasing the temperature, decoloring begins when the decoloring start temperature _t3 is reached, and in the temperature range of the complete decoloring temperature _t4 or higher, which is higher than the temperature _t3 , the color is completely decolored. In the descending process, it begins to develop color when it reaches the color development start temperature _t2 , and shows hysteresis characteristics in which the color is completely developed in the temperature range below the complete color development temperature _t1 , which is lower than the temperature _t2 . Regarding the color density-temperature curve, One of the thermochromic color-memory materials exhibits a hysteresis width (ΔH) of 8 to 100° C. and changes color, and one of the thermochromic color-memory materials is in a colored state and the other is in a bleached state, and the thermochromic color in the bleached state The complete discoloration temperature _t4 of the memory material is higher than the complete discoloration temperature _t4 of the thermochromic color-memory material in the color-developed state, and the complete color-development temperature t of the thermochromic color-memory material in the decolorized state. ₁ is higher than the complete coloring temperature _t1 of the thermochromic color-memory material in the coloring state, and in the thermochromic color-memory material in the coloring state, the component (C) is represented by the following formula (C). a compound having a complete decoloring temperature t ₄ in the range of −25° C. or more and 15° C. or less, and the decolorized thermochromic color-memory material having a complete color development temperature t ₁ exceeding −30° C. , 10°C or less.

[In the formula, 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)
Furthermore, R ₁ is a group in which X is a hydrogen atom or a methyl group, or a cyclohexyl group, R ₂ is a linear or branched alkyl group having 3 to 11 carbon atoms, The complete color development temperature t ₁ of the thermochromic color-memory material in the colored state is −30° C. or lower, and the complete color-erasing temperature t ₄ of the thermochromic color-memory material in the decolored state is 40° C. or higher. is required to be
Further, the thermochromic color-memory materials provided in the first reversible thermochromic body and the second reversible thermochromic body exhibit different colors in a developed state, and the first reversible thermochromic material a body and a second reversible thermochromic body arranged side by side; laminating the second reversible thermochromic body on the first reversible thermochromic body; and the second reversible thermochromic body has transparency, and at least one of the first reversible thermochromic material and the second reversible thermochromic material contains a thermochromic color-memory material on a support. It is a reversible thermochromic laminate provided with a color-changing layer, an adhesive layer is provided on the surface of the reversible thermochromic body in contact with an object, and the support is peeled off after being attached to the object. It is required to be a tamper-proof member provided with an adhesive layer that can be discerned when it has been peeled off.
Furthermore, a method of using a temperature control indicator is required, which is characterized by using the temperature control indicator provided on an object.

The present invention has an appropriate temperature range in a low temperature range, and an article such as fresh food, frozen food, pharmaceuticals, etc., which has a narrow appropriate temperature range, or a storage container thereof, does not deviate from the appropriate temperature range even once during distribution and storage. A temperature control indicator with irreversibility that can detect whether or not the material has been stored without temperature change by the color change of the thermochromic color-memory material, and once it deviates from the appropriate temperature range, it is difficult to return to the original color. and how to use it.

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

The "low temperature range" in the present invention is a temperature range that includes the appropriate temperature range for articles such as fresh food, frozen food, and pharmaceuticals to which the cold chain is applied, and is commonly used in everyday living environments such as refrigerators and freezers. It represents the temperature range that can be reached by the cooling equipment used in , specifically the temperature range above -30°C and below 10°C.
In addition, the "ultra-low temperature range" is a temperature range lower than the low temperature range, and is a temperature range that is difficult to reach with cooling tools commonly used in everyday living environments, specifically -30 ° C. or less. represents a range.

The hysteresis characteristic in the color density-temperature curve of the thermochromic color-memory composition (reversible thermochromic composition having color memory) applied to the present invention will be described below.
In FIG. 1, the vertical axis represents color density, and the horizontal axis represents temperature. Changes in color density due to temperature changes progress along the arrows. Here, A is the point indicating the density at the temperature t ₄ (hereinafter referred to as the completely decolored state) at which the completely decolored state is reached, and B is the temperature t ₃ (hereinafter referred to as the decolored state start temperature C is the point indicating the density at the temperature t ₂ at which the completely decolored state can be maintained (hereinafter referred to as the color development start temperature), and D is the temperature t ₁ at which the completely colored state is reached. (hereinafter referred to as the complete coloring temperature).
The color change temperature range is a temperature range between the complete color development temperature _t1 and the complete color disappearance temperature _t4 , where either the color developed state or the color erased state can be maintained, and the color development start temperature is an area where the difference in color density is large. The temperature range between _t2 and the discoloration start temperature _t3 is the substantial discoloration temperature range.
Specifically, by cooling the thermochromic color-memory composition in a decolored state to a temperature not higher than the color development initiation temperature _t2 , the change to the color development state can be initiated, and the complete color development temperature t By cooling to a temperature of ₁ or less, a completely colored state can be obtained, and that state can be maintained unless the temperature of the thermochromic color-memory composition is raised to the color disappearance start temperature _t3 . .
Further, by applying heat to the thermochromic color-memory composition in a colored state and heating it to a temperature equal to or higher than the decoloring start temperature _t3 , the change to the decolored state can be started, and the composition can be completely decolored. A completely decolored state can be obtained by heating to a temperature of _t4 or higher, and this state can be maintained unless the temperature of the thermochromic color-memory composition is lowered to the color development start temperature _t2 . can be done.
Further, the length of the line segment EF is a measure of the color change contrast, and the length of the line segment HG passing through the midpoint of the line segment EF indicates the degree of hysteresis. ], and the larger ΔH is, the easier it is to maintain each state before and after discoloration. ΔH that can maintain each state before and after discoloration is 8°C or more, specifically in the range of 8 to 100°C. ΔH is preferably 20 to 100° C., more preferably 30 to 100° C., since each state before and after discoloration can be more easily maintained. Here, Δt, which is the difference between the complete discoloration temperature _t4 and the discoloration start temperature _t3 , or the difference between the color development start temperature _t2 and the complete color development temperature _t1 , is a scale indicating the sensitivity of discoloration, and Δt= A range of 1 to 20°C is practical, and Δt is preferably 1 to 15°C, more preferably 1 to 10°C.
In the present invention, the thermochromic color-memory material uses a thermochromic color-memory composition, and the hysteresis characteristic in the color density-temperature curve of the thermochromic color-memory material It is the same as the hysteresis characteristic in the color density-temperature curve of the thermochromic color-memory composition.

The components (a), (b) and (c) of the thermochromic color-memory composition to be applied to the present invention are specifically described below.

Component (a), that is, an electron-donating color-developing organic compound is a component that determines color, and is a compound that provides electrons to component (b), which is a color developer, to develop color.
Electron-donating color-developing organic compounds include phthalide compounds, fluoran compounds, stilinoquinoline compounds, diazarhodamine lactone compounds, pyridine compounds, quinazoline compounds, and bisquinazoline compounds. preferable.
Examples of phthalide compounds include diphenylmethanephthalide compounds, phenylindolylphthalide compounds, indolylphthalide compounds, diphenylmethaneazaphthalide compounds, phenylindolylazaphthalide compounds, and derivatives thereof. Phenylindolylazaphthalide compounds and derivatives thereof are preferred.
Moreover, the fluoran compounds include aminofluoran compounds, alkoxyfluoran compounds, derivatives thereof, and the like.

Examples of electron-donating color-forming organic compounds 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)fluorane,
3,6-bis(N-phenyl-Np-tolylamino)fluorane,
3,6-dimethoxyfluorane,
3,6-di-n-butoxyfluorane,
2-methyl-6-(N-ethyl-Np-tolylamino)fluorane,
3-chloro-6-cyclohexylaminofluorane,
2-methyl-6-cyclohexylaminofluorane,
2-chloroamino-6-di-n-butylaminofluorane,
2-(2-chloroanilino)-6-di-n-butylaminofluorane,
2-(3-trifluoromethylanilino)-6-diethylaminofluorane,
2-(3-trifluoromethylanilino)-6-di-n-pentylaminofluorane,
2-dibenzylamino-6-diethylaminofluorane,
2-(N-methylanilino)-6-(N-ethyl-Np-tolylamino)fluorane,
1,3-dimethyl-6-diethylaminofluorane,
2-chloro-3-methyl-6-diethylaminofluorane,
2-anilino-3-methyl-6-diethylaminofluorane,
2-anilino-3-methoxy-6-diethylaminofluorane,
2-anilino-3-methyl-6-di-n-butylaminofluorane,
2-anilino-3-methoxy-6-di-n-butylaminofluorane,
2-xylidino-3-methyl-6-diethylaminofluorane,
2-anilino-3-methyl-6-(N-ethyl-Np-tolylamino)fluorane,
6-diethylamino-1,2-benzofluorane,
6-(N-ethyl-N-isobutylamino)-1,2-benzofluorane,
6-(N-ethyl-N-isoamylamino)-1,2-benzofluorane,
2-(3-methoxy-4-dodecoxystyryl)quinoline,
2-diethylamino-8-diethylamino-4-methylspiro[5H-[1]benzopyrano[2,3-d]pyrimidine-5,1′(3′H)-isobenzofuran]-3′-one,
2-di-n-butylamino-8-di-n-butylamino-4-methylspiro[5H-[1]benzopyrano[2,3-d]pyrimidine-5,1′(3′H)-isobenzofuran] -3′-on,
2-di-n-butylamino-8-diethylamino-4-methylspiro[5H-[1]benzopyrano[2,3-d]pyrimidine-5,1′(3′H)-isobenzofuran]-3′-one ,
2-di-n-butylamino-8-(N-ethyl-N-isoamylamino)-4-methylspiro[5H-[1]benzopyrano[2,3-d]pyrimidine-5,1′(3′H) -isobenzofuran]-3'-one,
2-di-n-butylamino-8-di-n-pentylamino-4-methylspiro[5H-[1]benzopyrano[2,3-d]pyrimidine-5,1′(3′H)-isobenzofuran] -3′-on,
9-ethyl-(3-methylbutyl)amino-spiro[12H-benzo[a]xanthene-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)-iso benzofuranone,
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)-isobenzo Furanones,
4,5,6,7-tetrachloro-3-(4-diethylamino-2-methylphenyl)-3-(1-ethyl-2-methylindol-3-yl)-1(3H)-isobenzofuranone,
3′,6′-bis[phenyl(2-methylphenyl)amino]spiro[isobenzofuran-1(3H),9′-[9H]xanthen]-3-one,
3′,6′-bis[phenyl(3-methylphenyl)amino]spiro[isobenzofuran-1(3H),9′-[9H]xanthen]-3-one,
3′,6′-bis[phenyl(3-ethylphenyl)amino]spiro[isobenzofuran-1(3H),9′-[9H]xanthen]-3-one,
2,6-bis(2'-ethyloxyphenyl)-4-(4'-dimethylaminophenyl)pyridine,
2,6-bis(2′,4′-diethyloxyphenyl)-4-(4′-dimethylaminophenyl)pyridine,
2-(4′-dimethylaminophenyl)-4-methoxyquinazoline,
4,4'-ethylenedioxy-bis[2-(4-diethylaminophenyl)quinazoline]
etc. can be exemplified.
As the fluoranes, in addition to compounds having a substituent on the phenyl group forming the xanthene ring, a substituent on the phenyl group forming the xanthene ring and a substituent on the phenyl group forming the lactone ring (for example, , an alkyl group such as a methyl group, a halogen atom such as a chlorine atom, etc.) and exhibiting a blue or black color.

Component (b), that is, an electron-accepting compound, is a compound that receives electrons from component (a) and functions as a color developer for component (a).
Examples of electron-accepting compounds include a group of compounds having an active proton and a group of pseudo-acidic compounds [a group of compounds that are not acids but that act as acids in the thermochromic color-memory composition to develop the color of the component (a)]. , and compounds selected from the group of compounds having electron vacancies. Among the components (b) above, compounds selected from the group of compounds having an active proton are preferred.

Compounds having an active proton include compounds having a phenolic hydroxyl group and its derivatives, carboxylic acids and their derivatives, acidic phosphoric acid esters and their derivatives, azole compounds and their derivatives, 1,2,3-triazoles and derivatives thereof, cyclic carbosulfimides, halohydrins having 2 to 5 carbon atoms, sulfonic acid and its derivatives, inorganic acids and the like. As the carboxylic acid and its derivative, an aromatic carboxylic acid and its derivative, or an aliphatic carboxylic acid having 2 to 5 carbon atoms and its derivative are preferable.
Pseudo-acidic compounds include metal salts of compounds having a phenolic hydroxyl group, metal salts of carboxylic acids, metal salts of acidic phosphoric acid esters, metal salts of sulfonic acids, aromatic carboxylic acid anhydrides, and aliphatic carboxylic acid anhydrides. , mixed anhydrides of aromatic carboxylic acids and sulfonic acids, cycloolefin dicarboxylic anhydrides, urea and its derivatives, thiourea and its derivatives, guanidine and its derivatives, and halogenated alcohols.
Examples of compounds having electron vacancies include borates, borate esters, and inorganic salts.

Among the above components (b), a compound having a phenolic hydroxyl group is preferred because it can more effectively exhibit thermochromic properties.
Compounds having a phenolic hydroxyl group include a wide range of compounds from monophenol compounds to polyphenol compounds, and further include bisphenol compounds, trisphenol compounds, phenol-aldehyde condensed resins, and the like. A compound having a phenolic hydroxyl group preferably has at least two benzene rings. Moreover, the compound having a phenolic hydroxyl group may have a substituent such as an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, a carboxyl group and its ester or amide group, and 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. etc. can be exemplified.

The compounds of component (b) are exemplified below.
Examples of compounds having one phenolic hydroxyl group include
phenol,
o-cresol,
m-cresol,
p-cresol,
4-ethylphenol,
4-n-propylphenol,
4-n-butylphenol,
2-tert-butylphenol,
3-tert-butylphenol,
4-tert-butylphenol,
4-n-pentylphenol,
4-tert-pentylphenol,
4-n-octylphenol,
4-tert-octylphenol,
4-n-nonylphenol,
4-n-dodecylphenol,
3-n-pentadecylphenol,
4-n-stearylphenol,
1-(4-hydroxyphenyl)decan-1-one,
4-chlorophenol,
4-bromophenol,
4-trifluoromethylphenol,
4-methylthiophenol,
4-nitrophenol,
2-phenylphenol,
4-phenylphenol,
2-benzylphenol,
2-benzyl-4-chlorophenol,
4-cumylphenol,
4-hydroxybenzophenone,
4-chloro-4'-hydroxybenzophenone,
4-fluoro-4'-hydroxybenzophenone,
4-cyclohexylphenol,
2-hydroxybenzyl alcohol,
3-hydroxybenzyl alcohol,
4-hydroxybenzyl alcohol,
4-(2-hydroxyethyl)phenol,
3-methoxyphenol,
4-ethoxyphenol,
4-n-propoxyphenol,
4-n-butoxyphenol,
4-n-heptyloxyphenol,
4-(2-methoxyethyl)phenol,
α-naphthol,
β-naphthol,
2,3-dimethylphenol,
2,4-dimethylphenol,
2,6-dimethylphenol,
2,6-di-tert-butylphenol,
2,4-dichlorophenol,
2,4-difluorophenol,
thymol,
3-methyl-4-methylthiophenol,
2-tert-butyl-5-methylphenol,
2,6-bis(hydroxymethyl)-4-methylphenol,
2,3,5-trimethylphenol,
2,6-bis(hydroxymethyl)-4-tert-octylphenol,
6-hydroxy-1,3-benzoxathiol-2-one,
2,4-bis(phenylsulfonyl)phenol,
2,4-bis(phenylsulfonyl)-5-methylphenol,
2,4-bis(4-methylphenylsulfonyl)phenol,
2-phenylphenol,
4-phenylphenol,
2,6-diphenylphenol,
3-benzylbiphenyl-2-ol,
3,5-dibenzylbiphenyl-4-ol,
4-cyano-4'-hydroxybiphenyl,
1-hydroxybenzotriazole,
1-hydroxy-5-methylbenzotriazole,
1-hydroxy-5-chlorobenzotriazole,
1-hydroxy-5-methoxybenzotriazole,
1-hydroxy-4-benzoylaminobenzotriazole,
1-hydroxy-4,5,6,7-tetrachlorobenzotriazole,
1,4-hydroxybenzotriazole,
1-hydroxy-5-nitrobenzotriazole,
1-hydroxy-5-phenylbenzotriazole,
1-hydroxy-5-benzylbenzotriazole,
1-hydroxy-5-ethylbenzotriazole,
1-hydroxy-5-n-octylbenzotriazole,
1-hydroxy-5-n-butylbenzotriazole,
n-butyl 4-hydroxybenzoate,
n-octyl 4-hydroxybenzoate,
4-hydroxybenzoic acid 2-heptadecafluorooctylethane,
benzyl 4-hydroxybenzoate,
4-hydroxybenzoic acid benzyl ester,
o-methylbenzyl 4-hydroxybenzoate,
m-methylbenzyl 4-hydroxybenzoate,
p-methylbenzyl 4-hydroxybenzoate,
p-ethylbenzyl 4-hydroxybenzoate,
4-hydroxybenzoate-p-propylbenzyl,
4-hydroxybenzoate-p-tert-butylbenzyl,
phenylethyl 4-hydroxybenzoate,
4-hydroxybenzoate-o-methylphenylethyl,
4-hydroxybenzoate-m-methylphenylethyl,
p-methylphenylethyl 4-hydroxybenzoate,
4-hydroxybenzoate-p-ethylphenylethyl,
4-hydroxybenzoate-p-propylphenylethyl,
4-Hydroxybenzoic acid-p-tert-butylphenylethyl and the like can be exemplified.

Examples of compounds having two phenolic hydroxyl groups include
Resorcinol,
2-methylresorcin,
4-n-hexylresorcin,
4-n-octylresorcin,
4-tert-octylresorcin,
4-benzoylresorcin,
4-nitroresorcin,
β-methyl resorcinate,
β-benzyl resorcinate,
2-chloro-4-pentanoylresorcin,
6-chloro-4-pentanoylresorcin,
2-chloro-4-hexanoylresorcin,
6-chloro-4-hexanoylresorcin,
2-chloro-4-propanoylresorcin,
6-chloro-4-propanoylresorcin,
2,6-dichloro-4-propanoylresorcin,
6-fluoro-4-propanoylresorcin,
2-chloro-4-phenylacetylresorcinol,
6-chloro-4-phenylacetylresorcin,
2-chloro-4-β-phenylpropanoylresorcin,
6-chloro-4-β-phenylpropanoylresorcin,
2-chloro-4-phenoxyacetylresorcin,
6-chloro-4-phenoxyacetylresorcin,
4-benzoyl-2-chlororesorcin,
6-chloro-4-m-methylbenzoylresorcin,
4-[1′,3′,4′,9′a-tetrahydro-6′-hydroxyspiro(cyclohexane-1,9′-[9H]-xanthene)-4′a-[2H]-yl]-1 , 3-benzenediol,
hydroquinone,
methyl hydroquinone,
trimethylhydroquinone,
catechol,
4-tert-butyl catechol,
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.

Furthermore, as a bisphenol compound, for example,
1,1-bis(4-hydroxyphenyl)ethane,
1,1-bis(4-hydroxyphenyl)propane,
1,1-bis(4-hydroxyphenyl)n-butane,
1,1-bis(4-hydroxyphenyl)n-pentane,
1,1-bis(4-hydroxyphenyl)n-hexane,
1,1-bis(4-hydroxyphenyl)n-heptane,
1,1-bis(4-hydroxyphenyl)n-octane,
1,1-bis(4-hydroxyphenyl)n-nonane,
1,1-bis(4-hydroxyphenyl)n-decane,
1,1-bis(4-hydroxy-3-methylphenyl)decane,
1,1-bis(4-hydroxyphenyl)n-dodecane,
1,1-bis(4-hydroxyphenyl)-2-methylpropane,
1,1-bis(4-hydroxyphenyl)-3-methylbutane,
1,1-bis(4-hydroxyphenyl)-3-methylpentane,
1,1-bis(4-hydroxyphenyl)-2,3-dimethylpentane,
1,1-bis(4-hydroxyphenyl)-2-ethylbutane,
1,1-bis(4-hydroxyphenyl)-2-ethylhexane,
1,1-bis(4-hydroxyphenyl)-3,7-dimethyloctane,
1,1-bis(4-hydroxyphenyl)cyclohexane,
1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane,
1,1-bis(4-hydroxy-3-methyl)cyclohexane,
diphenolic acid,
1-phenyl-1,1-bis(4-hydroxyphenyl)methane,
2,2-bis(4-hydroxyphenyl)propane,
2,2-bis(4-hydroxyphenyl)n-butane,
2,2-bis(4-hydroxyphenyl)n-pentane,
2,2-bis(4-hydroxyphenyl)n-hexane,
2,2-bis(4-hydroxyphenyl)n-heptane,
2,2-bis(4-hydroxyphenyl)n-octane,
2,2-bis(4-hydroxyphenyl)n-nonane,
2,2-bis(4-hydroxyphenyl)n-decane,
2,2-bis(4-hydroxyphenyl)n-dodecane,
2,2-bis(4-hydroxyphenyl)-6,10,14-trimethylpentadecane,
1-phenyl-1,1-bis(4-hydroxyphenyl)ethane,
2,2-bis(4-hydroxyphenyl)methylpropionate,
2,2-bis(4-hydroxyphenyl)butyl propionate,
2,2-bis(4-hydroxy-3-methylphenyl)methylpropionate,
2,2-bis(4-hydroxyphenyl)ethyl propionate,
2,2-bis(4-hydroxyphenyl)-4-methylpentane,
2,2-bis(4-hydroxyphenyl)-4-methylhexane,
2,2-bis(4-hydroxyphenyl)hexafluoropropane,
2,2-bis(3,5-dihydroxymethyl-4-hydroxyphenyl)hexafluoropropane,
2,2-bis(4-hydroxy-3-methylphenyl)propane,
2,2-bis(4-hydroxy-3-methylphenyl)butane,
2,2-bis(4-hydroxy-3-isopropylphenyl)propane,
2,2-bis(3-sec-butylphenyl-4-hydroxy)propane,
2,2-bis(4-hydroxy-3-phenylphenyl)propane,
2,2-bis(3-tert-butyl-4-hydroxyphenyl)propane,
2,2-bis(3-fluoro-4-hydroxyphenyl)propane,
2,2-bis(3,5-dihydroxymethyl-4-hydroxyphenyl)propane,
9,9-bis(4-hydroxy-3-methylphenyl)fluorene,
1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene,
1,4-bis[2-(4-hydroxyphenyl)-2-propyl]benzene,
3,3-bis(4-hydroxyphenyl)oxindole,
3,3-bis(4-hydroxy-3-methylphenyl)oxindole,
bis(2-hydroxyphenyl)methane,
bis(2-hydroxy-5-methylphenyl)methane,
bis(2-hydroxy-3-hydroxymethyl-5-methyl)methane,
4,4′-[1,4-phenylenebis(1-methylethylidene)]bis(2-methylphenol),
1,1-bis(4-hydroxy-3-phenylphenyl)cyclohexane,
3,3-ethyleneoxydiphenol,
1,4-bis(4-hydroxybenzoate)-3-methylbenzene,
4,4″-dihydroxy-3″-methyl-p-terphenyl,
4,4″-dihydroxy-3″-isopropyl-p-terphenyl,
2,2-dimethyl-1,3-bis(4-hydroxybenzoyloxy)propane,
2,2′-biphenol,
4,4′″-dihydroxy-p-quaterphenyl,
4,4-dihydroxydiphenyl ether,
bis(4-hydroxyphenylthioethyl) ether,
bis(4-hydroxyphenyl)sulfone,
4-benzyloxy-4'-hydroxydiphenylsulfone,
4-(4-methylbenzyloxy)-4'-hydroxydiphenylsulfone,
4-(4-ethylbenzyloxy)-4'-hydroxydiphenylsulfone,
4-(4-n-propylbenzyloxy)-4'-hydroxydiphenylsulfone,
4-(4-isopropylbenzyloxy)-4'-hydroxydiphenylsulfone,
4-(4-n-butylbenzyloxy)-4'-hydroxydiphenylsulfone,
4-(4-isobutylbenzyloxy)-4'-hydroxydiphenylsulfone,
4-(4-sec-butylbenzyloxy)-4'-hydroxydiphenylsulfone,
4-(4-tert-butylbenzyloxy)-4'-hydroxydiphenylsulfone,
4-(3-methylbenzyloxy)-4'-hydroxydiphenylsulfone,
4-(3-ethylbenzyloxy)-4'-hydroxydiphenylsulfone,
4-(3-n-propylbenzyloxy)-4'-hydroxydiphenylsulfone,
4-(3-isopropylbenzyloxy)-4'-hydroxydiphenylsulfone,
4-(3-n-butylbenzyloxy)-4'-hydroxydiphenylsulfone,
4-(3-isobutylbenzyloxy)-4'-hydroxydiphenylsulfone,
4-(3-sec-butylbenzyloxy)-4'-hydroxydiphenylsulfone,
4-(3-tert-butylbenzyloxy)-4'-hydroxydiphenylsulfone,
4-(2-methylbenzyloxy)-4'-hydroxydiphenylsulfone,
4-(2-ethylbenzyloxy)-4'-hydroxydiphenylsulfone,
4-(2-n-propylbenzyloxy)-4'-hydroxydiphenylsulfone,
4-(2-isopropylbenzyloxy)-4'-hydroxydiphenylsulfone,
4-(2-n-butylbenzyloxy)-4'-hydroxydiphenylsulfone,
4-(2-isobutylbenzyloxy)-4'-hydroxydiphenylsulfone,
4-(2-sec-butylbenzyloxy)-4'-hydroxydiphenylsulfone,
4-(2-tert-butylbenzyloxy)-4'-hydroxydiphenylsulfone,
2,4′-dihydroxydiphenyl sulfone,
3,4′-dihydroxydiphenyl sulfone,
4-hydroxydiphenyl sulfone,
4-methyl-4'-hydroxydiphenylsulfone,
4-ethyl-4'-hydroxydiphenylsulfone,
4-n-propyl-4'-hydroxydiphenylsulfone,
4-isopropyl-4'-hydroxydiphenylsulfone,
4-chloro-4'-hydroxydiphenylsulfone,
4-fluoro-4'-hydroxydiphenylsulfone,
4-chloro-2-methyl-4'-hydroxydiphenylsulfone,
4-methoxy-4'-hydroxydiphenylsulfone,
4-ethoxy-4'-hydroxydiphenylsulfone,
4-n-propoxy-4'-hydroxydiphenylsulfone,
4-isopropoxy-4'-hydroxydiphenylsulfone,
4-n-butoxy-4'-hydroxydiphenylsulfone,
4-isobutoxy-4'-hydroxydiphenylsulfone,
4-sec-butoxy-4'-hydroxydiphenylsulfone,
4-tert-butoxy-4′-hydroxydiphenylsulfone,
4-n-pentyloxy-4'-hydroxydiphenylsulfone,
4-isopentyloxy-4'-hydroxydiphenylsulfone,
4-(1-propenyloxy)-4'-hydroxydiphenylsulfone,
4-(2-propenyloxy)-4'-hydroxydiphenylsulfone,
4-benzyloxy-4'-hydroxydiphenylsulfone,
4-(β-phenoxyethoxy)-4′-hydroxydiphenylsulfone,
4-(β-phenoxypropoxyl)-4′-hydroxydiphenylsulfone,
bis(2-allyl-4-hydroxydiphenyl)sulfone,
bis[4-hydroxy-3-(2-propenyl)phenyl]sulfone,
bis(3,5-dibromo-4-hydroxyphenyl)sulfone,
bis(3,5-dichloro-4-hydroxyphenyl)sulfone,
bis(3-phenyl-4-hydroxyphenyl)sulfone,
bis(4-hydroxy-3-n-propylphenyl)sulfone,
bis(4-hydroxy-3-methylphenyl)sulfone,
3,4-dihydroxydiphenyl sulfone,
3′,4′-dihydroxy-4-methyldiphenylsulfone,
3,4,4′-trihydroxydiphenyl sulfone,
bis(3,4-dihydroxyphenyl)sulfone,
2,3,4-trihydroxydiphenyl sulfone,
4-isopropoxy-4'-hydroxydiphenylsulfone,
4-n-propoxy-4'-hydroxydiphenylsulfone,
4-allyloxy-4'-hydroxydiphenylsulfone,
4-benzyloxy-4'-hydroxydiphenylsulfone,
4-(2-propenyloxy)-4'-hydroxydiphenylsulfone,
3-benzyl-4-benzyloxy-4'-hydroxydiphenylsulfone,
3-phenethyl-4-phenethyloxy-4'-hydroxydiphenylsulfone,
3-methylbenzyl-4-methylbenzyloxy-4'-hydroxydiphenylsulfone,
4-benzyloxy-3′-benzyl-4′-hydroxydiphenylsulfone,
4-phenethyloxy-3′-phenethyl-4′-hydroxydiphenylsulfone,
4-methylbenzyloxy-3'-methylbenzyl-4'-hydroxydiphenylsulfone,
α,α'-bis{4-(p-hydroxyphenylsulfone)phenoxy}-p-xylene,
4,4′-{oxybis(ethylene oxide-p-phenylenesulfonyl)}diphenol,
bis(4-hydroxyphenyl) sulfide,
bis(4-hydroxy-3-methylphenyl)sulfide,
bis(3,5-dimethyl-4-hydroxyphenyl)sulfide,
bis(3-ethyl-4-hydroxyphenyl) sulfide,
bis(3,5-diethyl-4-hydroxyphenyl)sulfide,
bis(4-hydroxy-3-n-propylphenyl)sulfide,
bis(3,5-di-n-propyl-4-hydroxyphenyl)sulfide,
bis(3-tert-butyl-4-hydroxyphenyl)sulfide,
bis(3,5-di-tert-butyl-4-hydroxyphenyl)sulfide,
bis(4-hydroxy-3-n-pentylphenyl)sulfide,
bis(3-n-hexyl-4-hydroxyphenyl)sulfide,
bis(3-n-heptyl-4-hydroxyphenyl)sulfide,
bis(5-tert-octyl-2-hydroxyphenyl)sulfide,
bis(2-hydroxy-3-tert-octylphenyl)sulfide,
bis(2-hydroxy-5-n-octylphenyl)sulfide,
bis(5-chloro-2-hydroxyphenyl) sulfide,
bis(3-cyclohexyl-4-hydroxyphenyl)sulfide,
bis(4-hydroxyphenylthioethoxy)methane,
1,5-(4-hydroxyphenylthio)-3-oxypentane,
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.

Furthermore, as trisphenol compounds, for example,
4,4′,4″-methylidyne trisphenol,
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″-ethylidine trisphenol,
4,4′,4″-ethylidine tris(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-hydroxylphenyl)-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″-methylidyne trisphenol,
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-hydroxylophenyl)-1-methylethyl]phenyl}ethylidene]bis(2-tert-butylphenol),
4,4′-[1-{4-[1-(3,5-dimethyl-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis(2,6-dimethylphenol),
4,4′-[(3-ethoxy-4-hydroxyphenyl)methylene]bis(2-cyclohexyl-5-methylphenol),
4,4′-[(3-cyclohexyl-4-hydroxyphenyl)ethylidene]bis(2-cyclohexylphenol),
4,4′-[(5-cyclohexyl-4-hydroxy-2-methoxyphenyl)ethylidene]bis(2-cyclohexyl-5-methylphenol),
4,4′-[1-{4-[1-(3-cyclohexyl-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis(2-cyclohexylphenol),
4,4′-[1-{4-[1-(3-fluoro-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bisphenol,
4,4′-[1-{4-[1-(3-fluoro-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis(2-methylphenol),
4,4′-[1-{4-[1-(3-fluoro-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis(2,6-dimethylphenol),
2,6-bis[(5-fluoro-2-hydroxyphenyl)methyl]-4-methylphenol,
2,6-bis[(3,5-dimethyl-4-hydroxyphenyl)methyl]-4-methylphenol,
2,6-bis[(4-hydroxyphenyl)methyl]-4-methylphenol,
2,6-bis[(4-hydroxyphenyl)methyl]-4-ethylphenol,
2,4-bis[(4-hydroxy-3-methylphenyl)methyl]-6-methylphenol,
2,6-bis[(4-hydroxy-3-methylphenyl)methyl]-4-methylphenol,
2,6-bis[(4-hydroxy-3-methylphenyl)methyl]-4-ethylphenol,
2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-ethylphenol,
2,6-bis[(3,5-dimethyl-2-hydroxyphenyl)methyl]-4-methylphenol,
2,6-bis[(2,4-dimethyl-6-hydroxyphenyl)methyl]-4-methylphenol,
2,4-bis[(4-hydroxyphenyl)methyl]-6-cyclohexylphenol,
2,6-bis[(2,5-dimethyl-4-hydroxyphenyl)methyl]-3,4-dimethylphenol,
2,6-bis[(2,5-dimethyl-4-hydroxyphenyl)methyl]-4-ethylphenol,
2,6-bis[(4-hydroxy-2,3,6-trimethylphenyl)methyl]-4-methylphenol,
2,4-bis[(4-hydroxy-3-methylphenyl)methyl]-6-cyclohexylphenol,
2,6-bis[(4-hydroxy-3-methylphenyl)methyl]-4-cyclohexylphenol,
2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-cyclohexylphenol,
2,6-bis[(4-hydroxy-2,3,5-trimethylphenyl)methyl]-4-ethylphenol,
2,4-bis[(2,5-dimethyl-4-hydroxyphenyl)methyl]-6-cyclohexylphenol,
4,4′,4″-methylidinetris(2,6-dimethylphenol),
α-(4-hydroxy-3-methylphenyl)-α,α'-bis(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene,
α′-(4-hydroxy-3-methylphenyl)-α,α-bis(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene,
α,α-bis(4-hydroxy-3-methylphenyl)-α'-(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene,
α,α'-bis(4-hydroxy-3-methylphenyl)-α-(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene,
1,1-bis(4-hydroxyphenyl)-4-[1-(4-hydroxyphenyl)-1-methylpropyl]cyclohexane,
2,6-bis[(3,5-dimethyl-4-hydroxyphenyl)methyl]-4-ethylphenol,
1,1′-bis(4-hydroxyphenyl)-4-[1-(4-hydroxyphenyl)propyl]cyclohexane,
1,1′-bis(4-hydroxy-3-methylphenyl)-4-[1-(4-hydroxyphenyl)propyl]cyclohexane,
1,1′-bis(3,5-dimethyl-4-hydroxyphenyl)-4-[1-(4-hydroxyphenyl)propyl]cyclohexane,
1-(4-hydroxyphenyl)-1-[4,4-bis(4-hydroxyphenyl)cyclohexyl]-4-isopropylcyclohexane,
4,4′-[3-(2,5-dimethyl-4-hydroxyphenyl)butylene]bis(2,5-dimethylphenol),
1,3,5-tri(4-hydroxy-3-phenylphenyl)adamantane,
1,3,5-tri(3-cyclohexyl-4-hydroxyphenyl)adamantane,
2,4-bis[(3,5-dimethyl-4-hydroxyphenyl)methyl]-6-cyclohexylphenol,
2,6-bis[(2,5-dimethyl-4-hydroxyphenyl)methyl]-4-cyclohexylphenol,
2,4-bis[(3-cyclohexyl-4-hydroxyphenyl)methyl]-6-methylphenol,
2,4-bis[(4-hydroxy-2,3,5-trimethylphenyl)methyl]-6-cyclohexylphenol,
2,6-bis[(5-fluoro-2-hydroxyphenyl)methyl]-4-fluorophenol,
2,6-bis[(3-fluoro-4-hydroxyphenyl)methyl]-4-fluorophenol,
2,4-bis[(3-fluoro-4-hydroxyphenyl)methyl]-6-methylphenol,
4,4′-[3-(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3-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)
etc. can be exemplified.

Examples of compounds having 4 or more phenolic hydroxyl groups include
bis[2-hydroxy-3-(2-hydroxy-5-methylbenzyl)-5-methylphenyl]methane,
4,6-bis[(4-hydroxyphenyl)methyl)-1,3-benzenediol,
4,4′-[(3,4-dihydroxyphenyl)methylene]bis(2,6-dimethylphenol),
4,4′-[(3,4-dihydroxyphenyl)methylene]bis(2-cyclohexyl-5-methylphenol),
4,4′-[(3,4-dihydroxyphenyl)methylene]bis(2-methylphenol),
4,4′-[(3,4-dihydroxyphenyl)methylene]bis(2,3,6-trimethylphenol),
1,1,2,2-tetrakis(4-hydroxyphenyl)ethane,
4,4′,4″,4′″-(1,1,2,2-ethanetetrayl)tetrakis(2-methylphenol),
4,4′,4″,4′″-(1,1,2,2-ethanetetrayl)tetrakis(2,6-dimethylphenol),
4,4′,4″,4′″-(1,4-phenylene)bis(methylidine)tetrakis(2,6-dimethylphenol),
2,2′-bis[4,4-bis(4-hydroxy-3-methylphenyl)cyclohexyl]propane,
2,2′-[(3,4-dihydroxyphenyl)methylene]bis(3,5-dimethylphenol),
4,6-bis[(3,5-dimethyl-4-hydroxyphenyl)methyl)-1,3-benzenediol,
2,2′-[(3,4-dihydroxyphenyl)methylene]bis(3,5,6-trimethylphenol),
4,4′-[(3,4-dihydroxyphenyl)methylene]bis(2-cyclohexylphenol),
bis[4-hydroxy-3-(2-hydroxybenzyl)-5-methylphenyl]methane,
bis[4-hydroxy-3-(3-hydroxybenzyl)-5-methylphenyl]methane,
bis[4-hydroxy-3-(4-hydroxybenzyl)-5-methylphenyl]methane,
bis[2-hydroxy-3-(2-hydroxybenzyl)-5-methylphenyl]methane,
bis[2-hydroxy-3-(3-hydroxybenzyl)-5-methylphenyl]methane,
bis[2-hydroxy-3-(4-hydroxybenzyl)-5-methylphenyl]methane,
bis[2-hydroxy-3-(3-hydroxy-4-methylbenzyl)-5-methylphenyl]methane,
bis[2-hydroxy-3-(4-hydroxy-3-methylbenzyl)-5-methylphenyl]methane,
bis[2-hydroxy-3-(3-hydroxy-2-methylbenzyl)-5-methylphenyl]methane,
bis[2-hydroxy-3-(2-hydroxy-3-methylbenzyl)-5-methylphenyl]methane,
α,α′,α″,α′″-tetrakis(4-hydroxyphenyl)-p-xylene,
bis[2-hydroxy-3-(4-hydroxy-2,3,5-trimethylbenzyl)-5-methylphenyl]methane,
bis[2-hydroxy-3-(2,5-dimethyl-3-hydroxybenzyl)-5-methylphenyl]methane,
bis[2-hydroxy-3-(2,5-dimethyl-4-hydroxybenzyl)-5-methylphenyl]methane,
bis[2-hydroxy-3-(2,5-dimethyl-5-hydroxybenzyl)-5-methylphenyl]methane,
bis[2-hydroxy-3-(3,5-dimethyl-4-hydroxybenzyl)-5-methylphenyl]methane,
bis[2-hydroxy-3-(2-hydroxy-3,4,6-trimethylbenzyl)-5-methylphenyl]methane,
bis[2-hydroxy-3-(4-hydroxy-2,3,6-trimethylbenzyl)-5-methylphenyl]methane,
4,4′,4″,4′″-tetrakis(4-hydroxyphenyl)bicyclohexyl,
bis[4-hydroxy-3-(5-cyclohexyl-4-hydroxy-2-methylbenzyl)-5-methylphenyl]methane,
4,4′,4″,4′″-tetrakis(4-hydroxy-3-methylphenyl)bicyclohexyl,
4,6-bis(3,5-dimethyl-4-hydroxyphenyl)-1,2-benzenediol,
4,4′,4″,4′″-tetrakis(3,5-dimethyl-4-hydroxyphenyl)bicyclohexyl,
1,1-bis[5-cyclohexyl-4-hydroxy-3-(2-hydroxy-5-methylbenzyl)phenyl]cyclohexane,
1,1-bis[5-cyclohexyl-4-hydroxy-3-(3,5-dimethyl-4-hydroxybenzyl)phenyl]cyclohexane,
1,1-bis[5-cyclohexyl-4-hydroxy-3-(5-cyclohexyl-4-hydroxy-2-methylbenzyl)phenyl]cyclohexane,
4,6-bis[1-(4-hydroxyphenyl)ethyl-1,3-benzenediol,
2,2-bis[4-hydroxy-3-(4-hydroxy-3-methylbenzyl)-5-methylphenyl]propane,
2,6-bis[(3,5-dimethyl-4-hydroxyphenyl)benzyl]-4-[α-methyl-(3,5-dimethyl-4-hydroxyphenyl)benzyl]phenol,
4,4′,4″,4′″-tetrakis(3-isopropyl-4-hydroxyphenyl)bicyclohexyl,
4,4′-bis[(3,4-dihydroxyphenyl)methylene]bis(2-isopropylphenol),
2,2′-bis[4,4-bis(4-hydroxyphenyl)cyclohexyl]propane,
2,4,6-tris(4-hydroxybenzyl)-1,3-benzenediol,
4,6-bis(3,5-dimethyl-4-hydroxybenzyl)-1,2,3-benzenetriol,
3,3′-[(2-hydroxyphenyl)methylene]bis(5-methyl-1,2-benzenediol),
2,6-bis(2,4-dihydroxybenzyl)-4-ethylphenol,
2,4-bis(2,4-dihydroxybenzyl)-6-cyclohexylphenol,
2,6-bis(5-tert-butyl-2,3-dihydroxybenzyl)-4-methylphenol,
2,4,6-tris(3,5-dimethyl-4-hydroxybenzyl)-1,2-benzenediol,
2,4,6-tris(3,5-dimethyl-2-hydroxybenzyl)-1,2-benzenediol,
2,6-bis(2,4-dihydroxybenzyl)-3,4-dimethylphenol,
2,6-bis[3-(2-hydroxy-5-methylbenzyl)-2,5-dimethyl-4-hydroxybenzyl]-3,4-dimethylphenol,
4,6-bis(α-methyl-4-hydroxybenzyl)-1,2,3-benzenetriol,
4,4′-[1-{4-[1-(3,5-bis(4-hydroxybenzyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[2,6-bis( 4-hydroxybenzyl)phenol],
4,4′-[1-{4-[1-(3,5-bis(4-hydroxy-3-methylbenzyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[2, 6-bis(4-hydroxy-3-methylbenzyl)phenol],
4,4′-[1-{4-[1-(3,5-bis(3,5-dimethyl-4-hydroxybenzyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[ 2,6-bis(3,5-dimethyl-4-hydroxybenzyl)phenol],
4,4′-[1-{4-[1-(3,5-bis(4-hydroxy-2,3,6-trimethylbenzyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene] bis[2,6-bis(4-hydroxy-2,3,6-trimethylbenzyl)phenol],
bis[5-(2,4-dihydroxybenzyl)-4-hydroxy-3-methylphenyl]methane,
bis[3-(2,4-dihydroxybenzyl)-2,5-dimethyl-4-hydroxyphenyl]methane,
bis[3-(2,4-dihydroxy-3-methylbenzyl)-2,5-dimethyl-4-hydroxyphenyl]methane,
bis[5-(4-hydroxybenzyl)-2,3,4-trihydroxyphenyl]methane,
1,1-bis[5-(4-hydroxybenzoyl)-2,3,4-trihydroxyphenyl]ethane,
3,3′,5,5′-tetrakis(4-hydroxybenzyl)-4,4′-dihydroxybiphenyl,
3,3′,5,5′-tetrakis(4-hydroxy-3-methylbenzyl)-4,4′-dihydroxybiphenyl,
3,3′,5,5′-tetrakis(2-hydroxy-5-methylbenzyl)-4,4′-dihydroxybiphenyl,
3,3′,5,5′-tetrakis(3,5-dimethyl-4-hydroxybenzyl)-4,4′-dihydroxybiphenyl,
bis{3-[α,α-bis(4-hydroxy-3-methylphenyl)methyl]-4-hydroxyphenyl}methane,
bis[3,5-bis(2-hydroxy-5-methylbenzyl)-4-hydroxyphenyl]methane,
4,4′,4″-ethylidinetris{[2-(2-hydroxy-5-methyl)benzyl]-6-methylphenol},
2,2-bis[3,5-bis(2-hydroxy-5-methylphenylmethyl)phenyl]propane,
bis{3-[α,α-bis(2,5-dimethyl-4-hydroxyphenyl)methyl]-4-hydroxyphenyl}methane,
bis[5-(3,5-dimethyl-4-hydroxybenzyl)-2,3,4-trihydroxyphenyl]methane,
bis[3-(2,3,4-trihydroxybenzyl)-2,5-dimethyl-4-hydroxyphenyl]methane,
1,1-bis[3-(2,3,4-trihydroxybenzyl)-5-cyclohexyl-4-hydroxyphenyl]cyclohexane,
1,8,15,22-tetranonyl-3,5,10,12,17,19,24,26-octahydroxy[1,1,1,1]-metacyclophane,
4,4′-[1-{4-[1-(3,5-bis(4-hydroxy-2-methylbenzyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[2, 6-bis(4-hydroxy-2-methylbenzyl)phenol],
4,4′-[1-{4-[1-(3,5-bis(2-hydroxy-5-methylbenzyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[2, 6-bis(2-hydroxy-5-methylbenzyl)phenol],
4,4′-[1-{4-[1-(3,5-bis(3-ethyl-4-hydroxybenzyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[2, 6-bis(3-ethyl-4-hydroxybenzyl)phenol],
4,4′-[1-{4-[1-(3,5-bis(3,5-dimethyl-2-hydroxyphenyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[ 2,6-bis(3,5-dimethyl-2-hydroxyphenyl)phenol],
4,4′-[1-{4-[1-(3,5-bis(4-hydroxy-3-isopropylphenyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[2, 6-bis(4-hydroxy-3-isopropylphenyl)phenol],
bis{3-[α,α-bis(3,5-dimethyl-4-hydroxyphenyl)methyl]-4-hydroxyphenyl}methane,
bis{3-[α,α-bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)methyl]-4-hydroxyphenyl}methane,
4,4′-[4-hydroxy-3,5-bis(2-hydroxybenzyl)methylene]bis[2,6-bis(2-hydroxybenzyl)]phenol,
4,4′-[4-hydroxy-3,5-bis(4-hydroxybenzyl)methylene]bis[2,6-bis(4-hydroxybenzyl)]phenol,
4,4′,4″-ethylidinetris[2,6-bis(2-hydroxybenzyl)phenol],
4,4′,4″-ethylidinetris[2,6-bis(4-hydroxybenzyl)phenol],
2,2-bis[3,5-bis(4-hydroxy-3-methylbenzyl)-4-hydroxyphenyl]propane,
1,8,15,22-tetraethyl-3,5,10,12,17,19,24,26-octahydroxy[1,1,1,1]-metacyclophane,
α,α′,α″,α′″-tetrakis(3,5-dimethyl-4-hydroxyphenyl)-1,4-dimethylbenzene,
4,4′-[1-{4-[1-(3,5-bis(2-hydroxy-5-isopropylphenyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[2, 6-bis(2-hydroxy-5-isopropylphenyl)phenol],
4,4′-[1-{4-[1-(3,5-bis(4-hydroxy-2,3,5-trimethylphenyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene] bis[2,6-bis(4-hydroxy-2,3,5-trimethylphenyl)phenol],
4,4′-[1-{4-[1-(3,5-bis(3-sec-butyl-4-hydroxyphenyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[ 2,6-bis(3-sec-butyl-4-hydroxyphenyl)phenol],
4,4′-[1-{4-[1-(3,5-bis(3-tert-butyl-4-hydroxyphenyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[ 2,6-bis(3-tert-butyl-4-hydroxyphenyl)phenol],
2,6-bis{[3-(2,4-dihydroxybenzyl)-2,5-dimethyl-4-hydroxy]benzyl}-4-methylphenol,
1,1-bis[5-(2,4-dihydroxybenzyl)-3-cyclohexyl-4-hydroxyphenyl]cyclohexane,
1,1-bis[5-(2,3,4-trihydroxybenzyl)-3-cyclohexyl-4-hydroxyphenyl]cyclohexane,
2,2-bis[4,4',4'',4'''-tetrakis(3,5-dihydroxymethyl-4-hydroxyphenyl)cyclohexyl]propane and the like can be mentioned.

Examples of carboxylic acids and derivatives thereof include
3,5-di(α-methylbenzyl)salicylic acid,
4-(2-p-methoxyphenyloxyethoxy)salicylic acid,
4-hydroxyphenylbenzoic acid,
4-chlorobenzoic acid,
4-[2-(p-methoxyphenoxy)ethyloxy]salicylic acid,
4-[3-(p-tolylsulfonyl)propyloxy]salicylic acid,
5-[p-(2-p-methoxyphenoxyethoxy)cumyl]salicylic acid,
4-octyloxycarbonylaminosalicylic acid,
3,5-distyrenated salicylic acid,
N-(p-toluenesulfonyl)-glycine,
N-(p-toluenesulfonyl)-alanine,
N-(p-toluenesulfonyl)-β-alanine,
N-phenylaminocarbonyl-glycine,
N-phenylaminocarbonyl-valine,
N-(m-tolylaminocarbonyl)-phenylalanine,
N-(m-tolylaminocarbonyl)-cysteine-S-benzyl,
N-(m-tolylaminocarbonyl)-methionine,
N-(m-tolylaminocarbonyl)-tyrosine,
N-(p-tolylaminocarbonyl)-phenylalanine,
N-(p-tolylaminocarbonyl)-cysteine-S-benzyl,
N-(p-tolylaminocarbonyl)-methionine,
N-(phenylaminocarbonyl)-methionine,
N-(p-tolylaminocarbonyl)-tyrosine,
2-O-(phenylaminocarbonyl)-mandelic acid,
2-O-(p-tolylaminocarbonyl)-mandelic acid,
2-O-(m-tolylaminocarbonyl)-mandelic acid,
2-O-(o-tolylaminocarbonyl)-mandelic acid,
2-O-(1-naphthylaminocarbonyl)-mandelic acid,
2-O-(3-isopropenyl-α,α-dimethylbenzylaminocarbonyl)-mandelic acid,
2-O-(benzylaminocarbonyl)-mandelic acid,
2-O-(phenethylaminocarbonyl)-mandelic acid,
2-O-(phenylaminocarbonyl)-lactic acid,
2-O-(p-tolylaminocarbonyl)-lactic acid,
2-O-(m-tolylaminocarbonyl)-lactic acid,
2-O-(o-tolylaminocarbonyl)-lactic acid,
2-O-(1-naphthylaminocarbonyl)-lactic acid,
2-O-(3-isopropenyl-α,α-dimethylbenzylaminocarbonyl)-lactic acid,
2-O-(benzylaminocarbonyl)-lactic acid,
Examples include 2-O-(phenethylaminocarbonyl)-lactic acid and the like.

Acidic phosphoric ester compounds include, for example, 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, tetracosylate. Examples include luacid phosphate, monobutyl phosphate, dibutyl phosphate, monoisodecyl phosphate, bis(2-ethylhexyl) phosphate and the like.

As the component (b), a compound having a phenolic hydroxyl group is preferable because it can more effectively express the heat discoloration property. , acidic phosphates and their metal salts, or 1,2,3-triazoles and their derivatives.

The component (c) of the reaction medium for reversibly causing the electron transfer reaction by the components (a) and (b) in a specific temperature range will now be described.
Each of the thermochromic color-memory materials to be applied in the present invention has different thermochromic properties, that is, the color density-temperature curves are different from each other, one being in a colored state and the other in a decolored state. That is, the component (c) applied to each thermochromic color-memory material (thermochromic color-memory composition) is also different.

〔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 color-developing thermochromic color-memory material applied to the present invention exhibits the hysteresis characteristics described above, has a hysteresis width (ΔH) of 8 to 100° C., a complete color development temperature t ₄ of −25° C. or higher, It is in the range of 15°C or less. As the component (c) of the thermochromic color-memory material in a colored state, an ester compound having a specific structure represented by the formula (C) is used.
The ester compound represented by Formula (C) will be described.

[In the formula, 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) is an alcohol selected from benzyl alcohol, alkylbenzyl alcohol having a linear or branched alkyl group having 1 to 3 carbon atoms, or cycloalkylmethanol, and an alcohol having 2 carbon atoms. ∼14 can be obtained by esterification reaction with carboxylic acids.

Specific examples of alkylbenzyl alcohols having a linear or branched alkyl group having 1 to 3 carbon atoms include 2-methylbenzyl alcohol, 3-methylbenzyl alcohol, 4-methylbenzyl alcohol, 2-ethylbenzyl alcohol, 3- Ethylbenzyl alcohol, 4-ethylbenzyl alcohol, 2-n-propylbenzyl alcohol, 3-n-propylbenzyl alcohol, 4-n-propylbenzyl alcohol, 2-isopropylbenzyl alcohol, 3-isopropylbenzyl alcohol, 4-isopropylbenzyl alcohol alcohol etc. can be illustrated.
In the alkylbenzyl alcohol having a straight-chain or branched alkyl group having 1 to 3 carbon atoms, the substitution position of the alkyl group is not particularly limited. Alkylbenzyl alcohol substituted with an alkyl group at the (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 the formula (C), specific 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, Examples include benzyl caprylate, benzyl caprate, benzyl laurate, benzyl myristate and the like.
Further, as an ester compound obtained by an esterification reaction between an alkylbenzyl alcohol having a linear or branched alkyl group having 1 to 3 carbon atoms and a carboxylic acid having 2 to 14 carbon atoms, specifically, 4-methyl acetate benzyl, 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-methylbenzyl caprate n-propylbenzyl, 4-methylbenzyl laurate, 4-ethylbenzyl laurate, 4-n-propylbenzyl laurate, 4-methylbenzyl myristate, 4-ethylbenzyl myristate, 4-n-propylbenzyl myristate etc. can be exemplified.
Specific examples of ester compounds obtained by an esterification reaction between cycloalkylmethanol and a carboxylic acid having 2 to 14 carbon atoms include cyclopropylmethyl acetate, cyclobutylmethyl acetate, cyclopentylmethyl acetate, cyclohexylmethyl acetate, and acetic acid. Cycloheptylmethyl, cyclooctylmethyl acetate, cyclopropylmethyl butyrate, cyclobutylmethyl butyrate, cyclopentylmethyl butyrate, cyclohexylmethyl butyrate, cycloheptylmethyl butyrate, cyclooctylmethyl butyrate, cyclopropylmethyl caproate, cyclobutylmethyl caproate, capron cyclopentylmethyl caproate, cyclohexylmethyl caproate, cycloheptylmethyl caproate, cyclooctylmethyl caproate, cyclopropylmethyl caprylate, cyclobutylmethyl caprylate, cyclopentylmethyl caprylate, cyclohexylmethyl caprylate, cycloheptylmethyl caprylate, capryl cyclooctylmethyl caprate, cyclopropylmethyl caprate, cyclobutylmethyl caprate, cyclopentylmethyl caprate, cyclohexylmethyl caprate, cycloheptylmethyl caprate, cyclooctylmethyl caprate, cyclopropylmethyl laurate, cyclobutylmethyl laurate , cyclopentylmethyl laurate, cyclohexylmethyl laurate, cycloheptylmethyl laurate, cyclooctylmethyl laurate, cyclopropylmethyl myristate, cyclobutylmethyl myristate, cyclopentylmethyl myristate, cyclohexylmethyl myristate, cycloheptylmethyl myristate , cyclooctylmethyl myristate, and the like.

Regarding R ₁ , it is preferable that X is a hydrogen atom, a methyl group, or a cyclohexyl group, since a compound having a larger hysteresis width (ΔH) can be easily obtained.
As for R ₂ , a linear or branched alkyl group having 3 to 11 carbon atoms is preferable because it is likely to be a compound having a discoloration temperature in a lower range.

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

Two or more ester compounds represented by the formula (C) can be used in combination as the component (c) applied to the color-developing thermochromic color-memory material. In addition to the formula (C), conventionally known components (c) such as alcohols, esters, ketones, ethers, acid amides and the like, which will be described later, may be further included.
When the component (C) contains a compound other than the formula (C), the compounding ratio of the compound other than the formula (C) is preferably 1 to 30% by mass in the total amount of the component (C), and 2 to It is more preferably 25% by mass, and even more preferably 3 to 20% by mass.

The decolorized thermochromic color-memory material applied to the present invention exhibits the hysteresis characteristics described above, has a hysteresis width (ΔH) of 8 to 100°C, and a complete coloring temperature t ₁ of -30°C. above and below 10°C. The component (c) used in the decolorized thermochromic color-memory material is not particularly limited as long as it satisfies the above-mentioned hysteresis width and complete coloring temperature _t1 . Known alcohols, esters, ketones, ethers and acid amides can be mentioned.

When the thermochromic color-memory composition is encased in microcapsules and applied to secondary processing, low-molecular-weight ones evaporate out of the capsules when subjected to high heat treatment, so they are stably retained in the capsules. Therefore, a compound having 10 or more carbon atoms is preferably used.

As alcohols, aliphatic monohydric saturated alcohols having 10 or more carbon atoms are effective. Examples include heptadecyl alcohol, octadecyl alcohol, eicosyl alcohol, and docosyl alcohol.

Esters other than the compounds represented by the formula (C) are effective esters having 10 or more carbon atoms. Esters obtained from any combination of monohydric alcohols having a ring or aromatic ring, polyvalent carboxylic acids having aliphatic and alicyclic or aromatic rings, and monohydric alcohols having aliphatic and alicyclic or aromatic rings Esters obtained from a combination of monovalent carboxylic acids having aliphatic and alicyclic or aromatic rings and esters obtained from any combination of polyhydric alcohols having aliphatic and alicyclic or aromatic rings, For example, ethyl caprylate, octyl caprylate, stearyl caprylate, myristyl caprate, docosyl caprate, 2-ethylhexyl laurate, n-decyl laurate, 3-methylbutyl myristate, cetyl myristate, isopropyl palmitate, palmitic acid Neopentyl, nonyl palmitate, cyclohexyl palmitate, n-butyl stearate, 2-methylbutyl stearate, 3,5,5-trimethylhexyl stearate, n-undecyl stearate, pentadecyl stearate, stearyl stearate, cyclohexyl stearate methyl, isopropyl behenate, hexyl behenate, lauryl behenate, behenyl behenate, cetyl benzoate, 4-tert-butyl stearyl benzoate, dimyristyl phthalate, distearyl phthalate, dimyristyl oxalate, dicetyl oxalate, malonic acid Dicetyl, dilauryl succinate, dilauryl glutarate, diundecyl adipate, dilauryl azelate, di-(n-nonyl) sebacate, dineopentyl 1,18-octadecylmethylenedicarboxylate, ethylene glycol dimiristate, 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 di Examples include myristate, xylene glycol dicaprinate, xylene glycol distearate, and the like.

Ester compounds of saturated fatty acids and branched fatty alcohols, and ester compounds of unsaturated fatty acids or branched or substituted saturated fatty acids with branched or C 16 or more fatty alcohols are also effective. for example 2-ethylhexyl butyrate, 2-ethylhexyl behenate, 2-ethylhexyl myristate, 2-ethylhexyl caprate, 3,5,5-trimethylhexyl laurate, 3,5,5-trimethylhexyl palmitate, 3,5,5-trimethylhexyl stearate, 2-methylbutyl caproate, 2-methylbutyl caprylate, 2-methylbutyl caprate, 1-ethylpropyl palmitate, 1-ethylpropyl stearate, 1-ethylpropyl behenate, 1-Ethylhexyl Laurate, 1-Ethylhexyl Myristate, 1-Ethylhexyl Palmitate, 2-Methylpentyl Caproate, 2-Methylpentyl Caprylate, 2-Methylpentyl Caprate, 2-Methylpentyl Laurate, 2-Stearate Methylbutyl, 2-methylbutyl stearate, 3-methylbutyl stearate, 1-methylheptyl stearate, 2-methylbutyl behenate, 3-methylbutyl behenate, 1-methylheptyl stearate, 1-methylheptyl behenate, 1 caproic acid -ethylpentyl, 1-ethylpentyl palmitate, 1-methylpropyl stearate, 1-methyloctyl stearate, 1-methylhexyl stearate, 1,1-dimethylpropyl laurate, 1-methylpentyl caprate, palmitic acid 2-methylhexyl, 2-methylhexyl stearate, 2-methylhexyl behenate, 3,7-dimethyloctyl laurate, 3,7-dimethyloctyl myristate, 3,7-dimethyloctyl palmitate, stearic acid 3, 7-dimethyloctyl, 3,7-dimethyloctyl behenate, stearyl oleate, behenyl oleate, stearyl linoleate, behenyl linoleate, 3,7-dimethyloctyl erucate, stearyl erucate, isostearyl erucate, isostearic acid Cetyl, stearyl isostearate, 2-methylpentyl 12-hydroxystearate, 2-ethylhexyl 18-bromostearate, isostearyl 2-ketomyristate, 2-ethylhexyl 2-fluoromyristate, cetyl butyrate, stearyl butyrate, behenyl butyrate etc. can be exemplified.

Further, a fatty acid ester compound obtained from an odd aliphatic monohydric alcohol having 9 or more carbon atoms and an even aliphatic carboxylic acid having an even number of carbon atoms, n-pentyl alcohol or n-heptyl alcohol, and an even number having 10 to 16 carbon atoms Fatty acid ester compounds having a total carbon number of 17 to 23 obtained from aliphatic carboxylic acids are also effective, such as n-pentadecyl acetate, n-tridecyl butyrate, n-pentadecyl butyrate, n-undecyl caproate, and 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, caprine n-tridecyl acid, n-pentadecyl caprate, n-pentyl laurate, n-heptyl laurate, n-nonyl laurate, n-undecyl laurate, n-tridecyl laurate, n-pentadecyl laurate, n-myristate -pentyl, n-heptyl myristate, n-nonyl myristate, n-undecyl myristate, n-tridecyl myristate, n-pentadecyl myristate, n-pentyl palmitate, n-heptyl palmitate, n-nonyl palmitate , n-undecyl palmitate, n-tridecyl palmitate, n-pentadecyl palmitate, n-nonyl stearate, n-undecyl stearate, n-tridecyl stearate, n-pentadecyl stearate, n-nonyl eicosanoate, eicosane Acid n-undelsi, n-tridecyl eicosanoate, n-pentadecyl eicosanoate, n-nonyl behenate, n-undecyl behenate, n-tridecyl behenate, n-pentadecyl behenate and the like can be mentioned.

Effective ketones are aliphatic ketones having a total carbon number of 10 or more, such as 2-decanone, 3-decanone, 4-decanone, 2-undecanone, 3-undecanone, 4-undecanone, and 5-undecanone. , 2-dodecanone, 3-dodecanone, 4-dodecanone, 5-dodecanone, 2-tridecanone, 3-tridecanone, 2-tetradecanone, 2-pentadecanone, 8-pentadecanone, 2-hexadecanone, 3-hexadecanone, 9-heptadecanone, 2 -pentadecanone, 2-octadecanone, 2-nonadecanone, 10-nonadecanone, 2-eicosanone, 11-eicosanone, 2-heneicosanone, 2-docosanone, laurone, stearone and the like.

Furthermore, arylalkyl ketones having a total carbon number of 12 to 24, such as n-octadecanophenone, n-heptadecanophenone, n-hexadecanophenone, n-pentadecanophenone, n-tetradecanophenone. nophenone, 4-n-dodecaacetophenone, n-tridecanophenone, 4-n-undecanoacetophenone, n-laurophenone, 4-n-decanoacetophenone, n-undecanophenone, 4-n-nonylacetophenone, n-decanophenone, 4-n-octylacetophenone, n-nonanophenone, 4-n-heptylacetophenone, n-octanophenone, 4-n-hexylacetophenone, 4-n-cyclohexylacetophenone, 4-tert-butylpropiophenone , n-heptaphenone, 4-n-pentylacetophenone, cyclohexylphenyl ketone, benzyl-n-butyl ketone, 4-n-butylacetophenone, n-hexanophenone, 4-isobutylacetophenone, 1-acetonaphtone, 2-acenaphthone, cyclopentylphenyl A ketone etc. can be illustrated.

Aliphatic ethers having a total carbon number of 10 or more are effective as ethers. , 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. can be exemplified.

Acid amides include, for example, acetamide, propionamide, 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, olein Acid amide, erucamide, benzamide, caproic acid anilide, caprylic acid anilide, capric acid anilide, lauric acid anilide, myristate anilide, palmitic acid anilide, stearic acid anilide, behenic acid anilide, oleic acid anilide, erucic acid anilide, capron acid N-methylamide, caprylic acid N-methylamide, capric acid N-methylamide, lauric acid N-methylamide, myristate 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, myristate N-ethylamide, palmitic acid N-ethylamide, stearic acid N-ethylamide, oleic acid N-ethylamide, lauric acid N-butylamide, myristate N-butylamide , N-butylamide palmitate, N-butylamide stearate, N-butylamide oleate, N-octylamide laurate, N-octylamide myristate, N-octylamide palmitate, N-octylamide stearate, N-oleic acid - octylamide, lauric acid N-dodecylamide, myristate N-dodecylamide, palmitic acid N-dodecylamide, stearic acid N-dodecylamide, oleic acid N-dodecylamide, dilauric acid amide, dimyristate amide, dipalmitin Acid amide, distearic amide, dioleic amide, trilauric amide, trimyristic amide, tripalmitic amide, tristearic amide, trioleic amide, succinic amide, adipic amide, glutaric amide, malonic 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, adipate N-butylamide, glutaric acid N-butylamide, malonic acid N-butylamide, adipate N-octylamide, Examples include 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〕 A compound represented by the following formula (1) may also be used as the component (c) of the thermochromic color-memory material in a decolored state.

[In the formula, R ₁ represents a hydrogen atom or a methyl group, m represents an integer of 0 to 2, and one of X ₁ and X ₂ is -(CH ₂ ) _n OCOR ₂ or (CH ₂ ) _n COOR ₂ , the other represents a hydrogen atom, n represents an integer of 0 to 2, R ₂ represents an alkyl group or alkenyl group having 4 or more carbon atoms, Y ₁ and Y ₂ each independently represent a hydrogen atom, a carbon an alkyl group, a methoxy group, or a halogen atom of numbers 1 to 4, and r and p each independently represent an integer of 1 to 3]

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

（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 the formula (1), the compounds represented by the following formula (2) are more preferable.

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

Examples of compounds represented by formula (2) include 4-benzyloxyphenylethyl octanoate, 4-benzyloxyphenylethyl nonanoate, 4-benzyloxyphenylethyl decanoate, 4-benzyloxyphenylethyl undecanoate, and dodecane. 4-benzyloxyphenylethyl acid, 4-benzyloxyphenylethyl tridecanoate, 4-benzyloxyphenylethyl tetradecanoate, 4-benzyloxyphenylethyl pentadecanoate, 4-benzyloxyphenylethyl hexadecanoate, 4-benzyloxy heptadecanoate Examples include phenylethyl, 4-benzyloxyphenylethyl octadecanoate, and the like.

（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, a compound represented by the following formula (3) may be used as the component (c).

(Wherein, R represents an alkyl group or alkenyl group having 8 or more carbon atoms, m and n each independently represents an integer of 1 to 3, X and Y each independently represent a hydrogen atom, a carbon number 1 to 4 alkyl groups, C 1 to 4 alkoxy groups, or halogen atoms)

Examples of compounds represented by formula (3) include diphenylmethyl octanoate, diphenylmethyl nonanoate, diphenylmethyl decanoate, diphenylmethyl undecanoate, diphenylmethyl dodecanoate, diphenylmethyl tridecanoate, diphenylmethyl tetradecanoate, and pentadecanoate. Examples include diphenylmethyl, 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, a compound represented by the following formula (4) may be used as the component (c).

(Wherein, 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 diesters of malonic acid and 2-[4-(4-chlorobenzyloxy)phenyl]ethanol, and succinic acid and 2-(4-benzyloxyphenyl)ethanol. Diesters, diesters of succinic acid and 2-[4-(3-methylbenzyloxy)phenyl]ethanol, diesters of glutaric acid and 2-(4-benzyloxyphenyl)ethanol, glutaric acid and 2-[4-( 4-chlorobenzyloxy)phenyl]ethanol, diesters of adipic acid and 2-(4-benzyloxyphenyl)ethanol, diesters of pimelic acid and 2-(4-benzyloxyphenyl)ethanol, suberic acid and 2-(4-benzyloxyphenyl)ethanol diester, diester of suberic acid with 2-[4-(3-methylbenzyloxy)phenyl]ethanol, suberic acid with 2-[4-(4-chlorobenzyloxy ) phenyl] ethanol, diester of suberic acid with 2-[4-(2,4-dichlorobenzyloxy)phenyl]ethanol, diester of azelaic acid with 2-(4-benzyloxyphenyl)ethanol, sebacine acid with 2-(4-benzyloxyphenyl)ethanol, 1,10-decanedicarboxylic acid with 2-(4-benzyloxyphenyl)ethanol, 1,18-octadecanedicarboxylic acid with 2-(4 -benzyloxyphenyl)ethanol, diesters of 1,18-octadecanedicarboxylic acid and 2-[4-(2-methylbenzyloxy)phenyl]ethanol, and the like.

（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, a compound represented by the following formula (5) may be used as the component (c).

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

Examples of the compound represented by formula (5) include a diester of 1,3-bis(2-hydroxyethoxy)benzene and capric acid and a diester of 1,3-bis(2-hydroxyethoxy)benzene and undecanoic acid. , a diester of 1,3-bis(2-hydroxyethoxy)benzene and lauric acid, a diester of 1,3-bis(2-hydroxyethoxy)benzene and myristic acid, a diester of 1,4-bis(hydroxymethoxy)benzene and Diesters of butyric acid, diesters of 1,4-bis(hydroxymethoxy)benzene with isovaleric acid, diesters of 1,4-bis(2-hydroxyethoxy)benzene with acetic acid, 1,4-bis(2-hydroxy ethoxy)benzene with propionic acid, 1,4-bis(2-hydroxyethoxy)benzene with valeric acid, 1,4-bis(2-hydroxyethoxy)benzene with caproic acid, 1, Diesters of 4-bis(2-hydroxyethoxy)benzene and caprylic acid, diesters of 1,4-bis(2-hydroxyethoxy)benzene and capric acid, 1,4-bis(2-hydroxyethoxy)benzene and laurin Examples include diesters with acids, diesters with 1,4-bis(2-hydroxyethoxy)benzene and myristic acid, and the like.

（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, a compound represented by the following formula (6) may be used as the component (c).

(Wherein, 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; n represents 1 to 20 indicates an integer of

Examples of the compound represented by formula (6) include a diester of succinic acid and 2-phenoxyethanol, a diester of suberic acid and 2-phenoxyethanol, a diester of sebacic acid and 2-phenoxyethanol, and 1,10-decanedicarboxylic acid. and 2-phenoxyethanol, and diesters 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, a compound represented by the following formula (7) may be used as the component (c).

(wherein R is an alkyl group having 4 to 22 carbon atoms, a cycloalkylalkyl group, a cycloalkyl group, or an alkenyl group having 4 to 22 carbon atoms, X is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and n is 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, 4- nonyl biphenylacetate, decyl 4-biphenylacetate, lauryl 4-biphenylacetate, myristyl 4-biphenylacetate, tridecyl 4-biphenylacetate, pentadecyl 4-biphenylacetate, cetyl 4-biphenylacetate, cyclopentyl 4-biphenylacetate, 4-biphenylacetate Examples include cyclohexylmethyl, 4-biphenylhexylacetate, 4-biphenylacetate cyclohexylmethyl and the like.

（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, a compound represented by the following formula (8) may be used as the component (c).

(Wherein, 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 , a halogen atom, Y represents a hydrogen atom or a methyl group, 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, 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, a compound represented by the following formula (9) may be used as the component (c).

(Wherein, R represents an alkyl group having 4 to 22 carbon atoms, an alkenyl group having 4 to 22 carbon atoms, a cycloalkylalkyl group, or a cycloalkyl group, and X represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, Y is a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom, and n is 0 or 1)

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

（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） Further, the component (c) may be a compound represented by the following formula (10).

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

Examples of the compound represented by formula (10) include phenoxyethyl ether of nonyl 4-hydroxybenzoate, phenoxyethyl ether of decyl 4-hydroxybenzoate, phenoxyethyl ether of undecyl 4-hydroxybenzoate, and dodecyl vanillate. Phenoxyethyl ether etc. can be illustrated.

（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, a compound represented by the following formula (11) may be used as the component (c).

(Wherein, 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 the compound represented by formula (11) include diesters of 1,3-bis(2-hydroxyethoxy)benzene and cyclohexanecarboxylic acid, and 1,4-bis(2-hydroxyethoxy)benzene and cyclohexanepropionic acid. and diesters 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, a compound represented by the following formula (12) may be used as the component (c).

(Wherein, R represents either an alkyl group having 3 to 17 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a cycloalkylalkyl group having 5 to 8 carbon atoms; X is a hydrogen atom; 5 alkyl group, methoxy group, ethoxy group, or halogen atom, and n is an integer of 1 to 3)

Examples of the compound represented by formula (12) include diesters of 4-phenylphenol ethylene glycol ether and cyclohexanecarboxylic acid, diesters of 4-phenylphenol diethylene glycol ether and lauric acid, and 4-phenylphenol triethylene glycol ether. Diesters of cyclohexanecarboxylic acid, diesters of 4-phenylphenol ethylene glycol ether and octanoic acid, diesters of 4-phenylphenol ethylene glycol ether and nonanoic acid, diesters of 4-phenylphenol ethylene glycol ether and decanoic acid, 4 - A diester of phenylphenol ethylene glycol ether and myristic acid can be exemplified.

The proportions of components (a), (b), and (c) in the thermochromic color-memory composition depend on the concentration, color change temperature, color change form, and type of each component, but are generally desired. The component ratio that provides the characteristics of (a) component 1 is preferably 0.1 to 100, more preferably 0.1 to 50, and still more preferably 0.5 to 20. Especially preferably 2 to 20, component (C) is preferably 1 to 800, more preferably 5 to 200, still more preferably 5 to 100, particularly preferably 10 to 100 (the above ratios are all parts by mass).

The thermochromic color-memory composition is encapsulated in microcapsules to form a thermochromic color-memory microcapsule pigment (hereinafter sometimes referred to as "microcapsule pigment"), or a thermoplastic resin or Used as a thermochromic color-memory material by dispersing it in a thermosetting resin to form thermochromic color-memory resin particles (hereinafter sometimes referred to as "resin particles") However, the thermochromic color-memory composition is preferably encapsulated in microcapsules and used as a microcapsule pigment. By encapsulating it in microcapsules, it is possible to constitute a chemically and physically stable pigment, and furthermore, the composition of the thermochromic color-memory composition can be maintained at the same composition under various conditions of use. This is because the same action and effect can be achieved.

Microencapsulation can be performed by known interfacial polymerization method, in situ polymerization method, in-liquid curing coating method, phase separation method from aqueous solution, phase separation method from organic solvent, melting dispersion cooling method, air suspension coating method, spraying There is a drying method, etc., and it is appropriately selected according to the application. Furthermore, depending on the purpose, the surface of the microcapsules may be provided with a secondary resin film to impart durability, or the surface properties may be modified for practical use.
Incidentally, by blending a non-thermochromic colorant such as a general dye or pigment at the time of microencapsulation, a tautomatic color change from colored (1) to colored (2) can be brought about.
The thermochromic color-memory microcapsule pigment preferably has a mass ratio of inclusions to wall film of 7:1 to 1:1, and the mass ratio of inclusions to wall film is within the above range. Thus, it is possible to prevent deterioration of color density and sharpness at the time of color development. More preferably, the mass ratio of inclusions:wall membrane is from 6:1 to 1:1.

The average particle size of the microcapsule pigment or resin particles is preferably 0.1 to 50 μm, more preferably 0.1 to 30 μm, even more preferably 0.5 to 20 μm. When the average particle size of the microcapsule pigment or resin particles exceeds 50 μm, the dispersion stability and processability tend to be poor. On the other hand, if the average particle size is less than 0.1 μm, it becomes difficult to exhibit high density color development.
Further, by making the microcapsule pigment or resin particles into fine particles, ΔH can be increased relative to ΔH of the three-component composition.
In addition, the average particle size is measured by determining the area of the particles with image analysis type particle size distribution measurement software [manufactured by Mountec Co., Ltd., product name: Macview], and calculating the area of the area of the particles to determine the projected area circle equivalent diameter ( Heywood diameter) is calculated, and the average particle diameter of particles equivalent to a sphere of equal volume is measured as the value.
In addition, when the particle diameter of all or most of the particles exceeds 0.2 μm, a particle size distribution measuring device [manufactured by Beckman Coulter, Inc., product name: Multisizer 4e] is used to obtain isovolumetric spheres by the Coulter method. It can also be measured as the mean particle size of the equivalent particles.
Furthermore, a laser diffraction/scattering particle size distribution measuring device [manufactured by Horiba, Ltd., product name: LA- 300], the volume-based particle size and average particle size may be measured.

The temperature control indicator of the present invention is applied to articles that require temperature control, such as perishable foods, frozen foods, and pharmaceuticals to which cold chains are applied. The appropriate temperature range for these items is in the low temperature range, and from the aspect of hygiene control, the temperature is set at 0 to 10°C for fresh foods, and -18°C or lower for frozen foods, preferably -25°C or lower. In addition, pharmaceuticals are mainly set at 10°C or less, especially 2-8°C. The appropriate temperature range varies depending on the item, but the appropriate temperature range for the main items to which the cold chain is applied is in the low temperature range of over -30°C to 10°C or less, and is distributed and stored in a refrigerated or frozen state. be. The above goods or storage containers for which the appropriate temperature range is in the low temperature range are F1 class (temperature range exceeding -30°C and -20°C or less), C1 class (exceeding -20°C and -10°C) based on the Warehousing Act Warehouses or cooling such as refrigerators and freezers classified into Class C2 (temperature range above -10°C and below 0°C), Class C3 (temperature range above 0°C and below 10°C) Among cooling devices that are stored in equipment and are generally used in daily living environments, such as cooling devices using Peltier elements, cooling devices filled with a refrigerant such as cold water or ice chips, refrigerators, and freezers Therefore, it is possible to store the article within the appropriate temperature range by appropriately selecting it according to the appropriate temperature range of the article.

The temperature management indicator of the present invention uses two types of thermochromic color memory materials. Of the two types of thermochromic color-memory materials, the component (c) is the compound represented by the above formula (C), and the complete decoloring temperature _t4 is in the range of -25°C or higher and 15°C or lower. The thermochromic color-memory material (hereinafter sometimes referred to as "one thermochromic color-memory material") is in a colored state, and the complete color-developing temperature _t1 exceeds -30°C and is 10°C or less. (hereinafter sometimes referred to as "the other thermochromic color-memory material") is in a decolored state. Then, the color-developed thermochromic color-memory material is completely decolored at the complete decoloring temperature _t4 , or the decolorized thermochromic color-memory material is completely decolorized at the complete color-developing temperature _t1 . The coloring causes the temperature control indicator to change color, making it possible to determine whether or not the article requiring temperature control has deviated from the proper temperature range.
Here, the complete discoloration temperature _t4 of the color-developing thermochromic color-memory material is a temperature higher than the upper limit temperature of the appropriate temperature range, and the color-discoloring thermochromic color-memory material is completely developed. Since the temperature _t1 is lower than the lower limit temperature of the appropriate temperature range, the temperature control indicator of the present invention can effectively function for temperature control within the appropriate temperature range of the article.
In other words, the complete discoloration temperature t ₄ of the thermochromic color-memory material in the colored state and the upper limit temperature T _MAX of the appropriate temperature range of the article satisfy T _MAX < t ₄ , so that the article or its storage container is appropriate. Deviating from a temperature environment higher than the temperature range can be determined by the color change of the temperature control indicator. In order to strictly control the temperature, the difference (ΔT _MAX ) between the temperature t ₄ and the temperature T _MAX (=(Complete discoloration temperature t ₄ of the thermochromic color-memory material in the developing state)-(Appropriate temperature range The upper limit temperature T _MAX )] preferably satisfies 0<ΔT _MAX ≦3, more preferably 0<ΔT _MAX ≦2, and even more preferably 0<ΔT _MAX ≦1.
Similarly, the complete coloring temperature t ₁ of the thermochromic color-memory material in the decolored state and the lower limit temperature T _min of the appropriate temperature range of the article satisfy t ₁ <T _min , so that the article or its storage container It can be determined by the color change of the temperature control indicator that the temperature has deviated from the proper temperature range. In order to strictly control the temperature, the difference between the temperature t ₁ and the temperature T _min (ΔT _min ) [= (the lower limit temperature T _min of the appropriate temperature range) - (the temperature-sensitive color-changing color-memory material in the decolored state is The coloring temperature t ₁ )] is preferably 0<ΔT _min ≦3, more preferably 0<ΔT _min ≦2, and even more preferably 0<ΔT _min ≦1.

The complete discoloration temperature _t4 of the thermochromic color-memory material in the decolored state is higher than the complete discoloration temperature _t4 of the thermochromic color-memory material in the decolored state, and the temperature-sensitive in the decolored state. The complete color development temperature _t1 of the color-changing color-memory material is higher than the complete color-developing temperature _t1 of the color-developed thermochromic color-memory material. As a result, once the temperature control indicator deviates from the proper temperature range of the article, it becomes difficult to return to the temperature control indicator before discoloration, in which one of the initial thermochromic color-memory materials is in a colored state. The temperature control indicator makes it possible to irreversibly determine whether or not the article requiring temperature control or its storage container has been stored without deviating from the appropriate temperature range even once.

In the temperature control indicator of the present invention, the color-developing thermochromic color-memory material becomes a colorless state in a temperature range of a complete color-changing temperature _t4 or higher, or the colorless thermochromic color-memory material is in a colorless state. It is possible to determine whether the article or its storage container has deviated from the appropriate temperature range by the material becoming colored in the temperature range of the complete coloring temperature _t1 , and the upper limit temperature of the appropriate temperature range and the coloring state , _the lower limit temperature of the proper temperature range and the complete color development temperature _t1 of the thermochromic color-memory material in the decolored state correspond to each other.
Here, when one type of thermochromic color-memory material is used as a temperature control indicator, the complete decoloring temperature _t4 is set to the upper limit temperature of the appropriate temperature range, and the complete coloring temperature _t1 is set to the lower limit temperature of the appropriate temperature range. Although it is necessary to correspond to each, since the complete color erasing temperature t ₄ and the complete color development temperature t ₁ are determined by the type of the component (c) used in the thermochromic color-memory material, both the temperature t ₄ and the temperature t ₁ correspond to the upper limit temperature and lower limit temperature of the appropriate temperature range. In other words, depending on the proper temperature range of the article, it may be difficult to control the temperature with a temperature control indicator using a thermochromic color-memory material.
The temperature control indicator of the present invention also determines the complete color erasing temperature _t4 and the complete coloring temperature _t1 depending on the type of component (c) of each thermochromic color memory material. By using two kinds of thermochromic color-memorizing materials, it becomes unnecessary to correspond the temperature _t4 and the temperature _t1 of each thermochromic color-memory material to the upper limit temperature and the lower limit temperature of the appropriate temperature range, respectively. That is, the complete discoloration temperature _t4 of the color-developing thermochromic color-memory material is set to the upper limit temperature of the appropriate temperature range, and the complete color-development temperature _t1 of the decolorized thermochromic color-memory material is set to the appropriate temperature. It is sufficient to correspond to the lower limit temperature of the range, and regardless of the proper temperature range of the article, the temperature control indicator using the thermochromic color-memory material facilitates temperature control.
Furthermore, by changing the type of the component (c) used in each thermochromic color-memory material, it is possible to change the complete color disappearance temperature _t4 of the thermochromic color-memory material in the colored state and the temperature sensitivity in the color-discolored state. Since the complete color development temperature _t1 of the discoloration color-memory material can be adjusted to any temperature, it is easy to use the temperature control indicator of the present invention to control the temperature even for articles with a narrow appropriate temperature range. Become.

In the initial state of the temperature control indicator of the present invention, one thermochromic color-memory material (thermochromic color-memory material A) is in a coloring state, and the other thermochromic color-memory material (thermochromic color-memory material A) is in a colored state. When the thermochromic color-memorizing material B) is in a decolored state and within the appropriate temperature range of the article requiring temperature control, only the color of the thermochromic color-memory material in a colored state is visible.
An example of the color change behavior of the temperature control indicator in the initial state is shown in FIG. 2, and another example is shown in FIG. In FIGS. 2 and 3, the vertical axis represents color density and the horizontal axis represents temperature, and the change in color density due to temperature changes progresses along the arrows. 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 bleached state. Here, t ₁ , t ₂ , t ₃ , and t ₄ respectively represent the complete coloring temperature, the color development start temperature, the color change start temperature, and the complete color change temperature of the thermochromic color-memory material in the colored state, and t. ₁ ', _t2 ', _t3 ', and _t4 ' represent the complete color development temperature, color development start temperature, color change start temperature, and complete color change temperature, respectively, of the thermochromic color-memory material in the colorless state. there is Hereinafter, the complete color development temperature t ₁ , the color development start temperature t ₂ , the color change start temperature t ₃ , and the complete color change temperature t ₄ of the color-removed thermochromic color-memory material are referred to as "complete color development temperature t ₁ '. ”, “color development start temperature t ₂ ′”, “discoloration start temperature t ₃ ′”, and “complete discoloration temperature t ₄ ′”.
In the temperature control indicator in the initial state, a is a point representing the concentration of the thermochromic color-memory material in the developing state at a certain temperature t within the appropriate temperature range, and b is a point in the temperature control indicator in the initial state. , the point representing the density of the thermochromic color-memory material in the 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 (temperature range exceeding temperature _t1 ' and below 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 of temperature t ₄ or higher), the color-developing thermochromic color-memory material disappears (arrow 1), Each thermochromic color-memory material becomes a decolorized state (state 1). Cooling is required to return _the thermochromic color- _memory material from this state to the color-developing state. temperature range), the other thermochromic color-memory material (thermochromic color-memory material that is decolored in the initial state) develops color (arrow 2), and the other thermochromic color Only the memory material becomes colored (state 2). When placed in a temperature range equal to or lower than temperature _t1 , one of the thermochromic color-memory materials develops color (arrow 3), and each thermochromic color-memory material develops 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 (temperature range exceeding temperature _t1 ' and below 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 t ₁ '), the decolorized thermochromic color-memory material develops color (arrow 1' ), each thermochromic color-memorizing material becomes a colored state (state 3'). _In order to return the thermochromic color-memory material from this state to the decolorized state, heating _is required. temperature range), one of the thermochromic color-memory materials (the thermochromic color-memory material that develops color in the initial state) decolors (arrow 2'), and the other thermochromic color-change The thermochromic color-memorizing material (the color-removing thermochromic color-memorizing material in the initial state) is in the colored state (state 2'). When placed in a temperature range equal to or higher than the temperature t ₄ ′, the other thermochromic color-memory material is decolored (arrow 3 ′), and both of the thermochromic color-memory materials are in a decolorized state. becomes (state 1').
From the above, the temperature management indicator of the present invention is placed in a temperature environment higher than the appropriate temperature range of the article even once from the initial state, or in a temperature environment lower than the appropriate temperature range. Since it is difficult for the memory material to return to the color-developed state of the temperature control indicator before discoloration, whether the article requiring temperature control or its storage container has been stored without deviating from the appropriate temperature range even once. can be irreversibly determined.

The temperature control indicator of the present invention indicates that each thermochromic color-memory material has deviated from a temperature environment that is higher than the appropriate temperature range by causing both of the thermochromic color-memory materials to be in a decolored state. When both materials become colored, it can be determined that the temperature environment has deviated from the appropriate temperature range. The article deviates from a temperature environment higher than the appropriate temperature range and a temperature environment lower than the appropriate temperature range by keeping only the state in which only the thermochromic color-memory material) is in the coloring state. can be determined.
This is because the complete decoloring temperature t ₄ (complete decoloring temperature t ₄ ′) of the thermochromic color-memory material in the decolored state is the complete decoloring temperature t of the thermochromic color-memory material in the developed state. ₄ and the complete color-developing temperature t ₁ (complete color-developing temperature t ₁ ′) of the thermochromic color-memory material in the color-developed state is equal to the complete color-developing temperature t This is because it is greater than ₁ .
When the temperature t ₄ ′ is higher than the temperature t ₄ , the temperature environment deviates from the initial state to a temperature environment lower than the proper temperature range, and the temperature-sensitive color-changing color-memory materials both develop colors (state 3 ′). When the temperature environment deviates from the appropriate temperature range, only the other thermochromic color-memory material develops color under a specific temperature environment (temperature range of temperature _t4 or more and temperature _t4 ' or less). state. This state is expressed only when the temperature environment deviates from the initial state to a temperature environment lower than the appropriate temperature range and then to a temperature environment higher than the appropriate temperature range. Each deviation can be determined below.
Since it becomes easier for the temperature control indicator to distinguish when the temperature is higher than the proper temperature range or when the temperature is lower than the proper temperature range, the difference (Δt ₄ ) between the temperature t ₄ ′ and the temperature t ₄ (= (complete consumption) Color temperature t ₄ ′)−(Complete decoloring temperature t ₄ )] preferably satisfies Δt ₄ ≧5, more preferably Δt ₄ ≧10. When Δt ₄ satisfies the above range, one of the thermochromic color-memory materials (initial When one of the thermochromic color-memory materials in the color-developing state in the first state disappears at temperature _t4 , the other thermochromic color-memory material is easily maintained in a completely developed state.

Similarly, when the temperature t ₁ ′ is higher than the temperature t ₁ , the temperature environment deviates from the initial state to a temperature environment higher than the appropriate temperature range, and the temperature-sensitive color-changing color-memory materials are both decolored. When deviating from (state 1) under a temperature environment lower than the appropriate temperature range, the other temperature-sensitive color-changing color memory under a specific temperature environment (temperature range exceeding temperature t ₁ and not exceeding temperature t ₁ ′) Only the material becomes colored. This state is expressed only 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. Each deviation can be determined below.
Since it becomes easier for the temperature control indicator to distinguish when the temperature is higher than the appropriate temperature range or when the temperature is lower than the appropriate temperature range, the difference (Δt ₁ ) between the temperature t ₁ ′ and the temperature t ₁ [= (complete coloring The temperature t ₁ ′)−(complete coloring temperature t ₁ )] preferably satisfies Δt ₁ ≧5, more preferably Δt ₁ ≧10. When Δt ₁ satisfies the above range, in the process of cooling the other thermochromic color-memory material from the decolored state (state 1), the other thermochromic color-memory material reaches temperature t. When the color is developed in ₁ ', one of the thermochromic color-memory materials is easily maintained in a completely decolored state.

Since the temperature control indicator makes it easy to determine that the temperature control indicator has deviated from the appropriate temperature range in a temperature environment higher or lower than the appropriate temperature range, the decoloration start temperature t ₃ ( The discoloration start temperature t ₃ ′) is preferably higher than the complete discoloration temperature t ₄ of the thermochromic color-memory material in the colored state (t ₃ ′>t ₄ ). As a result, in the process of heating the thermochromic color-memory materials from the state in which both the thermochromic color-memory materials develop colors (state 3'), one of the thermochromic color-memory materials (the thermochromic color-memory material in the initial state) When one thermochromic color-memory material) is completely bleached at temperature _t4 , the other thermochromic color-memory material (the thermochromic color-memory material that is bleached in the initial state) completely develops color. It becomes easy to be held in a state where Therefore, it becomes easy to clearly determine whether the article has deviated from the temperature environment lower than the proper temperature range or the temperature environment higher than the proper temperature range.
Further, since the other thermochromic color-memory material is more easily retained in a completely colored state, the difference between temperature t ₃ ′ and temperature t ₄ (t ₃ ′−t ₄ ) [=( The decoloring start temperature t ₃ ′)−(complete decoloring temperature t ₄ )] preferably satisfies (t ₃ ′−t ₄ )≧1, and preferably satisfies (t ₃ ′−t ₄ )≧3. More preferably, (t ₃ ′−t ₄ )≧5.

Since the temperature control indicator makes it easier to distinguish between a temperature environment higher than the appropriate temperature range and a temperature environment lower than the appropriate temperature range, the complete color development temperature t ₁ (complete The color development temperature t ₁ ′) is preferably higher than the color development start temperature t ₂ of the thermochromic color-memory material in the color developed state (t ₁ ′>t ₂ ). As a result, in the process in which both of the thermochromic color-memory materials are cooled from the bleached state (state 1), the other thermochromic color-memory material (the thermochromic color-memory material in the bleached state in the initial state When one of the thermochromic color-memory materials (thermochromic color-memory material that develops color in the initial state) completely loses color at temperature t ₁ ′ It becomes easy to be held in a state where Therefore, it becomes easy to clearly determine whether the article has deviated from the temperature environment lower than the proper temperature range or the temperature environment higher than the proper temperature range.
Further, since one of the thermochromic color-memory materials is more likely to be maintained in a completely decolored state, the difference between temperature t ₁ ′ and temperature t ₂ (t ₁ ′−t ₂ ) [= (Complete coloring temperature t ₁ ′)−(Coloring start temperature t ₂ )] preferably satisfies (t ₁ ′−t ₂ )≧1, more preferably (t ₁ ′−t ₂ )≧3. Preferably, (t ₁ ′−t ₂ )≧5.

Since the temperature control indicator makes it easy to determine that the temperature control indicator has deviated from the appropriate temperature range under a temperature environment higher or under a temperature environment lower than the appropriate temperature range, the completely decoloring temperature t ₄ ( The complete decoloring temperature t ₄ ′) is preferably 40° C. or higher (t ₄ ′≧40). As a result, the other thermochromic color-memory material in a colored state (the thermochromic color-memory material in a decolored state in the initial state) is difficult to decolor under a daily living environment (for example, normal temperature range). Thus, in the process in which each thermochromic color-memory material develops color (state 3') and is heated, the other thermochromic color-memory material is easily maintained in a completely developed state. . Therefore, it is possible to easily determine whether or not the article has deviated from a temperature environment lower than or higher than the appropriate temperature range. The normal temperature is based on 20±15° C. specified in JIS Z 8703, and the normal temperature range is the temperature range of 5° C. or more and 35° C. or less.
The complete decoloring temperature t ₄ ′ is more preferably 50° C. or higher, more preferably 60° C. or higher. When the temperature t ₄ ′ satisfies the above range, the other thermochromic color-memory material in the coloring state becomes even more difficult to decolor under everyday living conditions, and is heated from the state 3′. In the process, it is more likely to be retained in a completely colored state.

Since the temperature control indicator makes it easy to distinguish between a temperature environment higher than the appropriate temperature range and a temperature environment lower than the appropriate temperature range, the complete color development temperature t ₁ of the color-developing thermochromic color-memory material is -30. ° C. or less (t ₁ ≦−30).
The temperature range of −30° C. or less is a temperature range that is difficult to reach with cooling tools commonly used in everyday living environments _. In the cooler generally used below, the thermochromic color-memory material in the decolored state becomes difficult to develop color, and the state (state 1) in which each thermochromic color-memory material is decolored. In the process of cooling, one of the thermochromic color-memory materials (the thermochromic color-memory material in the initial state of color development) is likely to be maintained in a decolored state. Therefore, only the other thermochromic color-memory material (the thermochromic color-memory material that is decolored in the initial state) is in a completely colored state, and the article is in a temperature environment higher than the appropriate temperature range. It is possible to easily determine whether or not the temperature has deviated from the low temperature environment.
The complete color development temperature t ₁ is more preferably −40° C. or lower, more preferably −50° C. or lower. When the complete color development temperature _t1 satisfies the above range, one of the decolorized thermochromic color-memory materials becomes even more difficult to develop color with a cooling device generally used in daily living environment. Thus, only the other thermochromic color-memory material is easily maintained in a completely developed state.

In the temperature control indicator of the present invention, the color-developing start temperature _t3 of the thermochromic color-memory material in the color-developing state is the color-developing start temperature _t2 of the color-developing thermochromic color-memory material (color-developing start temperature t ₂ ') (t ₃ >t ₂ '). As a result, the temperature control indicator in the initial state indicates a completely colored state for the thermochromic color-memory material in the color developing state at a certain temperature within the appropriate temperature range, becomes easy to maintain a completely decolored state, and only the color of one thermochromic color-memory material becomes easy to be visually recognized. Therefore, when the temperature control indicator deviates from the appropriate temperature range and changes color, the temperature control indicator clearly changes color from the initial state, making it easy to determine whether the temperature has deviated from the appropriate temperature range. be able to.

Each thermochromic color-memory material applied to the present invention has a decoloration start temperature _t3 higher than a color development start temperature _t2 ', and a decoloration start temperature _t3 ' is higher than a complete decoloration temperature _t4. It is preferred that the full color development temperature t ₁ ′ is greater than the color initiation temperature t ₂ . Further, it is preferable that the complete decoloring temperature t ₄ ′ is 40° C. or higher and the complete coloring temperature t ₁ is −30° C. or lower.

The temperature management indicator of the present invention comprises a first reversible thermochromic body comprising a thermochromic color-memory material and a second reversible thermochromic body comprising a thermochromic color-memory material. It is a thing. Here, as the configuration of the temperature control indicator (10), for example, as shown in FIGS. and a structure in which the second reversible thermochromic body (30) is laminated on the first reversible thermochromic body (20). If the temperature management indicator is of laminated construction, the size of the second reversible thermochromic body is preferably smaller than the first reversible thermochromic body.
An example of color change when two reversible thermochromic bodies are arranged side by side will be described with reference to FIG. 6, and an example of color change when laminated will be described with reference to FIG.

In FIGS. 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 at a certain temperature t within the proper temperature range, the thermochromic color in the colored state Only the color due to the memory material 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 t ₄ or higher), the color shown by each thermochromic color-memory material in the decolored state is visually recognized (state b ). From this state, when placed in a specific temperature environment lower than the appropriate temperature range (temperature range exceeding temperature _t1 and not exceeding temperature _t1 '), the other thermochromic color-memory material (disappears in the initial state) The color exhibited by the thermochromic color-memory material in the color state) in the developed state is visually recognized (state c). Furthermore, when placed in a temperature range equal to or lower than the temperature t ₁ , the color exhibited by each thermochromic color-memory material in the developed state is visually recognized (state d).
Similarly, when the temperature control indicator in state a is placed in a temperature environment lower than the proper temperature range (temperature range below temperature t ₁ '), the color exhibited by each thermochromic color-memory material in the developed state changes to It is visible (state d'). From this state, when placed in a specific temperature environment higher than the proper temperature range (temperature range of temperature t ₄ or more and temperature t ₄ ′), the other temperature-sensitive color-changing color-memory material (discolored in the initial state) The color exhibited by the thermochromic color-memory material in the state) in the developed state is visually recognized (state c'). Furthermore, when placed in a temperature range equal to or higher than the temperature t ₄ ′, the color exhibited by each thermochromic color-memory material in the decolorized state is visually recognized (state b′).
In other words, once the temperature control indicator of the present invention deviates from the proper temperature range even once from the initial state, it is difficult to return one of the thermochromic color-memory materials to the initial temperature control indicator before discoloration, in which the color develops. Therefore, it is possible to irreversibly determine whether or not the article requiring temperature control or its storage container has been stored without deviating from the appropriate temperature range even once.

Here, when the temperature control indicator has a structure in which the second reversible thermochromic body is laminated on the first reversible thermochromic body, for example, as shown in FIG. 8, the second reversible thermochromic body is transparent. may have gender. In this case, the first reversible thermochromic material and the second reversible thermochromic material may have the same size.
An example of 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 a certain temperature t within the appropriate temperature range In this case, a mixed color of the color shown by the thermochromic color-memory material in the developed state and the color shown by the thermochromic color-memory material in the decolorized state is visually recognized (state a). When the temperature control indicator is placed in a temperature environment higher than the appropriate temperature range (temperature range of temperature t ₄ or higher), the color that each thermochromic color-memory material shows in the decolorized state becomes a mixed color. (state b). From this state, when placed in a specific temperature environment lower than the appropriate temperature range (temperature range exceeding temperature _t1 and not exceeding temperature _t1 '), the other thermochromic color-memory material (disappears in the initial state) The color that the thermochromic color-memory material in the color state) shows in the colored state, and the one thermochromic color-memory material (the thermochromic color-memory material that develops the color in the initial state) is in the decolored state. A mixed color of the colors indicated by is visually recognized (state c). Furthermore, when placed in a temperature range of t ₁ or less, a color obtained by mixing the colors shown by each thermochromic color-memory material in the developed state is visually recognized (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 equal to or lower than temperature t ₁ ′), the color exhibited by each thermochromic color-memory material in the developed state is mixed. The resulting color is visually recognized (state d'). From this state, when placed in a specific temperature environment higher than the proper temperature range (temperature range of temperature t ₄ or more and temperature t ₄ ′), the other temperature-sensitive color-changing color-memory material (discolored in the initial state) The color shown in the color-developed state of the thermochromic color-memory material in the state) and the color of one thermochromic color-memory material (the thermochromic color-memory material in the initial state) in the decolored state A color obtained by mixing the indicated colors is visually recognized (state c'). Furthermore, when placed in a temperature range of t ₄ ′ or higher, a color obtained by mixing the colors shown in the decolorized state of each thermochromic color-memory material is visually recognized (state b′).
In other words, once the above temperature control indicator deviates from the proper temperature range even once from the initial state, it is difficult to return one of the thermochromic color-memory materials to the initial temperature control indicator before discoloration, in which the color develops. Therefore, it is possible to irreversibly determine whether or not the article requiring temperature control or its storage container has been stored without deviating from the proper temperature range even once.
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 visually recognized through the second reversible thermochromic body, and each thermochromic color memory A color that is a mixture of the colors shown by the material is visually recognized. Therefore, the color change indicated by the temperature control indicator can be varied, and it becomes easy to determine whether the temperature control indicator has deviated from the proper temperature range. It is preferable to have transparency.

It is preferable that each thermochromic color-memory material applied to the present invention presents a different color in the developed state, that is, the component (a) of each thermochromic color-memory material is different from each other.
In this case, the color visually recognized when one of the thermochromic color-memory materials is developed is different from the color visually recognized when the other thermochromic color-memory material is developed. It becomes easy for the management indicator to determine whether or not the temperature has deviated from the proper temperature range.
In particular, in a structure in which the temperature control indicator is formed by laminating a transparent second reversible thermochromic material on the first reversible thermochromic material, both the thermochromic color-memory materials are in a color development state. In this case, since the color obtained by mixing the colors shown by each thermochromic color-memory material in the colored state is visually recognized, it is visually recognized when only one of the initial thermochromic color-memory materials is in the colored state. and 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. , the temperature control indicator has deviated from the initial state to a temperature environment that is lower than the appropriate temperature range, a temperature environment that is higher than the appropriate temperature range, or a temperature environment that is lower or higher than the appropriate temperature range. Whether or not can be easily and clearly determined.

The hysteresis width (ΔH) of each thermochromic color-memory material is 8 to 100°C, preferably 20 to 100°C, more preferably 30 to 100°C, and 30 to 80°C. is more preferred, and 30 to 60°C is particularly preferred. When the hysteresis width (ΔH) is within the above range, the temperature control indicator can easily function effectively for temperature control of articles whose proper temperature range is in the low temperature range.

The color-developing thermochromic color-memory material applicable to the present invention has a complete decoloring temperature t ₄ in the range of −25° C. or more and 15° C. or less (−25≦t ₄ ≦15). The color-state thermochromic color-memory material has a complete color development temperature t ₁ (complete color development temperature t ₁ ′) in a range exceeding −30° C. and 10° C. or less [−30<t ₁ (t ₁ ′). ≦10]. As a result, the temperature control indicator of the present invention can effectively function for temperature control of articles having an appropriate temperature range in the low temperature range.
Since the temperature control indicator of the present invention can effectively function in an article having an appropriate temperature range in a lower temperature range, the complete discoloration temperature t ₄ of the color-developing thermochromic color-memory material is −25. C. to 10.degree. C. ( _{-25.ltoreq.t.sub.4.ltoreq.10} ), and more preferably -25.degree. C. to _5.degree . Further, the complete coloring temperature t ₁ (t ₁ ') of the thermochromic color-memory material in the decolored state is in the range of -30°C to 5°C [-30 < t ₁ (t ₁ ') ≤ 5], and more preferably in the range [-30<t ₁ (t ₁ ')≦0] of more than −30° C. and 0° C. or less.

As the first reversible thermochromic body (20), as shown in FIG. 10, a thermochromic color-memory material such as a thermochromic color-memory microcapsule pigment or resin particles is coated on a support (201). Use a reversible thermochromic laminate [first reversible thermochromic laminate (20')] having a reversible thermochromic layer [first reversible thermochromic layer (202)] containing In addition, a reversible thermochromic molded article (first reversible thermochromic molded article (20″)) comprising a thermochromic color-memory material in a support may also be used.

As the second reversible thermochromic body (30), as shown in FIG. 11, a thermochromic color-memory material such as a thermochromic color-memory microcapsule pigment or resin particles is coated on a support (301). Use a reversible thermochromic laminate [second reversible thermochromic laminate (30')] having a reversible thermochromic layer [second reversible thermochromic layer (302)] containing In addition, a reversible thermochromic molded article (second reversible thermochromic molded article (30″)) comprising a support containing a thermochromic color-memory material can also be used.

Both the first reversible thermochromic material and the second reversible thermochromic material may have transparency, and in this case, the thermochromic color-memory material has transparency of the reversible thermochromic material. Blended within a range that does not damage.

The configuration of the temperature control indicator (10) is not particularly limited. For example, as shown in FIG. 12, a first reversible thermochromic laminate (20') and a second reversible thermochromic laminate ( 30') arranged side by side or laminated. Further, for example, as shown in FIG. 13, 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 laminated can be exemplified. . In addition, a structure in which the first reversible thermochromic laminate and the second reversible thermochromic molded body are arranged side by side or laminated, or the first reversible thermochromic molded body and the second reversible thermochromic molded body It may be constructed by arranging or stacking the flexible laminates.

A reversible thermochromic laminate having a reversible thermochromic layer provided on a support is a thermochromic color such as ink or paint in which a thermochromic color memory material is dispersed in a vehicle containing a binder resin. The memory liquid composition is subjected to printing methods such as screen printing, offset printing, gravure printing, coater, and transfer printing, or brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, and immersion. It can be obtained by printing or coating by a coating method such as coating.

The support is not particularly limited, and examples thereof include paper, synthetic paper, fibers, fabrics such as knitted fabrics, woven fabrics, and non-woven fabrics, synthetic leathers, leathers, plastics, glass, elastomers, rubbers, ceramics, metals, Wood, stone and the like can be exemplified. Although the shape may be uneven, a planar shape, a sheet shape, or a film shape is preferable.
When the reversible thermochromic laminate has transparency, a support having transparency is used. The support having transparency is colorless and transparent, or colored and transparent, so that patterns, letters, etc. of adjacent objects can be visually recognized. There is no particular limitation as long as the color change or the like can be visually recognized.
Examples of transparent supports include plastics, glass, elastomers, and rubbers.
Plastic is preferred as the support because it is easy to handle. 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 support is not easily embrittled in a low-temperature range or an ultra-low temperature range. - Plastics composed of styrene copolymer resins are preferred.

The binder resin is not particularly limited as long as it does not affect the color development, discoloration, discoloration, etc. of the thermochromic color-memory material, and general-purpose resins such as ionomer resins, isobutylene-maleic anhydride copolymer resins. , 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, polyacrylate, polymethylmethacrylate, epoxy acrylate resin, alkylphenol resin, rosin-modified phenolic resin, rosin-modified alkyd resin, phenolic resin-modified alkyd resin, Epoxy resin-modified alkyd resin, styrene-modified alkyd resin, acrylic-modified alkyd resin, amino alkyd 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 hydrocarbon resin, shellac, cyclized rubber, vinyl acetate emulsion resin, styrene-butadiene emulsion resin, acrylic Examples include acid ester emulsion resins, water-soluble alkyd resins, water-soluble melamine resins, water-soluble urea resins, water-soluble phenol resins, water-soluble epoxy resins, water-soluble polybutadiene, cellulose acetate, cellulose nitrate, ethyl cellulose, and the like.

In the reversible thermochromic laminate, by further using a non-thermochromic colorant such as general dyes and pigments in combination, it is possible to bring about a reversible color change from colored (1) to colored (2). Specifically, a structure in which a non-thermochromic layer containing a non-thermochromic colorant is provided between a support and a reversible thermochromic layer, or a non-thermochromic colorant in the reversible thermochromic layer. can be exemplified. When the reversible thermochromic laminate has transparency, the non-thermochromic colorant is blended within a range that does not impair the transparency.

A reversible thermochromic molded article comprising a support containing a thermochromic color-memory material is prepared by adding the above-mentioned thermochromic color-memory material to a molding resin selected from thermoplastic resins and thermosetting resins. The thermochromic color-memory molding resin composition obtained by melt-blending the material can be obtained by molding using a general-purpose molding method such as injection molding, extrusion molding, blow molding, or cast molding.

Molding resins that form the support include, for example, linear low-density polyethylene, low-density polyethylene, medium-density polyethylene, ultra-high-density polyethylene, chlorinated polyethylene, polypropylene, chlorinated polypropylene, polyisobutylene, polybutadiene, polymethyl Pentene, polystyrene, polyethylene terephthalate, polybutylene terephthalate, polycyclohexylene-dimethylene-terephthalate, polyvinyl acetate, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, polyacrylate, polymethacrylate, polyamide, co- Polymerized polyamide, polyamideimide, polyacetal, polyvinylformal, polyvinylbutyral, polyarylate, polyetherimide, polyetheretherketone, polycarbonate, polyphenylene ether, polyphenylene sulfide, polysulfone, fluororesin, ionomer resin, ethylene-propylene copolymer resin, ethylene -vinyl acetate copolymer resin, ethylene-vinyl alcohol copolymer resin, ethylene-acrylate copolymer resin, ethylene-methacrylate copolymer resin, ethylene-vinyl chloride copolymer resin, vinyl chloride-propylene copolymer resin, chloride Vinyl-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-styrene copolymer resin, styrene thermoplastic elastomer, Olefin thermoplastic elastomer, urethane thermoplastic elastomer, polyester thermoplastic elastomer, 1,2-polybutadiene thermoplastic elastomer, vinyl chloride thermoplastic elastomer, petroleum hydrocarbon resin, cellulose acetate, cellulose acetate propionate, Thermoplastic resins such as cellulose acetate butyrate, nitrocellulose, low molecular weight polyethylene, low molecular weight polypropylene, polybutene, coumarone-indene copolymer, phenoxy plastic,
Thermosetting of 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, silicone resin, etc. can be exemplified by flexible resins.

When the reversible thermochromic molded article has transparency, a molding resin that forms a transparent support is used. Molding resins for forming transparent supports include, for example, polyethylene, polypropylene, polyisobutylene, polybutadiene, polymethylpentene, polystyrene, polyethylene terephthalate, polybutylene terephthalate, polycyclohexylene-dimethylene-terephthalate, and polyvinyl acetate. , polyvinyl chloride, polyvinylidene chloride, acrylic acid ester resin, methacrylic acid ester resin, polyvinyl butyral, polyarylate, polyetherimide, polycarbonate, polysulfone, ionomer resin, ethylene-propylene copolymer resin, ethylene-vinyl acetate copolymer resin , ethylene-vinyl alcohol copolymer resin, ethylene-acrylate copolymer resin, ethylene-methacrylate copolymer resin, acrylonitrile-styrene copolymer resin, thermoplastic resin such as cycloolefin copolymer,
Thermosetting resins such as epoxy resins, epoxy acrylates, phenol resins, unsaturated polyester resins, urea resins, aryl resins and silicone resins can be exemplified.

In the reversible thermochromic molded article, by further using a non-thermochromic colorant such as general dyes and pigments in combination, a reversible color change from colored (1) to colored (2) can be brought about. Specifically, a configuration in which a non-thermochromic colorant is contained in the support can be exemplified. When the reversible thermochromic molded article has transparency, the non-thermochromic colorant is blended within a range that does not impair the transparency.

On the reversible thermochromic layer of the reversible thermochromic laminate or on the reversible thermochromic molding, a transparent protective layer is provided 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 a role of protecting the thermochromic color-memory material contained in the adjacent reversible thermochromic layer or reversible thermochromic molding from physical impact, and contains a resin or resin emulsion. The transparent protective layer can be provided by printing or applying a solution, or by adhering plastic, elastomer, rubber, or the like in the form of a plane, sheet, film, or the like.
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 resistant to embrittlement in a low-temperature range or an ultra-low temperature range, such as polyethylene, polyethylene terephthalate, acrylonitrile-butadiene. - It is preferably composed of a resin such as a styrene copolymer resin.
The transparent protective layer is provided by ordinary lamination, for example, dry lamination or hot melt lamination, or between the transparent protective layer and the adjacent reversible thermochromic layer or reversible thermochromic molding. It can be provided by thermocompression bonding with a heat-sealable film interposed therebetween.

Light stabilizers include ultraviolet absorbers, antioxidants, anti-aging agents, singlet oxygen quenchers, superoxide anion quenchers, ozone quenchers, visible light absorbers, infrared absorbers and the like.
Examples of transparent metallic luster pigments include natural mica, synthetic mica, glass flakes, alumina, and pigments obtained by coating the surface of transparent film flakes with a metal oxide such as titanium oxide as a core material.
Light resistance can be imparted by providing a layer in which these light stabilizers or transparent metallic luster pigments are fixed in a dispersed state.

The reversible thermochromic material can be easily adhered to the object by providing an adhesive layer on the surface in contact with the object.
In the structure in which the second reversible thermochromic body is laminated on the first reversible thermochromic body, for example, as shown in FIG. A configuration in which an adhesive layer [first adhesive layer (203)] is provided on the opposite surface [the surface in contact with the object (article or its storage container, etc.)], and the object is provided with the first reversible heat It is possible to use as a temperature control indicator by attaching a color change body and laminating a second reversible thermochromic body on the first reversible thermochromic body. Further, for example, as shown in FIG. 15, a configuration in which 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). Also, the second reversible thermochromic material can be adhered to the first reversible thermochromic material and laminated on the object for use.
Furthermore, a first adhesive layer is provided on the surface of the first reversible thermochromic body opposite to the surface on which the second reversible thermochromic body is provided, and the second reversible thermochromic body has the first By providing a second adhesive layer on the surface in contact with the reversible thermochromic body, the first reversible thermochromic body can be attached to an object such as an article or its storage container, and the first reversible A second reversible thermochromic body may be adhered to the thermochromic body for use.
Here, when the reversible thermochromic body is a reversible 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, the first reversible thermochromic body is provided with a first adhesive layer on the surface in contact with the object (article or its storage container, etc.), and the second reversible thermochromic body is provided with the object (article or The second adhesive layer is provided on the surface in contact with the storage container, etc.), and by attaching both the first reversible thermochromic body and the second reversible thermochromic body to the object, the first It can also be used as a temperature control indicator in which a reversible thermochromic body and a 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, discoloration, discoloration, etc. of the thermochromic color-memory material provided in the reversible thermochromic body and can be attached to an object. When the reversible thermochromic material has transparency, the patterns, characters, etc. of the adjacent object are visible, and when the object is the reversible thermochromic material, the patterns, characters, color change, etc. It is not particularly limited as long as it is visible.
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. etc. can be exemplified.
Considering that the temperature control indicator of the present invention is used in a low temperature range or an ultra-low temperature range, the adhesive is preferably one whose adhesiveness does not easily decrease in a low temperature range or an ultra-low temperature range. , silicone-based resins, and epoxy resins are suitable.
The adhesive layer may be provided with a release layer in order to improve convenience during use and workability of the reversible thermochromic body provided with the adhesive layer.

Further, when the reversible thermochromic body is a reversible thermochromic laminate and the support has transparency, the reversible thermochromic layer is provided on the support having transparency, and the reversible thermochromic layer has transparency. A configuration in which an adhesive layer is provided on the surface opposite to the support is also possible. The reversible thermochromic laminate having the above structure functions as a protective layer for the reversible thermochromic layer because the support having transparency is the outermost layer when attached, and the transparent protective layer is formed on the reversible thermochromic layer. Durability can be imparted to the reversible thermochromic layer without providing it.

The first reversible thermochromic laminate and the second reversible thermochromic laminate can use a falsification prevention member as a support. For example, as shown in FIG. 16, the support of the first reversible thermochromic laminate [20 (20')] may be a falsification prevention member (204) provided with an adhesive layer. By attaching the first reversible thermochromic body having the above-described structure to an object and stacking the second reversible thermochromic body on the first reversible thermochromic body, the article or its storage container is outside the appropriate temperature range. If the temperature environment deviates from the temperature environment, 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. .
Further, the support of the second reversible thermochromic laminate may be a tamper-proof member provided with an adhesive layer. By laminating or attaching a temperature control indicator in which the second reversible thermochromic body having the above configuration is attached to the first reversible thermochromic body, the temperature of the article or its storage container exceeds the appropriate temperature range. If the environment deviates, it is possible to prevent tampering such as peeling off the second reversible thermochromic body, re-cooling or re-heating and pasting, or exchanging with a new temperature control indicator.
Further, the support of the first reversible thermochromic material and the support of the second reversible thermochromic material may be tamper-proof members provided with adhesive layers. Tampering is further prevented by attaching the first reversible thermochromic body having the above structure to an object and attaching the second reversible thermochromic body having the above structure to the first reversible thermochromic body. can do.
Further, as shown in FIG. 17, the support of the transparent second reversible thermochromic laminate [31 (31′)] was combined with a transparent falsification prevention member (314) provided with an adhesive layer. You can also By laminating or attaching the temperature control indicator in which the second reversible thermochromic body having the above configuration is attached to the first reversible thermochromic body, the article or its storage container is kept outside the proper temperature range. When the temperature environment deviates, 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.

The tampering prevention member exhibits a tampering prevention function by providing an adhesive layer on the outermost layer of a member having a laminated structure.
As the tampering prevention member, a tampering prevention label, tape, sticker, or the like can be used. A tamper-proof member having a tamper-proof function of a type that is transferred to an object can be exemplified.
In addition, when peeled off after being attached to an object, separation occurs at the interface of the laminated structure, and the deformation of the layers leaves no residue on the object. An example of a tamper-preventing member having tamper-preventing properties, such as a type in which the base material is destroyed when it is peeled off after being attached to an object, leaving a trace of peeling on the adherend, can be exemplified.

Transparency in the present invention means the property of transmitting light in the visible light region (380 to 780 nm wavelength region defined by JIS B 7079).
When the first reversible thermochromic material or the second reversible thermochromic material has transparency, the light transmittance in the visible light region (visible light transmittance) is preferably 5% or more. % or more, more preferably 20% or more. When the visible light transmittance satisfies the above range, the pattern, characters, color change, etc. of the adjacent reversible thermochromic material, or the pattern, character, etc. of the adjacent object can be clearly visually recognized.
Further, 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, patterns, characters, color changes, etc. of the adjacent reversible thermochromic layer or reversible thermochromic molded article can be clearly and easily recognized.
Visible light transmittance, for example, can be measured using a spectrophotometer [manufactured by Hitachi, Ltd., product name: U-3210], on a transparent substrate that transmits light with a wavelength in the visible light region It can be obtained by providing a reversible thermochromic material or a transparent protective layer, measuring in a wavelength range from 380 nm to 780 nm using a spectrophotometer, and taking the intermediate value between the maximum and minimum values.

The temperature management 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 the _temperature -sensitive color-memory material (one of the sensitivity A reversible thermochromic body provided with a thermochromic color-memory material) is used as a first reversible thermochromic body, and the first reversible thermochromic body is used to bring the thermochromic color-memory material into a colored state. is cooled to a temperature below the complete coloring temperature _t1 to maintain the coloring 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 t ₁ ^′ in the range of more than −30° C. and 10° C. or less. The second reversible thermochromic body is heated at a temperature equal to or higher than the complete decoloring temperature t ₄ ′ in order to make the above-mentioned thermochromic color-memory material into a decolorized state as the second reversible thermochromic body. , to maintain the erased state.
Next, cooling of the first reversible thermochromic body and heating of the second reversible thermochromic body are stopped, and the first reversible thermochromic body and the second reversible thermochromic body are placed on the article or storage container under a temperature environment within the proper temperature range. Two reversible thermochromic bodies are arranged side by side to form a temperature control indicator. Alternatively, the second reversible thermochromic material is layered on the first reversible thermochromic material under a temperature environment within the proper temperature range to form a temperature control indicator, which is then layered on an article or storage container. The temperature control indicator in the initial state is such that 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 an article that requires temperature control or its storage is used. A change in the temperature of the container can be detected. From this state, it is possible to irreversibly determine that the article or its storage container has deviated from the appropriate temperature range by changing the color of the temperature management indicator.
Here, if the temperature control indicator is mistakenly placed in an environment with a temperature higher than the proper temperature range before use, and each reversible thermochromic body becomes colorless, the first reversible heat The discoloration body is removed and cooled again at a temperature not higher than the temperature _t1 to maintain the coloring state. Next, cooling of the first reversible thermochromic body is stopped, and the first reversible thermochromic body and the second reversible thermochromic body are arranged side by side again under a temperature environment within the appropriate temperature range, or the first reversible thermochromic body is By laminating the second reversible thermochromic body on the reversible thermochromic body, the temperature control indicator can be set to the initial state.
In addition, if the temperature control indicator is mistakenly placed in an environment with a temperature lower than the proper temperature range before use, and each reversible thermochromic body becomes colored, the temperature control indicator may be replaced with the second reversible thermochromic body is removed, and heated again at a temperature higher than the temperature t ₄ ′ to keep it in a decolorized state. Next, the heating of the second reversible thermochromic body is stopped, and the first reversible thermochromic body and the second reversible thermochromic body are again arranged side by side in a temperature environment within the proper temperature range, or the first By laminating the second reversible thermochromic body on the reversible thermochromic body, the temperature control indicator can be initialized.
In addition, a reversible thermochromic body provided with a thermochromic color-memory material (the other thermochromic color-memory material) having a complete coloring temperature t ₁ ^′ exceeding −30° C. and not more than 10° C. A thermochromic color as the first reversible thermochromic material, wherein the component (c) is a compound represented by the above formula (C), and the complete decoloring temperature _t4 is in the range of -25°C or higher and 15°C or lower. A reversible thermochromic body provided with a memory material (one thermochromic color memory material) can be used as the second reversible thermochromic body. In this case, the first reversible thermochromic body in the decolored state and the second reversible thermochromic body in the colored state are provided side by side, or the first reversible thermochromic body in the decolored state is placed on the first reversible thermochromic body in the decolored state. Two reversible thermochromic bodies can be laminated to form a temperature control indicator and used in a manner similar to that described above.

Examples are shown below, but the present invention is not limited thereto. In addition, the part in an Example shows a mass part.

Example 1
Preparation of thermochromic color-memory material A (thermochromic color-memory microcapsule pigment A) 1.5 parts of 2-methylindol-3-yl)-4-azaphthalide, 5 parts of 2,2-bis(4-hydroxyphenyl)hexafluoropropane as component (b), and capryl as component (c) A thermochromic color-memory composition consisting of 50 parts of 4-methylbenzyl acid was uniformly heated and dissolved to form a mixed solution consisting of 30 parts of an aromatic isocyanate prepolymer as a wall film material and 50 parts of a co-solvent. After the addition, the mixture was emulsified and dispersed in a 6% polyvinyl alcohol aqueous solution, and after continuing stirring while heating, 2.5 parts of a water-soluble aliphatic modified amine was 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 has an average particle size of 4.6 μm, complete color development temperature t ₁ : −55° C., color development start temperature t ₂ : −45° C., decoloration start temperature t ₃ : −10° C., complete decolorization. Temperature t ₄ : −6° C., ΔH: 42° C., and reversibly changed from blue to colorless with temperature change.

Preparation of thermochromic color-memory material B (thermochromic color-memory microcapsule pigment B) (A) As component, 6-(N-ethyl-N-isoamylamino)-1,2-benzofluorane 2 parts, 5 parts of 2,2-bis(4-hydroxyphenyl)hexafluoropropane and 10 parts of 1,1-bis(4-hydroxyphenyl)n-decane as components (b), and (c) as components , and 50 parts of 4-benzyloxyphenylethyl caprate are uniformly heated and dissolved, and 30 parts of an aromatic isocyanate prepolymer as a wall film material and 50 parts of a co-solvent are mixed. After being put into the mixed solution, emulsified and dispersed in an 8% polyvinyl alcohol aqueous solution, and after continuing stirring while heating, 2.5 parts of water-soluble aliphatic modified amine was added, and further stirring was continued to disperse microcapsules. A liquid was prepared. Microcapsule pigment B was obtained from the above microcapsule dispersion by centrifugation.
The microcapsule pigment B has an average particle size of 2.0 μm, complete color development temperature t ₁ ′: −21° C., color development start temperature t ₂ ′: −13° C., decoloration start temperature t ₃ ′: 38° C., complete Discoloration temperature t ₄ ′: 60° C., ΔH: 66° C., and reversibly changed from magenta to colorless with temperature change.

Fabrication of temperature control indicator (see Figure 12)
30 parts of the above microcapsule pigment A, 62 parts of a urethane emulsion, 2 parts of a thickener, 0.5 parts of a leveling agent, and an antifoaming agent were placed on a white polyester film having a thickness of 25 μm as a support (201). A thermochromic color-memory ink in which 0.5 part and 5 parts of a cross-linking agent are uniformly dispersed is solidly printed using a 120-mesh screen, dried and cured to form a first reversible thermal color change. A layer (202) was provided to obtain a first reversible thermochromic body (20) [first reversible thermochromic laminate (20')]. Next, the first reversible thermochromic body was cut to prepare a perfect circular first reversible thermochromic body with a diameter of 5 cm, in which the reversible thermochromic layer was visible on the entire surface.
30 parts of the above microcapsule pigment B, 62 parts of a urethane emulsion, 2 parts of a thickener, 0.5 parts of a leveling agent, and an antifoaming agent were placed on a white polyester film having a thickness of 25 μm as a support (301). 0.5 parts and 5 parts of a cross-linking agent are evenly dispersed in a thermochromic color-memory ink, which is solidly printed using a 120-mesh screen, dried and cured to form a second reversible thermal color change. A layer (302) was provided to obtain a second reversible thermochromic body (30) [second reversible thermochromic laminate (30')]. Next, the second reversible thermochromic body was cut to prepare a perfect circular second reversible thermochromic body with a diameter of 3 cm, in which the reversible thermochromic layer was visible on the entire surface.
The first reversible thermochromic material was cooled to −55° C. or below to maintain the colored state, and the second reversible thermochromic material was heated to 60° 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 are stopped, and the second reversible thermochromic body is placed on the first reversible thermochromic body in a temperature environment of -12°C. were laminated to produce a temperature control indicator (10).

Temperature control during distribution and storage of fresh fish (determines whether or not it deviates from the appropriate temperature range of -20°C or higher and -7°C or lower)
In a temperature environment of -12°C, when a temperature control indicator is layered on a storage container containing fresh fish whose proper temperature range is -20°C or higher and -7°C or lower, blue color due to the first reversible thermochromic body was visually recognized in a donut shape (initial state).

When the storage container is placed in a temperature environment of -6 ° C. or higher, the thermochromic color-memory material A provided in the first reversible thermochromic body disappears, the temperature control indicator changes color, and the first A white color was visually recognized as a perfect circle between the support of the reversible thermochromic material and the support of the second reversible thermochromic material (state 1).
When the temperature control indicator in state 1 exceeds −55° C. and is placed in a temperature environment of −21° C. or less, the thermochromic color-memory material B provided in the second reversible thermochromic body develops color, The magenta color due to the second reversible thermochromic material was visually recognized as a perfect circle (state 2).
When the temperature control indicator in state 2 is placed in a temperature environment of −55° C. or less, the thermochromic color-memory material A provided in the first reversible thermochromic body develops color, and the second reversible thermochromic material develops color. A perfect circle of magenta due to the body was visually observed, and a donut-like blue due to the first reversible thermochromic material was visually observed so as to surround the perfect circle of magenta (state 3).

Further, when the storage container is placed in a temperature environment of −21° C. or less, the thermochromic color-memory material B provided in the second reversible thermochromic body develops color, the temperature control indicator changes color, and the second reversible thermochromic body changes color. The magenta color by the second reversible thermochromic body was visually recognized in a perfect circle, and the blue color by the first reversible thermochromic body was visually recognized in a donut shape so as to surround the magenta perfect circle (state 3 ′).
When the temperature control indicator in state 3′ is placed in a temperature environment of −6° C. or more and less than 60° C., the thermochromic color-memory material A provided in the first reversible thermochromic body decolors, The magenta color due to the second reversible thermochromic body was visually recognized as a perfect circle (state 2').
When the temperature control indicator in state 2′ is placed in a temperature environment of 60° C. or higher, the thermochromic color-memory material B provided in the second reversible thermochromic body decolors, and the first reversible heat A white color was visually recognized as a perfect circle between the support of the color change material and the support of the second reversible thermochromic material (state 1').

If the storage container containing fresh fish is placed in a temperature environment outside the appropriate temperature range, the temperature control indicator will change color, and then one of the initial thermochromic color-memory materials (thermochromic color-memory Since it was difficult to restore the material A) to the color-developing temperature control indicator before discoloration, it was possible to irreversibly determine that the storage container deviated from the appropriate temperature range. Here, since the temperature _t3 is higher than the temperature _t2 ', it was easy to determine that the storage container deviated from the appropriate temperature range.
In addition, when the temperature environment deviates from the proper temperature range to a higher temperature environment or a lower temperature environment, only the other thermochromic color-memory material (thermochromic color-memory material B) develops color under a specific temperature environment. In order to maintain the state, it was possible to irreversibly determine whether the storage container deviated from the appropriate temperature range to a higher temperature environment or a lower temperature environment. Here, the temperature t ₄ ′ is 60° C., which is higher than the normal temperature range, the temperature t ₁ is −55° C., which is in the ultra-low temperature range, and Δt ₄ (t ₄ ′−t ₄ ): 66° C., ₁ (t ₁ '-t ₁ ): 34°C, (t ₃ '-t ₄ ): 44°C, (t ₁ '-t ₂ ): 24°C. It was easy to distinguish between deviations under the environment and under the low temperature environment.
Further, the difference (ΔT _MAX ) between the temperature t ₄ and the upper limit temperature T _MAX of the proper temperature range of the storage container satisfies 0<ΔT _MAX ≦1, and the temperature t ₁ ′ and the lower limit temperature T of the proper temperature range of the storage container Since the difference (ΔT _min ) from _min satisfies 0<ΔT _min ≦1, it was possible to more strictly control the temperature of fresh fish.

Example 2
Fabrication of temperature control indicator (see Figure 12)
30 parts of the microcapsule pigment A of Example 1, 62 parts of a urethane emulsion, 2 parts of a thickening agent, 0.5 parts of a leveling agent, and 0.5 parts of an antifoaming agent were placed on a white synthetic paper as a support (201). and 5 parts of a cross-linking agent are uniformly dispersed, and solid printing is performed using a 120-mesh screen plate, followed by drying and curing to form the first reversible thermochromic layer (202 ) to obtain a first reversible thermochromic body (20) [first reversible thermochromic laminate (20')]. Next, the first reversible thermochromic body was cut to prepare a semicircular first reversible thermochromic body with a radius of 5 cm, in which the reversible thermochromic layer was visible on the entire surface.
On a white synthetic paper as a support (301), 30 parts of the microcapsule pigment B of Example 1, 62 parts of a urethane emulsion, 2 parts of a thickening agent, 0.5 parts of a leveling agent, and 0.5 parts of an antifoaming agent. and 5 parts of a cross-linking agent are uniformly dispersed, and solid printing is performed using a 120-mesh screen plate, followed by drying and curing to form a second reversible thermochromic layer (302 ) to obtain a second reversible thermochromic body (30) [second reversible thermochromic laminate (30')]. Next, the second reversible thermochromic body was cut to prepare a semicircular second reversible thermochromic body with a radius of 5 cm, in which the reversible thermochromic layer was visible on the entire surface.
The first reversible thermochromic material was cooled to −55° C. or below to maintain the colored state, and the second reversible thermochromic material was heated to 60° C. or higher to maintain the decolored state and stored.

Temperature control during distribution and storage of fresh fish (determines whether or not it deviates from the appropriate temperature range of -20°C or higher and -7°C or lower)
In a temperature environment of -12°C, a first reversible thermochromic body and a second reversible thermochromic body are placed in a storage container for storing fresh fish with an appropriate temperature range of -20°C or higher and -7°C or lower. , were arranged side by side so as to form a perfect circle with a diameter of 5 cm to form a temperature control indicator (10). As for the temperature control indicator, a semicircular blue color due to the first reversible thermochromic body was visible on the right half (initial state).

When the storage container is placed in a temperature environment of -6 ° C. or higher, the thermochromic color-memory material A provided in the first reversible thermochromic body disappears, the temperature control indicator changes color, and the first White was visually recognized as a perfect circle by the support of the reversible thermochromic material and the support of the second reversible thermochromic material (state 1).
When the temperature control indicator in state 1 exceeds −55° C. and is placed in a temperature environment of −21° C. or less, the thermochromic color-memory material B provided in the second reversible thermochromic body develops color, On the left half of the temperature control indicator, a semicircular magenta color due to the second reversible thermochromic material was visually recognized (state 2).
When the temperature control indicator in state 2 is placed in a temperature environment of -55 ° C or less, the thermochromic color-memory material A provided in the first reversible thermochromic body develops color, and the left half of the temperature control indicator A semicircular magenta color due to the second reversible thermochromic material was visually recognized on the right half, and a semicircular blue color due to the first reversible thermochromic material was visually recognized on the right half (state 3).

Further, when the storage container is placed in a temperature environment of −21° C. or less, the thermochromic color-memory material B provided in the second reversible thermochromic body develops color, the temperature control indicator changes color, and the temperature A semicircular magenta color due to the second reversible thermochromic material was visible on the left half of the management indicator, and a semicircular blue color due to the first reversible thermochromic material was visible on the right half (state 3' ).
When the temperature control indicator in state 3′ is placed in a temperature environment of −6° C. or more and less than 60° C., the thermochromic color-memory material A provided in the first reversible thermochromic body decolors, A semicircular magenta color due to the second reversible thermochromic material was visually observed on the left half of the temperature control indicator (state 2').
When the temperature control indicator in state 2′ is placed in a temperature environment of 60° C. or higher, the thermochromic color-memory material B provided in the second reversible thermochromic body decolors, and the first reversible heat A white color was visually recognized as a perfect circle between the support of the color change material and the support of the second reversible thermochromic material (state 1').

If the storage container containing fresh fish is placed in a temperature environment outside the appropriate temperature range, the temperature control indicator will change color, and then one of the initial thermochromic color-memory materials (thermochromic color-memory Since it was difficult to restore the material A) to the color-developing temperature control indicator before discoloration, it was possible to irreversibly determine that the storage container deviated from the appropriate temperature range. Here, since the temperature _t3 is higher than the temperature _t2 ', it was easy to determine that the storage container deviated from the proper temperature range.
In addition, when the temperature environment deviates from the proper temperature range to a higher temperature environment or a lower temperature environment, only the other thermochromic color-memory material (thermochromic color-memory material B) develops color under a specific temperature environment. In order to maintain the state, it was possible to irreversibly determine whether the storage container deviated from the appropriate temperature range to a higher temperature environment or a lower temperature environment. Here, the temperature t ₄ ′ is 60° C., which is higher than the normal temperature range, the temperature t ₁ is −55° C., which is in the ultra-low temperature range, and Δt ₄ (t ₄ ′−t ₄ ): 66° C., ₁ (t ₁ '-t ₁ ): 34°C, (t ₃ '-t ₄ ): 44°C, (t ₁ '-t ₂ ): 24°C. It was easy to distinguish between deviations under the environment and under the low temperature environment.
Further, the difference (ΔT _MAX ) between the temperature t ₄ and the upper limit temperature T _MAX of the proper temperature range of the storage container satisfies 0<ΔT _MAX ≦1, and the temperature t ₁ ′ and the lower limit temperature T of the proper temperature range of the storage container Since the difference (ΔT _min ) from _min satisfies 0<ΔT _min ≦1, it was possible to more strictly control the temperature of fresh fish.

Example 3
Preparation of thermochromic color-memory material A (thermochromic color-memory microcapsule pigment A) As components (a), 2.5 parts of 1,3-dimethyl-6-diethylaminofluorane, and (b) A temperature-sensitive color change consisting of 5 parts of 2,2-bis(4-hydroxyphenyl)hexafluoropropane as components and 49 parts of cyclohexylmethyl caprate and 1 part of 4-benzyloxyphenylethyl palmitate as components (c). The color-memorizing composition is uniformly heated and dissolved, and added to a mixed solution of 30 parts of an aromatic isocyanate prepolymer as a wall film material and 50 parts of a co-solvent, and then emulsified and dispersed in a 6% polyvinyl alcohol aqueous solution. After continuing stirring while heating, 2.5 parts of a water-soluble modified aliphatic amine was 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 has an average particle size of 3.9 μm, complete color development temperature t ₁ : −44° C., color development start temperature t ₂ : −31° C., decoloration start temperature t ₃ : −15° C., complete decolorization. Temperature t ₄ : −9° C., ΔH: 25.5° C., and reversibly changed from orange to colorless with temperature change.

Preparation of thermochromic color-memory material B (thermochromic color-memory microcapsule pigment B) (A) As component, 3,3-bis(2-ethoxy-4-diethylaminophenyl)-4-azaphthalide 1 4 parts of 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 4 parts of 1,1-bis(4-hydroxyphenyl)n-decane as components (b), and 4 parts of 1,1-bis(4-hydroxyphenyl)n-decane as components (c) A thermochromic color-memory composition comprising 50 parts of bis(4-methoxyphenyl)methyl hexadecanoate was uniformly heated and dissolved, and 30 parts of an aromatic isocyanate prepolymer as a wall film material and 50 parts of a co-solvent were added. After being put into a mixed solution consisting of, emulsifying and dispersing in an 8% polyvinyl alcohol aqueous solution, continuing to stir while heating, adding 2.5 parts of a water-soluble aliphatic modified amine, and continuing to stir Microcapsules A dispersion was prepared. Microcapsule pigment B was obtained from the above microcapsule dispersion by centrifugation.
The microcapsule pigment B has an average particle diameter of 2.0 μm, complete color development temperature t ₁ ′: -21° C., color development start temperature t ₂ ′: -16° C., decoloration start temperature t ₃ ′: 41° C., complete Discoloration temperature t ₄ ′: 52° C., ΔH: 65° C., and reversibly changed from bluish green to colorless with temperature change.

Fabrication of temperature control indicator (see Figure 18)
30 parts of the above microcapsule pigment A, 62 parts of a urethane emulsion, 2 parts of a thickening agent, 0.5 parts of a leveling agent, and 0.5 parts of an antifoaming agent were placed on a white synthetic paper as a support (201). , 5 parts of a cross-linking agent are uniformly dispersed, and solid printing is performed using a 120-mesh screen plate, followed by drying and curing to form the first reversible thermochromic layer (202). A first reversible thermochromic body (20) [first reversible thermochromic laminate (20')] was obtained. Next, the first reversible thermochromic body was cut to prepare a 5 cm square first reversible thermochromic body in which the reversible thermochromic layer was visible over the entire surface.
As a transparent support (311), 30 parts of the above microcapsule pigment B, 62 parts of urethane emulsion, 2 parts of a thickening agent, and 0.5 parts of a leveling agent were coated on a transparent polyester film having a thickness of 25 μm. , 0.5 parts of an antifoaming agent and 5 parts of a cross-linking agent are uniformly dispersed in a thermochromic color-memory ink, which is solidly printed using a 120-mesh screen plate, dried and cured. Two reversible thermochromic layers (302) were provided to obtain a transparent second reversible thermochromic body (31) [transparent second reversible thermochromic laminate (31')]. Next, the second reversible thermochromic body was cut to prepare a 5 cm square second reversible thermochromic body in which the reversible thermochromic layer was visible over the entire surface.
The first reversible thermochromic material was cooled to −44° C. or below to maintain the colored state, and the second reversible thermochromic material 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 are stopped, the second reversible thermochromic body is laminated on the first reversible thermochromic body, and the temperature control indicator (10 ) was produced, but was mistakenly laminated in a temperature environment of 18 ° C., and the first reversible thermochromic body in the colored state disappeared, so the first reversible thermochromic body was removed from the temperature control indicator. It was removed, cooled again to −44° C. or lower, and stored while maintaining the coloring state.
The cooling of the first reversible thermochromic body is stopped, and the second reversible thermochromic body is laminated on the first reversible thermochromic body in a temperature environment of -18°C, thereby producing the desired temperature control indicator. I was able to

Temperature control during distribution and storage of bread dough (determines whether or not it deviates from the appropriate temperature range of -20°C or higher and -10°C or lower)
In a temperature environment of -18 ° C., when a temperature control indicator is laminated on a storage container for storing bread dough with an appropriate temperature range of -20 ° C. or higher and -10 ° C. or lower, a temperature-sensitive color-changing color-memory material B starts to develop color, a light brown color obtained by mixing the orange color by the first reversible thermochromic material and the light blue-green color by the second reversible thermochromic material was visually recognized in a square shape (initial state).

When the storage container is placed in a temperature environment of -9 ° C. or higher, the thermochromic color-memory material A provided in the first reversible thermochromic body and the thermochromic property provided in the second reversible thermochromic body. The color-memorizing material B was decolored, the temperature control indicator changed color, and the white color due to the support of the first reversible thermochromic material was visually recognized as a square (state 1).
When the temperature control indicator in state 1 exceeds -44 ° C. and is placed in a temperature environment of -21 ° C. or less, the thermochromic color-memory material B provided in the second reversible thermochromic body develops color, A bluish-green square was visually recognized by the second reversible thermochromic material (state 2).
When the temperature control indicator in state 2 is placed in a temperature environment of −44° C. or less, the thermochromic color-memory material A provided in the first reversible thermochromic body develops a color, and the first reversible thermochromic color occurs. Brown (dark brown), which is a mixture of orange due to the body and bluish green due to the second reversible thermochromic material, was visually recognized in a square shape (state 3).

Further, when the storage container is placed in a temperature environment of −21° C. or less, the thermochromic color-memory material B provided in the second reversible thermochromic body develops color, the temperature control indicator changes color, and the second reversible thermochromic body changes color. Brown (dark brown), which is a mixture of orange color by one reversible thermochromic body and blue-green color by the second reversible thermochromic body, was visually recognized in a square shape (state 3').
When the temperature control indicator in state 3′ is placed in a temperature environment of −9° C. or more and less than 52° C., the thermochromic color-memory material A provided in the first reversible thermochromic body decolors, A bluish-green square was visually recognized by the second reversible thermochromic material (state 2').
When the temperature control indicator in state 2′ is placed in a temperature environment of 52° C. or higher, the thermochromic color-memory material B provided in the second reversible thermochromic body decolors, and the first reversible heat White squares due to the discoloration support were 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 then one of the initial thermochromic color-memory materials (thermochromic color-memory material Material A) is in a colored state, and the other thermochromic color-memory material (thermochromic color-memory material B) is in a slightly colored state, and it is difficult to return to the temperature control indicator before discoloration. Therefore, it was possible to irreversibly determine that the storage container deviated from the appropriate temperature range. Here, since the temperature _t3 is higher than the temperature _t2 ', it was easy to determine that the storage container deviated from the proper temperature range.
In addition, when the temperature environment deviates from the proper temperature range to a higher temperature environment or a lower temperature environment, only the other thermochromic color-memory material (thermochromic color-memory material B) develops color under a specific temperature environment. In order to maintain the state, it was possible to irreversibly determine whether the storage container deviated from the appropriate temperature range to a higher temperature environment or a lower temperature environment. Here, the temperature t ₄ ′ is 52° C., which is higher than the normal temperature range, the temperature t ₁ is −44° C., which is in the ultra-low temperature range, and Δt ₄ (t ₄ ′−t ₄ ): 61° C., ₁ (t ₁ '-t ₁ ): 23°C, (t ₃ '-t ₄ ): 50°C, (t ₁ '-t ₂ ): 10°C. It was easy to distinguish between deviations under the environment and under the low temperature environment.
In addition, the difference (ΔT _MAX ) between the temperature t ₄ and the upper limit temperature T _MAX of the appropriate temperature range of the storage container satisfies 0<ΔT _MAX ≤ 1, and the temperature t ₁ ′ and the lower limit temperature T of the appropriate temperature range of the storage container Since the difference (ΔT _min ) from _min satisfies 0<ΔT _min ≦1, it was possible to more strictly control the temperature of the bread dough.

Example 4
Fabrication of temperature control indicator (see Figure 19)
As a transparent support (211), 30 parts of the microcapsule pigment B of Example 3, 62 parts of a urethane-based emulsion, 2 parts of a thickening agent, and 0.5 parts of a leveling agent were coated on a transparent polyester film having a thickness of 25 μm. 5 parts of an antifoaming agent, 0.5 parts of an antifoaming agent, and 5 parts of a cross-linking agent are uniformly dispersed in a thermochromic color-memory ink. to provide a first reversible thermochromic layer (202) to obtain a transparent first reversible thermochromic body (21) [transparent first reversible thermochromic laminate (21')]. rice field. Next, the first reversible thermochromic body was cut to prepare a first reversible thermochromic body having a rectangular shape of 3 cm×5 cm, in which the reversible thermochromic layer was visible on the entire surface.
As a transparent support (311), 30 parts of the microcapsule pigment A of Example 3, 62 parts of a urethane-based emulsion, 2 parts of a thickening agent, and 0.5 parts of a leveling agent were coated on a transparent polyester film having a thickness of 25 μm. 5 parts of an antifoaming agent, 0.5 parts of an antifoaming agent, and 5 parts of a cross-linking agent are uniformly dispersed in a thermochromic color-memory ink. to provide a second reversible thermochromic layer (302) to obtain a transparent second reversible thermochromic body (31) [transparent second reversible thermochromic laminate (31')]. rice field. Next, a second adhesive layer (303) was provided on the surface of the support opposite to the second reversible thermochromic layer, and a release layer was provided on the outer surface of the adhesive layer. Next, the second reversible thermochromic body was cut to prepare a second rectangular reversible thermochromic body of 3 cm×5 cm in which the reversible thermochromic layer was visible on the entire surface.
The first reversible thermochromic material was heated to 52° C. or higher to retain the decolored state, and the second reversible thermochromic material was cooled to −44° C. or lower to retain the colored state and stored. Next, the heating of the first reversible thermochromic body and the cooling of the second reversible thermochromic body are stopped, and the release layer of the second reversible thermochromic body is removed under a temperature environment of −15.5° C. The second reversible thermochromic body was adhered to the first reversible thermochromic body by using the above method to prepare a temperature control indicator (10).

Temperature control during distribution and storage of bread dough (determines whether or not it deviates from the appropriate temperature range of -20°C or higher and -10°C or lower)
In a temperature environment of -15.5 ° C., when a temperature control indicator is laminated on a storage container for storing bread dough with an appropriate temperature range of -20 ° C. or higher and -10 ° C. or lower, a second reversible thermochromic body An orange color was visually recognized in a rectangular shape (initial state).

When the storage container is placed in a temperature environment of -9 ° C. or higher, the thermochromic color-memory material A provided in the second reversible thermochromic body disappears, the temperature control indicator changes color, and the storage container was visually recognized (state 1).
When the temperature control indicator in state 1 exceeds −44° C. and is placed in a temperature environment of −21° C. or less, the thermochromic color-memory material B provided in the first reversible thermochromic body develops color, A rectangular bluish-green color due to the first reversible thermochromic material was observed (state 2).
When the temperature control indicator in state 2 is placed in a temperature environment of −44° C. or less, the thermochromic color-memory material A provided in the second reversible thermochromic body develops color, and the first reversible thermochromic color is obtained. A brown color, which is a mixture of bluish-green due to the body and orange due to the second reversible thermochromic material, was visually recognized in a rectangular shape (state 3).

Further, when the storage container is placed in a temperature environment of −21° C. or less, the thermochromic color-memory material B provided in the first reversible thermochromic body develops color, the temperature control indicator changes color, and the second Brown, which is a mixture of bluish-green from one reversible thermochromic body and orange from the second reversible thermochromic body, was visually recognized in a rectangular shape (state 3').
When the temperature control indicator in state 3′ is placed in a temperature environment of −9° C. or more and less than 52° C., the thermochromic color-memory material A provided in the second reversible thermochromic body decolors, A rectangular bluish-green color due to the first reversible thermochromic material was observed (state 2').
When the temperature control indicator in state 2′ is placed in a temperature environment of 52° C. or higher, the thermochromic color-memory material B provided in the first reversible thermochromic body disappears, and the color of the storage container changes. Visually recognized (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 then one of the initial thermochromic color-memory materials (thermochromic color-memory material Since it is difficult to restore the color-developing temperature control indicator of material A) to the state before discoloration, it was possible to irreversibly determine that the storage container deviated from the appropriate temperature range. Here, since the temperature _t3 is higher than the temperature _t2 ', it was easy to determine that the storage container deviated from the proper temperature range.
In addition, when the temperature environment deviates from the proper temperature range to a higher temperature environment or a lower temperature environment, only the other thermochromic color-memory material (thermochromic color-memory material B) develops color under a specific temperature environment. In order to maintain the state, it was possible to irreversibly determine whether the storage container deviated from the appropriate temperature range to a higher temperature environment or a lower temperature environment. Here, the temperature t ₄ ′ is 52° C., which is higher than the normal temperature range, the temperature t ₁ is −44° C., which is in the ultra-low temperature range, and Δt ₄ (t ₄ ′−t ₄ ): 61° C., ₁ (t ₁ '-t ₁ ): 23°C, (t ₃ '-t ₄ ): 50°C, (t ₁ '-t ₂ ): 10°C. It was easy to distinguish between deviations under the environment and under the low temperature environment.
In addition, the difference (ΔT _MAX ) between the temperature t ₄ and the upper limit temperature T _MAX of the appropriate temperature range of the storage container satisfies 0<ΔT _MAX ≤ 1, and the temperature t ₁ ′ and the lower limit temperature T of the appropriate temperature range of the storage container Since the difference (ΔT _min ) from _min satisfies 0<ΔT _min ≦1, it was possible to more strictly control the temperature of the bread dough.

Example 5
Preparation of thermochromic color-memory material A (thermochromic color-memory microcapsule pigment A) 1.5 parts of 2-methylindol-3-yl)-4-azaphthalide, 5 parts of 2,2-bis(4-hydroxyphenyl)hexafluoropropane as component (b), and laurin as component (c) A thermochromic color-memory composition comprising 50 parts of cyclohexylmethyl acid was uniformly heated and dissolved, and then added to a mixed solution comprising 30 parts of an aromatic isocyanate prepolymer as a wall film material and 50 parts of a co-solvent. After that, the mixture was emulsified and dispersed in a 6% aqueous solution of polyvinyl alcohol and stirred while heating. Then, 2.5 parts of a water-soluble modified aliphatic amine was 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 has an average particle size of 4.9 μm, complete color development temperature t ₁ : −36° C., color development start temperature t ₂ : −32° C., decoloration start temperature t ₃ : 4° C., complete decolorization temperature t ₄ : 8° C., ΔH: 40° C., and reversibly changed from blue to colorless with temperature change.

Preparation of thermochromic color-memory material B (thermochromic color-memory microcapsule pigment B) (A) As component, 6-(N-ethyl-N-isoamylamino)-1,2-benzofluorane 2 parts, 5 parts of 2,2-bis(4-hydroxyphenyl)hexafluoropropane as component (b), and 1,4-bis(2-hydroxyethoxy)benzene and caproic acid as component (c) A thermochromic color-memory composition consisting of 50 parts of a diester of is uniformly heated and dissolved, and is added to a mixed solution consisting of 20 parts of an aromatic isocyanate prepolymer as a wall film material and 40 parts of a co-solvent. , emulsified and dispersed in a 15% aqueous gelatin solution, stirred while heating, 2 parts of a water-soluble modified aliphatic amine was added, and further stirred to prepare a microcapsule dispersion. A microcapsule pigment B was obtained from the above microcapsule dispersion by centrifugation.
The microcapsule pigment B has an average particle size of 5.0 μm, complete color development temperature t ₁ ′: −3° C., color development start temperature t ₂ ′: 3° C., decoloration start temperature t ₃ ′: 58° C. Color temperature t ₄ ′: 80° C., ΔH: 69° C., and reversibly changed from magenta to colorless with temperature change.

Fabrication of temperature control indicator (see Figure 20)
10 parts of the microcapsule pigment A, 1 part of the dispersant, and 89 parts of the polypropylene homopolymer were melt-mixed in an extruder at 180° C. to obtain reversible thermochromic pellets. Using the reversible thermochromic pellets, an injection molding machine is used at a cylinder temperature of 180 ° C. to form a plate with a length of 3 cm, a width of 5 cm, and a height of 0.5 cm to form a transparent first reversible thermochromic pellet. A body (21) [transparent first reversible thermochromic molded body (21'')] was obtained.
10 parts of the microcapsule pigment B, 1 part of the dispersant, and 89 parts of the polypropylene homopolymer were melt-mixed in an extruder at 180° C. to obtain reversible thermochromic pellets. Using the reversible thermochromic pellets, at a cylinder temperature of 180 ° C. in an injection molding machine, molded into a plate with a length of 3 cm, a width of 5 cm, and a height of 0.5 cm to form a second reversible thermochromic material having transparency. A body (31) [second reversible thermochromic molded body (31'') having transparency] was obtained.
The first reversible thermochromic material was cooled to −36° C. or below to maintain the colored state, and the second reversible thermochromic material was heated to 80° C. or higher to maintain the decolored state and stored. Next, cooling of the first reversible thermochromic body and heating of the second reversible thermochromic body are stopped, and a second reversible thermochromic material is applied onto the first reversible thermochromic body in a temperature environment of 3.5°C. The body was laminated to create a temperature management indicator (10).

Temperature control in the process of distribution and storage of vegetables (determines whether the temperature has deviated from the appropriate temperature range of 0°C or higher and 5°C or lower)
In a temperature environment of 3.5 ° C, when a temperature control indicator is stacked on a storage container containing vegetables whose proper temperature range is 0 ° C or higher and 5 ° C or lower, blue color due to the first reversible thermochromic body It was visually recognized as a rectangle (initial state).

When the storage container is placed in a temperature environment of 8 ° C. or higher, the thermochromic color-memory material A provided in the first reversible thermochromic body disappears and the temperature control indicator changes color, and the storage container Color was visible (state 1).
When the temperature control indicator in state 1 exceeds −36° C. and is placed in a temperature environment of −3° C. or less, the thermochromic color-memory material B provided in the second reversible thermochromic body develops color, A rectangular magenta color due to the second reversible thermochromic material was observed (state 2).
When the temperature control indicator in state 2 is placed in a temperature environment of −36° C. or less, the thermochromic color-memory material A provided in the first reversible thermochromic body develops a color, and the first reversible thermochromic color is obtained. A purple color obtained by mixing the blue due to the body and the magenta due to the second reversible thermochromic material was visually recognized in a rectangular shape (state 3).

Further, when the storage container is placed in a temperature environment of −3° C. or less, the thermochromic color-memory material B provided in the second reversible thermochromic body develops color, the temperature control indicator changes color, and the second reversible thermochromic body changes color. A purple color obtained by mixing the blue color by one reversible thermochromic body and the magenta color by the second reversible thermochromic body was visually recognized in a rectangular shape (state 3').
When the temperature control indicator in state 3′ is placed in a temperature environment of 8° C. or more and less than 80° C., the thermochromic color-memory material A provided in the first reversible thermochromic body decolors, and the second A rectangular magenta color was observed due to the two reversible thermochromic materials (state 2').
When the temperature control indicator in state 2′ is placed in a temperature environment of 80° C. or higher, the temperature-sensitive color-changing color-memory material B provided in the second reversible thermochromic body disappears, and the color of the storage container changes. Visually recognized (state 1').

When the storage container containing vegetables is placed in a temperature environment outside the appropriate temperature range, the temperature control indicator changes color, and then the initial thermochromic color-memory material (thermochromic color-memory material Since it was difficult to restore the material A) to the color-developing temperature control indicator before discoloration, it was possible to irreversibly determine that the storage container deviated from the appropriate temperature range. Here, since the temperature _t3 is higher than the temperature _t2 ', it was easy to determine that the storage container deviated from the proper temperature range.
In addition, when the temperature environment deviates from the proper temperature range to a higher temperature environment or a lower temperature environment, only the other thermochromic color-memory material (thermochromic color-memory material B) develops color under a specific temperature environment. In order to maintain the state, it was possible to irreversibly determine whether the storage container deviated from the appropriate temperature range to a higher temperature environment or a lower temperature environment. Here, the temperature t ₄ ′ is 80° C., which is higher than the normal temperature range, the temperature t ₁ is −36° C., which is in the ultra-low temperature range, and 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 distinguish between deviations under the environment and under the low temperature environment.
Further, the difference (ΔT _MAX ) between the temperature t ₄ and the upper limit temperature T _MAX of the proper temperature range of the storage container satisfies 0<ΔT _MAX ≤ 3, and the temperature t ₁ ′ and the lower limit temperature T of the proper temperature range of the storage container Since the difference (ΔT _min ) from _min satisfies 0<ΔT _min ≦3, it was possible to strictly control the temperature of the vegetables.

Example 6
Preparation of thermochromic color-memory material A (thermochromic color-memory microcapsule pigment A) 1 part of methylspiro[5H-[1]benzopyrano[2,3-d]pyrimidine-5,1′(3′H)-isobenzofuran]-3′-one and 2,2-bis A thermochromic color-memory composition comprising 5 parts of (4-hydroxyphenyl)hexafluoropropane and 50 parts of cyclohexylmethyl laurate as the component (c) was uniformly heated and dissolved to obtain an aromatic composition as a wall film material. 30 parts of group isocyanate prepolymer and 50 parts of a co-solvent, then emulsified and dispersed in a 6% aqueous solution of polyvinyl alcohol, continued stirring while heating, and water-soluble aliphatic modified amine 2 0.5 part was 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 has an average particle diameter of 5.5 μm, complete color development temperature t ₁ : −37° C., color development start temperature t ₂ : −31° C., decoloration start temperature t ₃ : 4° C., complete decolorization temperature t ₄ : 9°C, ΔH: 40.5°C, and reversibly changed from pink to colorless with temperature change.

Preparation of thermochromic color-memory material B (thermochromic color-memory microcapsule pigment B) 2 parts of 2-methylindol-3-yl)-4-azaphthalide, 5 parts of 2,2-bis(4-hydroxyphenyl)hexafluoropropane as component (b), and 4-phenyl as component (c) A thermochromic color-memory composition comprising 50 parts of a diester of phenol ethylene glycol ether and lauric acid was uniformly heated and dissolved, and 20 parts of an aromatic isocyanate prepolymer as a wall film material and 40 parts of a co-solvent were added. After putting it into a mixed solution consisting of, emulsifying and dispersing in a 15% gelatin aqueous solution, continuing to stir while heating, adding 2 parts of a water-soluble aliphatic modified amine, and further stirring to obtain a microcapsule dispersion. prepared. A microcapsule pigment B was obtained from the above microcapsule dispersion by centrifugation.
The microcapsule pigment B has an average particle diameter of 2.5 μm, complete color development temperature t ₁ ′: 1° C., color development start temperature t ₂ ′: 6° C., decoloration start temperature t ₃ ′: 39° C. Temperature t ₄ ′: 48° C., ΔH: 40° C., and reversibly changed from blue to colorless with temperature change.

Fabrication of temperature control indicator (see Figure 21)
0.5 parts of a yellow non-thermochromic coloring agent, 91.5 parts of a urethane emulsion, 2 parts of a thickening agent, and 0.5 parts of a leveling agent were applied onto a white polyester film having a thickness of 25 μm as a support (201). 5 parts, 0.5 parts of an antifoaming agent, and 5 parts of a cross-linking agent are uniformly dispersed in a non-thermochromic ink. A color change layer (401) was provided. Furthermore, on the non-thermochromic layer, 30 parts of the above microcapsule pigment B, 62 parts of urethane emulsion, 2 parts of a thickener, 0.5 parts of a leveling agent, 0.5 parts of an antifoaming agent, and a cross-linking agent A thermochromic color-memory ink in which 5 parts are uniformly dispersed is solidly printed using a 120-mesh screen plate, dried and cured to form a first reversible thermochromic layer (202), A first reversible thermochromic body (20) [first reversible thermochromic laminate (20')] was thus obtained. Next, a first adhesive layer (203) is provided on the surface of the support opposite to the surface on which the non-thermochromic layer and the first reversible thermochromic layer are provided, and a release layer is provided on the outer surface of the adhesive layer. rice field. Next, the first reversible thermochromic body was cut to prepare a first reversible thermochromic body having a rectangular shape of 3 cm×5 cm, in which the reversible thermochromic layer was visible on the entire surface.
As a transparent support (311), 30 parts of the above microcapsule pigment A, 62 parts of urethane emulsion, 2 parts of a thickening agent, and 0.5 parts of a leveling agent were coated on a transparent polyester film having a thickness of 25 μm. , 0.5 parts of an antifoaming agent and 5 parts of a cross-linking agent are uniformly dispersed in a thermochromic color-memory ink, which is solidly printed using a 120-mesh screen plate, dried and cured. Two reversible thermochromic layers (302) were provided to obtain a transparent second reversible thermochromic body (31) [transparent second reversible thermochromic laminate (31')]. Next, a second adhesive layer (303) was provided on the surface of the support opposite to the second reversible thermochromic layer, and a release layer was 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×5 cm.
The first reversible thermochromic material was heated to 48° C. or higher to maintain the decolored state, and the second reversible thermochromic material 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 are stopped, and the release layer of the second reversible thermochromic body is removed in a temperature environment of 5 ° C. to form the first reversible thermochromic body. A temperature control indicator (10) was produced by attaching a second reversible thermochromic body to the reversible thermochromic body.

Temperature control during the distribution and storage of pharmaceuticals (determines whether the temperature has deviated from the appropriate temperature range of 2°C or higher and 8°C or lower)
In a temperature environment of 5°C, remove the release layer of the first reversible thermochromic body and attach a temperature control indicator to a storage container containing pharmaceuticals with an appropriate temperature range of 2°C or higher and 8°C or lower. When attached, the thermochromic color-memory material A starts decoloring, and the thermochromic color-memory material B starts developing color. An ocher color obtained by mixing the light blue color due to the discoloration layer, the yellow color due to the non-thermochromic layer, and the light pink color due to the second reversible thermochromic material was visually recognized in a rectangular shape (initial state).

When the storage container is placed in a temperature environment of 9 ° C. or higher, the thermochromic color-memory material A provided in the second reversible thermochromic body and the thermochromic color provided in the first reversible thermochromic body. The memory material B was decolored, the color of the temperature control indicator was changed, and yellow due to the non-thermochromic layer of the first reversible thermochromic body was visually recognized in a rectangular shape (state 1).
When the temperature control indicator in state 1 exceeds -37 ° C. and is placed in a temperature environment of 1 ° C. or less, the thermochromic color-memory material B provided in the first reversible thermochromic body develops color, and the second A green color obtained by mixing the blue due to the first reversible thermochromic layer and the yellow due to the non-thermochromic layer of one reversible thermochromic body was visually recognized in a rectangular shape (state 2).
When the temperature control indicator in state 2 is placed in a temperature environment of −37° C. or less, the thermochromic color-memory material A provided in the second reversible thermochromic body develops a color, and the first reversible thermochromic color occurs. A rectangular color of brown, which is a mixture of blue due to the first reversible thermochromic layer of the body, yellow due to the non-thermochromic layer, and pink due to the second reversible thermochromic body, was visually recognized (state 3).

Further, when the storage container is placed in a temperature environment of 1 ° C. or less, the thermochromic color-memory material B provided in the first reversible thermochromic body develops color, the temperature control indicator changes color, and the first A brown color that is a mixture of blue from the first reversible thermochromic layer of the reversible thermochromic body, yellow from the non-thermochromic layer, and pink from the second reversible thermochromic body was visually recognized in a rectangular shape (state 3' ).
When the temperature control indicator in state 3′ is placed in a temperature environment of 9° C. or more and less than 48° C., the thermochromic color-memory material A provided in the second reversible thermochromic body decolors, and the second A green color obtained by mixing the blue due to the first reversible thermochromic layer and the yellow due to the non-thermochromic layer of one reversible thermochromic body was visually recognized in a rectangular shape (state 2').
When the temperature control indicator in state 2′ is placed in a temperature environment of 48° C. or higher, the thermochromic color-memory material B provided in the first reversible thermochromic body decolors, and the first reversible heat A rectangular yellow color was observed due to the non-thermochromic layer of the color-change body (state 1').

When the storage container containing the drug is placed in a temperature environment outside the appropriate temperature range, the temperature control indicator changes color, and then the initial thermochromic color-memory material (thermochromic color-memory material A) is in a slightly decolored state, and the other thermochromic color-memory material (thermochromic color-memory material B) is in a slightly colored state, returning to the temperature control indicator before discoloration. Therefore, it was possible to irreversibly determine that the storage container deviated from the appropriate temperature range.
In addition, when the temperature environment deviates from the proper temperature range to a higher temperature environment or a lower temperature environment, only the other thermochromic color-memory material (thermochromic color-memory material B) develops color under a specific temperature environment. In order to maintain the state, it was possible to irreversibly determine whether the storage container deviated from the appropriate temperature range to a higher temperature environment or a lower temperature environment. Here, the temperature t ₄ ′ is 48° C., which is higher than the normal temperature range, the temperature t ₁ is −37° C., which is in the ultra-low temperature range, and 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. It was easy to distinguish between deviations under the environment and under the low temperature environment.
Further, the difference (ΔT _MAX ) between the temperature t ₄ and the upper limit temperature T _MAX of the proper temperature range of the storage container satisfies 0<ΔT _MAX ≦1, and the temperature t ₁ ′ and the lower limit temperature T of the proper temperature range of the storage container Since the difference (ΔT _min ) from _min satisfies 0<ΔT _min ≦1, it was possible to more strictly control the temperature of the medicine.

Example 7
Preparation of thermochromic color-memory material A (thermochromic color-memory microcapsule pigment A) (a) As a component, 9-ethyl-(3-methylbutyl)amino-spiro[12H-benzo[a]xanthene -12,1'(3'H)-isobenzofuran]-3'-one 3 parts, (b) 5 parts of 2,2-bis(4-hydroxyphenyl)hexafluoropropane as a component, and (c) A thermochromic color-memory composition comprising 50 parts of cyclohexylmethyl laurate as components is uniformly heated and dissolved, and a mixture comprising 30 parts of an aromatic isocyanate prepolymer as a wall film material and 50 parts of a co-solvent. After adding to the solution, emulsify and disperse in a 6% polyvinyl alcohol aqueous solution, continue stirring while heating, add 2.5 parts of water-soluble aliphatic modified amine, and continue stirring to obtain a microcapsule dispersion. prepared. Microcapsule pigment A was obtained from the above microcapsule dispersion by centrifugation.
Microcapsule pigment A has an average particle diameter of 5.5 μm, complete color development temperature t ₁ : −37° C., color development start temperature t ₂ : −30° C., decoloration start temperature t ₃ : 3° C., complete decolorization temperature t ₄ : 8° C., ΔH: 39° C., and reversibly changed from magenta to colorless with temperature change.

Preparation of thermochromic color-memory material B (thermochromic color-memory microcapsule pigment B) (a) 2-(2-chloroanilino)-6-di-n-butylaminofluorane as component4. 5 parts, 5 parts of 1,1-bis(4-hydroxyphenyl)n-decane, 5 parts of 2,2-bis(4-hydroxyphenyl)hexafluoropropane as components (b), and 5 parts of 2,2-bis(4-hydroxyphenyl)hexafluoropropane as components (c) and 50 parts of 4-methylbenzyl palmitate are uniformly heated and dissolved, and a mixture of 35 parts of an aromatic isocyanate prepolymer as a wall film material and 40 parts of a co-solvent is mixed. After adding to the solution, emulsify and disperse in an 8% polyvinyl alcohol aqueous solution, continue stirring while heating, add 2.5 parts of water-soluble aliphatic modified amine, and continue stirring to obtain a microcapsule dispersion. prepared. A microcapsule pigment B was obtained from the above microcapsule dispersion by centrifugation.
The microcapsule pigment B has an average particle diameter of 2.4 μm, complete color development temperature t ₁ ′: −3° C., color development start temperature t ₂ ′: 6° C., decoloration start temperature t ₃ ′: 37° C. Color temperature t ₄ ′: 45° C., ΔH: 39.5° C., and reversibly changed from black to colorless with temperature change.

Fabrication of temperature control indicator with anti-tampering function (see Figure 22)
As the tamper-preventing member (support) (204) provided with an adhesive layer, an 80 μm-thick tamper-preventing label made of a white polypropylene film [manufactured by Lintec Corporation, product name: TE80W PAT1 8K] is provided with an adhesive layer. 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 cross-linking agent Using a 120-mesh screen plate, solid printing is performed on the entire surface of the tamper-proof label with a thermochromic color-memory ink in which the parts are uniformly dispersed, and dried and cured to form a reversible thermochromic layer (202). was provided to obtain a first reversible thermochromic body (20) [first reversible thermochromic laminate (20')].
As a transparent support (311), 30 parts of the above microcapsule pigment B, 62 parts of urethane emulsion, 2 parts of a thickening agent, and 0.5 parts of a leveling agent were coated on a transparent polyester film having a thickness of 25 μm. , 0.5 parts of an antifoaming agent and 5 parts of a cross-linking agent are uniformly dispersed in a thermochromic color-memory ink, which is solidly printed using a 120-mesh screen plate, dried and cured. Two reversible thermochromic layers (302) were provided to obtain a transparent second reversible thermochromic body (31) [transparent second reversible thermochromic laminate (31')]. Next, a second adhesive layer (303) was provided on the surface of the support opposite to the second reversible thermochromic layer, and a release layer was provided on the outer surface of the adhesive layer. Next, the second reversible thermochromic body was cut into the same size as the first reversible thermochromic body to prepare a rectangular second reversible thermochromic body in which the reversible thermochromic layer was visible on the entire surface. .
The first reversible thermochromic material was cooled to −37° C. or below to maintain the colored state, and the second reversible thermochromic material was heated to 45° 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 are stopped, and the release layer of the second reversible thermochromic body is removed in a temperature environment of 2° C. to form the first reversible thermochromic body. A temperature control indicator (10) was produced by attaching a second reversible thermochromic body to the reversible thermochromic body.

Temperature control in the process of distribution and storage of vegetables (determines whether the temperature has deviated from the appropriate temperature range of 0°C or higher and 5°C or lower)
In a temperature environment of 2°C, remove the release sheet of the tamper-proof label and attach a temperature control indicator to a storage container that stores vegetables whose proper temperature range is 0°C or higher and 5°C or lower. Then, since the thermochromic color-memory material B starts to develop color, a reddish brown color obtained by mixing the magenta color by the first reversible thermochromic body and the light black color by the second reversible thermochromic body becomes a rectangle. Visible (initial state).

When the storage container is placed in a temperature environment of 8° C. or higher, the thermochromic color-memory material A provided in the first reversible thermochromic body and the thermochromic color provided in the second reversible thermochromic body. The color of memory B disappeared, the color of the temperature control indicator changed, and the white color due to the support was visually recognized as a rectangular shape (state 1).
When the temperature control indicator in state 1 exceeds −37° C. and is placed in a temperature environment of −3° C. or less, the thermochromic color-memory material B provided in the second reversible thermochromic body develops color, A rectangular black color due to the second reversible thermochromic material was visually recognized (state 2).
When the temperature control indicator in state 2 is placed in a temperature environment of −37° C. or less, the thermochromic color-memory material A provided in the first reversible thermochromic body develops color, and the first reversible thermochromic color is obtained. A brown color obtained by mixing magenta due to the body and black due to the second reversible thermochromic material was visually recognized in a rectangular shape (state 3).

Further, when the storage container is placed in a temperature environment of −3° C. or less, the thermochromic color-memory material B provided in the second reversible thermochromic body develops color, the temperature control indicator changes color, and the second reversible thermochromic body changes color. A brown color obtained by mixing the magenta color by one reversible thermochromic body and the black color by the second reversible thermochromic body was visually recognized in a rectangular shape (state 3').
When the temperature control indicator in state 3′ is placed in a temperature environment of 8° C. or more and less than 45° C., the thermochromic color-memory material A provided in the first reversible thermochromic body decolors, and the second A rectangular black color due to the two reversible thermochromic bodies was visually recognized (state 2').
When the temperature control indicator in state 2′ is placed in a temperature environment of 45° C. or higher, the thermochromic color-memory material B provided in the second reversible thermochromic body disappears, and the white color of the support changes. It was visually recognized as a rectangle (state 1').

When the storage container containing vegetables is placed in a temperature environment outside the appropriate temperature range, the temperature control indicator changes color, and then one of the initial 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 slightly colored state, and it is difficult to return to the temperature control indicator before discoloration. Therefore, it was possible to irreversibly determine that the storage container deviated from the proper temperature range.
In addition, when the temperature environment deviates from the proper temperature range to a higher temperature environment or a lower temperature environment, only the other thermochromic color-memory material (thermochromic color-memory material B) develops color under a specific temperature environment. Therefore, it was possible to irreversibly determine whether the storage container deviated from the appropriate temperature range to a higher temperature environment or a lower temperature environment. Here, the temperature t ₄ ′ is 45° C., which is higher than the normal temperature range, the temperature t ₁ is -37° C., which is in the ultra-low temperature range, and Δt ₄ (t ₄ ′−t ₄ ): 37° C., ₁ (t ₁ '-t ₁ ): 34°C, (t ₃ '-t ₄ ): 29°C, (t ₁ '-t ₂ ): 27°C. It was easy to distinguish between deviations under the environment and under the low temperature environment.
Further, the difference (ΔT _MAX ) between the temperature t ₄ and the upper limit temperature T _MAX of the proper temperature range of the storage container satisfies 0<ΔT _MAX ≤ 3, and the temperature t ₁ ′ and the lower limit temperature T of the proper temperature range of the storage container Since the difference (ΔT _min ) from _min satisfies 0<ΔT _min ≦3, it was possible to strictly control the temperature of the vegetables.
The temperature control indicator was removed from the storage container in order to replace the first reversible thermochromic body with a first reversible thermochromic body in a different color development state so that the vegetables would not leave a history of deviating from the appropriate temperature range. , The surface base material of the tamper-proof label of the first reversible thermochromic body was destroyed and peeled off, leaving a mark on the storage container. Therefore, the temperature control indicator has a function of preventing tampering such as replacement or reattachment.

Application example 1
Preparation of counterfeit prevention medium On a white polyester film as a support, 30 parts of the microcapsule pigment A of Example 1, 62 parts of a urethane emulsion resin, 2 parts of a thickener, 0.5 parts of a leveling agent, and defoaming 0.5 parts of the agent and 5 parts of the cross-linking agent are uniformly dispersed in the thermochromic color-memorizing ink. A color changing layer was provided to obtain a first reversible thermochromic body (first reversible thermochromic laminate). Next, the first reversible thermochromic body was cut to prepare a first reversible thermochromic body having a rectangular shape of 3 cm×5 cm, in which the reversible thermochromic layer was visible on the entire surface.
As a transparent support, 30 parts of the microcapsule pigment B of Example 1, 62 parts of a urethane emulsion, 2 parts of a thickening agent, and 0.5 parts of a leveling agent were placed on a transparent polyester film having a thickness of 25 μm. , 0.5 parts of an antifoaming agent and 5 parts of a cross-linking agent are uniformly dispersed in a thermochromic color-memory ink. was provided to obtain a second reversible thermochromic body having transparency (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 prepare a second rectangular reversible thermochromic body of 3 cm×5 cm in which the reversible thermochromic layer was visible on the entire surface.
The first reversible thermochromic material was cooled to −55° C. or below to maintain the colored state, and the second reversible thermochromic material was heated to 60° 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 are stopped, and the release layer of the second reversible thermochromic body is removed in a temperature environment of -12 ° C. to remove the second reversible thermochromic body. A second reversible thermochromic body was adhered to one reversible thermochromic body to prepare an anti-counterfeiting medium.

Under a temperature environment of −12° C., the anti-counterfeiting medium was visible in a rectangular blue color due to the first reversible thermochromic material (initial state).
When the anti-counterfeit medium is placed in a temperature environment of −6° C. or higher, the thermochromic color-memory material A provided in the first reversible thermochromic body is decolored, and the first reversible thermochromic body is formed. A rectangular white color due to the support was observed (state 1).
When the anti-counterfeit medium in state 1 is placed in a temperature environment of -55°C or higher and -21°C or lower, the thermochromic color-memory material B provided in the second reversible thermochromic body develops color, A rectangular magenta color due to the second reversible thermochromic material was observed (state 2).
Next, when placed in a temperature environment of −55° C. or less, the thermochromic color-memory material A provided in the first reversible thermochromic body develops a blue color by the first reversible thermochromic body and the second Purple, which is a mixture of magenta due to the two reversible thermochromic materials, was visually recognized in a rectangular shape (state 3).
Further, when the anti-counterfeit medium is placed in a temperature environment of −21° C. or less, the thermochromic color-memory material B provided in the second reversible thermochromic body develops color, and the first reversible thermochromic body develops color. A purple color obtained by mixing the blue color from the second reversible thermochromic material and the magenta color from the second reversible thermochromic material was visually recognized in a rectangular shape (state 3').
When the anti-counterfeiting medium in state 3′ is placed in a temperature environment of −6° C. or more and less than 60° C., the temperature-sensitive color-changing color-memory material A provided in the first reversible thermochromic body decolors, A rectangular magenta color was observed due to the second reversible thermochromic material (state 2').
Next, when placed in a temperature environment of 60° C. or higher, the thermochromic color-memory material B provided in the second reversible thermochromic material is decolored, and the support of the first reversible thermochromic material disappears. A white rectangle was visually recognized (state 1').
Therefore, the above anti-counterfeiting medium changes color when it deviates from a specific temperature range (in a temperature environment exceeding −21° C. and less than −6° C.), and then one of the initial thermochromic color-memory materials Since it is difficult to return the (thermochromic color-memory material A) to a color-developing state, the anti-counterfeiting medium before discoloration, it has an anti-counterfeiting function.

t Complete color development temperature of the thermochromic color-memory material in _{the 1-} color developing state t Color-development start temperature of the thermochromic color-memory material in _{the 2-} color developing state t Discoloration of the thermochromic color-memory material in _{the 3-} color developing state Start temperature t Complete discoloration temperature of the thermochromic color-memory material in the ₄ colored state t ₁ ′ Complete color development temperature of the thermochromic color-memory material in the decolored state t ₂ ′ Thermochromic property in the decolored state Color-development start temperature of color-memory material _t3 ' Color-discoloration start temperature of thermochromic color-memory material in bleached state _t4 ' Complete color-discoloration temperature of thermochromic color-memory material in bleached state ΔH Hysteresis Width 10 Temperature control 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 Anti-tampering member provided with adhesive layer 21 First reversible thermochromic body having transparency 21 ′ First reversible thermochromic laminate having transparency 21 ″ Second reversible heat having transparency Color-changing molded body 211 Transparent support 30 Second reversible thermochromic body 30' Second reversible thermochromic laminate 30'' Second reversible thermochromic molded body 301 Support 302 Second reversible heat Color change 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 transparent support 314 transparent falsification prevention member provided with an adhesive layer 401 non-thermochromic layer

Claims (13)

A temperature control indicator comprising a first reversible thermochromic body comprising a thermochromic color-memory material and a second reversible thermochromic body comprising a thermochromic color-memory material, The thermochromic color-memory material comprises (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a color reaction of the components (a) and (b). A thermochromic color-memory microcapsule pigment encapsulating a thermochromic color-memory composition comprising at least a reaction medium that controls the thermochromic color-memory composition, or a thermoplastic resin or a thermo Thermochromic color-memory resin particles dispersed in a curable resin exhibit hysteresis characteristics with respect to the color density-temperature curve, exhibiting tautomorphism between the colored state and the decolored state, and the temperature rises from the colored state. In the process, decoloring begins when the decoloring start temperature _t3 is reached, and the color is completely decolored in the temperature range of the complete decoloring temperature _t4 or higher, which is higher than the temperature _t3 . , it begins to develop color when it reaches the color development start temperature t ₂ , and exhibits a hysteresis characteristic in which the color is completely developed in the temperature range below the complete color development temperature t ₁ which is lower than the temperature t ₂ . One of the thermochromic color-memory materials is in a developing state and the other is in a decolored state, The complete discoloration temperature _t4 is higher than the complete discoloration temperature _t4 of the thermochromic color-memory material in the color-developed state, and the complete color-development temperature _t1 of the thermochromic color-memory material in the decolorized state is In the _{thermochromic} color-memory material in the coloring state, the component (C) is a compound represented by the following formula (C), The completely decoloring temperature t ₄ is in the range of −25° C. or more and 15° C. or less, and the decolorized thermochromic color-memory material has a complete color development temperature t ₁ of more than −30° C. and 10° C. or less. A temperature control indicator characterized by being in the range of .

[In the formula, 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 said 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 said R ₂ is a linear or branched alkyl group having 3 to 11 carbon atoms. The temperature control indicator according to any one of claims 1 to 3, wherein the complete coloring temperature _t1 of the thermochromic color-memory material in the coloring state is -30°C or lower. 5. The temperature control indicator according to any one of claims 1 to 4, wherein the completely decoloring temperature _t4 of the decolorized thermochromic color-memory material is 40°C or higher. 6. The temperature control according to any one of claims 1 to 5, wherein the thermochromic color-memory materials provided in the first reversible thermochromic body and the second reversible thermochromic body exhibit different colors in a colored state. indicator. The temperature management indicator according to any one of claims 1 to 6, wherein the first reversible thermochromic body and the second reversible thermochromic body are arranged side by side. 7. The temperature control indicator according to any one of claims 1 to 6, wherein the second reversible thermochromic body is laminated on the first reversible thermochromic body. 9. The temperature control indicator according to claim 8, wherein said second reversible thermochromic body is transparent. reversible thermochromic property wherein at least one of the first reversible thermochromic material and the second reversible thermochromic material is provided with a reversible thermochromic layer containing a thermochromic color-memory material on a support; The temperature management indicator according to any one of claims 1 to 9, which is a laminate. 11. The temperature management indicator according to any one of claims 1 to 10, wherein an adhesive layer is provided on a surface of said reversible thermochromic body that contacts an object. 11. The temperature control indicator according to claim 10, wherein said support is a tamper-preventing member provided with an adhesive layer, which enables determination of peeling after being attached to an object. A method of using a temperature control indicator, comprising providing the temperature control indicator according to any one of claims 1 to 12 on an object.

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