JP2020071232A - Temperature management indicator and method of using the same - Google Patents

Abstract

To provide a temperature management indicator capable of irreversibly determining, by color change in reversible thermal discoloring material, whether articles such as drinks, medicament, natural flowers, etc. each having narrow proper temperature range have been stored without once departing from a proper temperature range, and a method of using the same.SOLUTION: A temperature management indicator (1) comprises: a first reversible thermal discoloring body (2) obtained by providing on a transparent support medium (5) a reversible thermal discoloring layer (4) containing a reversible thermal discoloring material discoloring while exhibiting a hysteresis band of 5 to 30°C; and a second reversible thermal discoloring body (3) obtained by providing a reversible thermal discoloring layer (4) containing the reversible thermal discoloring material on a support medium (6). One reversible thermal discoloring material of the reversible thermal discoloring body is in a colored state, and the other reversible thermal discoloring material is in a colorless state. The first reversible thermal discoloring body (2) is stacked on the second reversible thermal discoloring body (3).SELECTED DRAWING: Figure 11

Description

  The present invention relates to temperature control indicators and methods of using the same. More specifically, the present invention relates to a temperature control indicator that can control the temperature of an article or the like that needs to be stored within an appropriate temperature range by changing the color of a reversible thermochromic material, and a method of using the same.

Conventionally, a temperature-sensitive display indicator has been disclosed in which a temperature-sensitive display layer is formed of a color material containing a color-memory temperature-sensitive dye that exhibits a hysteresis characteristic due to a temperature change (see, for example, Patent Document 1).
The temperature-sensitive display indicator has a difference between the substantially low-temperature side color change point and the substantially high-temperature side color change point of the color-memory thermosensitive dye of 10 ° C. to 50 ° C., and the color-memory temperature-sensitive indicator is within the appropriate holding temperature range of the article. The dye is held in a colored state, and if the temperature rises above the proper holding temperature range too much, the color-storing temperature-sensitive dye is decolored and the decolored state is maintained even after returning to the proper holding temperature range. Alternatively, the color memory thermosensitive dye is held in a decolored state within the proper holding temperature range, and if the temperature falls below the proper holding temperature range too much, the color memory thermosensitive dye colors and returns to the proper holding temperature range. Also, the colored state is maintained. When the temperature-sensitive indicator is placed in a temperature environment outside the proper holding temperature range, whether or not the article deviates from the proper holding temperature range by storing and holding a color different from the color initially stored and held. However, even if the article discolors by deviating from the proper holding temperature range, it is possible to return to the color before the discoloration, and whether the article was kept without deviating from the proper holding temperature range. It was difficult to confirm.
Further, there is disclosed a forgery prevention medium capable of discriminating forgery by changing the color of the reversible thermochromic layer due to temperature increase or decrease (for example, refer to Patent Document 2).
The anti-counterfeit medium, one colored state, the other is a colorless state, comprising a reversible thermochromic layer containing each thermochromic memory composition showing a large hysteresis characteristics, when the temperature rises or falls, Both of the temperature-sensitive color-changing memory compositions are in a colorless state or a colored state, and it is difficult to return to the state before the color change in which one of the temperature-sensitive color-changing memory compositions is colored, and deviates from a predetermined temperature range. Although it has a function as a temperature indicator that can be surely confirmed whether or not, the temperature-sensitive color-changing memory composition is difficult to selectively retain and retain the color in an article having a narrow proper temperature range. It was difficult to irreversibly confirm whether an attempt was made to increase or decrease.

Japanese Utility Model Publication No. 6-46335 JP, 2017-170664, A

  The present invention is a reversible thermochromic property of whether foods, drugs, flowers, etc. having a narrow proper temperature range have been retained without deviating from the proper temperature range even during distribution and storage. An object of the present invention is to provide a temperature control indicator that can be irreversibly identified by a color change of a material and a method of using the temperature control indicator.

The present invention is a temperature control indicator comprising a transparent first reversible thermochromic material having a reversible thermochromic material and a second reversible thermochromic material having a reversible thermochromic material. The reversible thermochromic material controls (a) the electron-donating color-forming organic compound, (b) the electron-accepting compound, and (c) the color reaction of (a) and (b). A reversible thermochromic microcapsule pigment containing a reversible thermochromic composition comprising at least a reaction medium, or reversible thermochromic resin particles obtained by dispersing the reversible thermochromic composition in a thermoplastic or thermosetting resin. The color density-temperature curve shows a hysteresis characteristic and exhibits a mutual change between a colored state and a decolored state, and in the process of increasing the temperature from the colored state, when the decoloring start temperature t ₃ is reached, decoloring starts, higher than the temperature t ₃ complete decoloring temperature t become completely decolorized state in ₄ above temperature range, the process temperature is lowered from the colorless state, begins to color to reach coloring initiation temperature t _2, lower complete coloring temperature t ₁ following temperature than t ₂ It exhibits a hysteresis characteristic that becomes a completely colored state in a range, exhibits a hysteresis width (ΔH) of 5 to 30 ° C. with respect to a color density-temperature curve, and discolors, and one of the reversible thermochromic materials of the reversible thermochromic material is It is required that the color-developed state and the other reversible thermochromic material are in the decolored state, and that the first reversible thermochromic material is laminated on the second reversible thermochromic material.
Furthermore, (a) the electron-donating color-developing organic compounds of the reversible thermochromic materials provided in the first reversible thermochromic body and the second reversible thermochromic body are different from each other, and Each reversible thermochromic material provided in the thermochromic body and the second reversible thermochromic material, exhibiting different colors in a colored state, in the first reversible thermochromic material and the second reversible thermochromic material. (C) Each of the reversible thermochromic materials provided has different reaction media for controlling the color reaction of (a) and (b), the first reversible thermochromic material and the second reversible thermochromic material. each reversible thermochromic material is provided, the complete coloring temperature t ₁ of the complete coloring temperature t ₁ and thermochromic material decolored state of the thermochromic material colored _state, and, reversibly thermochromic coloring state Of the reversible thermochromic material in the decolored state with the color development start temperature t ₂ of the volatile material Color starting temperature t ₂ are each substantially identical, and, is substantially the same decoloring starting temperature t ₃ of the reversible thermochromic material of decoloring starting temperature t ₃ of the reversible thermochromic material colored state decolored state And the complete decolorization temperature t ₄ of the reversible thermochromic material in the colored state is lower than the complete decolorization temperature t ₄ of the reversible thermochromic material in the decolorized state, the first reversible thermochromic material and the second each reversible thermochromic material is provided on the reversible thermochromic material is complete coloring temperature t ₁ of the complete coloring temperature t ₁ and thermochromic material decolored state of the thermochromic material of the color state _and the colored state The color development start temperature t ₂ of the reversible thermochromic material is substantially the same as the color development start temperature t ₂ of the reversible thermochromic material in the decolored state, and the decolorization start temperature of the reversible thermochromic material in the color developed state is t ₃ is less than the decoloring starting temperature t ₃ of the reversible thermochromic material decolored state, or Greater than the decoloring starting temperature t ₃ of the reversible thermochromic material decolored state, complete decoloring temperature t ₄ of thermochromic material colored state is the complete decoloring temperature t of the thermochromic material decolored state _{4 or} less, and the reversible thermochromic materials provided in the first reversible thermochromic material and the second reversible thermochromic material have a decolorization starting temperature t ₃ and a decoloring temperature of the reversible thermochromic material in a colored state. state of reversible thermochromic material decoloring starting temperature t _3, and, the complete decoloring temperature t ₄ of thermochromic material complete decoloring temperature t ₄ decolored state of the thermochromic material colored state The reversible thermochromic materials in the color-developed state have substantially the same full-color development temperature t _{1 that} is lower than the full-color development temperature t ₁ of the reversible thermochromic material in the decolored state. is substantially the same color starting temperature t ₂ with a color start temperature t ₂ of the thermochromic material decolored state It is the first reversibly thermochromic material and a second of each thermochromic material provided in reversibly thermochromic material is colorless state and decoloring starting temperature t ₃ of the reversible thermochromic material colored state the thermochromic material of the erasing start temperature t _3, and, the complete decoloring temperature t ₄ is each thermochromic material complete decoloring temperature t ₄ decolored state of the thermochromic material colored state It is substantially the same, and, complete coloring temperature t ₁ of the reversibly thermochromic material colored state is smaller than the complete coloring temperature t ₁ of the thermochromic material decolored state, the color development of the reversible thermochromic material colored state start temperature t ₂ chromogenic start temperature t ₂ less than a reversible thermochromic material decolored state, or is required for the larger than coloring starting temperature t ₂ of the thermochromic material decolored state.
Furthermore, the first reversible thermochromic body is a reversible thermochromic body in which a reversible thermochromic layer containing a reversible thermochromic material is provided on a transparent support, and the second reversible thermochromic body is provided. The thermochromic body is a reversible thermochromic body in which a reversible thermochromic layer containing a reversible thermochromic material is provided on a support, and between the support and the reversible thermochromic layer of the second reversible thermochromic material. A non-thermochromic layer containing a non-thermochromic colorant, the first reversible thermochromic body, the first adhesive layer provided on the surface in contact with the second reversible thermochromic body. The second reversible thermochromic material, wherein the second adhesive layer is provided on the surface of the second reversible thermochromic material opposite to the first reversible thermochromic material, The support is a transparent tamperproof member provided with an adhesive layer, which can be discriminated when the support is peeled off after being attached to an adherend. It, support the second reversibly thermochromic material is peeled off after adhering to an adherend, it can be determined be peeled off, which requires that a tamper-evident member provided with the adhesive layer.
Furthermore, the method of using the temperature control indicator, which is provided by using the temperature control indicator on an article requiring temperature control or a storage container thereof, is required.

  The present invention is a reversible thermochromic material for foods and drinks, medicines, fresh flowers, etc. having a narrow proper temperature range, whether or not they were held at all during distribution and storage without departing from the proper temperature range. It is possible to provide a temperature management indicator which has an irreversible property and which is irreversible and which is difficult to restore to the original color once it deviates from the proper temperature range, and a method of using the same.

It is a graph explaining the hysteresis characteristic in the color density-temperature curve of the reversible thermochromic material applied to the present invention. It is a graph explaining an example of the color change behavior of the temperature management indicator in the color density-temperature curve of each reversible thermochromic material in the color development state and the color erasing state applied to the present invention. It is a graph explaining another example of the color change behavior of the temperature management indicator in the color density-temperature curve of each reversible thermochromic material in the color-developed state and the color-erased state applied to the present invention. It is a graph explaining another example of the color change behavior of the temperature management indicator in the color density-temperature curve of each reversible thermochromic material in the color-developed state and the color-erased state applied to the present invention. It is a graph explaining another example of the color change behavior of the temperature management indicator in the color density-temperature curve of each reversible thermochromic material in the color-developed state and the color-erased state applied to the present invention. It is a graph explaining another example of the color change behavior of the temperature management indicator in the color density-temperature curve of each reversible thermochromic material in the color-developed state and the color-erased state applied to the present invention. It is a graph explaining another example of the color change behavior of the temperature management indicator in the color density-temperature curve of each reversible thermochromic material in the color-developed state and the color-erased state applied to the present invention. It is a longitudinal section explanatory view of an example of a temperature control indicator of the present invention. It is a longitudinal section explanatory view of an example of the first reversible thermochromic substance of the present invention. It is a longitudinal section explanatory view of an example of the second reversible thermochromic body of the present invention. It is a longitudinal section explanatory view of other examples of a temperature control indicator of the present invention. It is a longitudinal section explanatory view of other examples of a temperature control indicator of the present invention. It is a longitudinal section explanatory view of other examples of a temperature control indicator of the present invention. It is a longitudinal section explanatory view of other examples of a temperature control indicator of the present invention. It is a longitudinal section explanatory view of other examples of the second reversible thermochromic body of the present invention. It is a longitudinal section explanatory view of other examples of a temperature control indicator of the present invention. It is a longitudinal section explanatory view of other examples of a temperature control indicator of the present invention. It is a longitudinal section explanatory view of other examples of a temperature control indicator of the present invention. It is a longitudinal section explanatory view of other examples of a temperature control indicator of the present invention.

Examples of the reversible thermochromic material applied to the present invention include (a) an electron-donating color-developing organic compound, (b) an electron-accepting compound, (c) a color reaction of (a) component and (b) component The reversible thermochromic microcapsule pigment containing a reversible thermochromic composition composed of a reaction medium that determines the occurrence temperature of the microcapsules, or the reversible thermochromic composition is dispersed in a thermoplastic or thermosetting resin. Examples of the reversible thermochromic resin particles include
The reversible thermochromic composition is described in Japanese Patent Publication No. 51-44706, Japanese Patent Publication No. 51-44707, and Japanese Patent Publication No. 1-29398, and the like before and after a predetermined temperature (color change point) as a boundary. Discoloration occurs in the temperature range above the high-temperature side discoloration point, and in the temperature range below the low-temperature side discoloration point, there is only one specific state at room temperature, and the other The state of is maintained while the heat or cold required to develop the state is applied, but returns to the state exhibited at room temperature when the application of heat or cold is removed, and has a relatively small hysteresis characteristic. A reversible thermochromic composition having a heat erasable type (erasable by heating and develops color by cooling) can be used.

  Further, large hysteresis characteristics described in Japanese Patent Publication No. 4-17154, Japanese Patent Laid-Open No. 7-179777, Japanese Patent Laid-Open No. 7-33997, Japanese Patent Laid-Open No. 8-39936, Japanese Patent Laid-Open No. 2005-1369, and the like. The shape of the curve that plots the change in color density due to temperature change is large when the temperature is increased from the low temperature side of the discoloration temperature range and when it is decreased from the high temperature side of the discoloration temperature range. Heat-erasable type (color erasable by heating, color develops by cooling) with color memory that can change color in different temperature paths and keep color developed at low temperature or erased at high temperature Reversible thermochromic composition (see FIG. 1) can be used.

The hysteresis characteristic of the color density-temperature curve of the reversible thermochromic composition will be described.
In FIG. 1, the vertical axis represents color density and the horizontal axis represents temperature. The change in color density due to the temperature change progresses along the arrow. Here, A is a point showing the density at the complete decoloring temperature t ₄ , B is a point showing the density at the decoloring start temperature t ₃ , C is a point showing the density at the color developing start temperature t ₂ , D is a point indicating the density at the complete color development temperature t ₁ .
The color change temperature range is a temperature range between t ₁ and t ₄ , and can exhibit any of a coloring state and a erasing state, and is a region between t ₂ and t ₃ which is a region having a large difference in color density. The temperature range is the substantial discoloration temperature range.
Further, the length of the line segment EF is a scale showing the contrast of discoloration, and the length of the line segment HG passing through the midpoint of the line segment EF is a temperature width (hereinafter referred to as hysteresis width ΔH) showing the degree of hysteresis. However, if this ΔH value is small, only one specific state can exist in the normal temperature region of both states before and after discoloration. Further, when the ΔH value is large, it becomes easy to maintain each state before and after the color change.
The reversible thermochromic composition can selectively retain one of a color-developed state and a decolorized state throughout the substantial color-changing temperature range (between t ₂ and t ₃ ).

  The temperature control indicator of the present invention has a ΔH value of the reversible thermochromic composition of 5 to 30 ° C., preferably 7 to 25 ° C., more preferably 10 to 20 ° C. It can effectively function for temperature control of a narrow article or its storage container. When the ΔH value is less than 5 ° C., it is difficult for the reversible thermochromic composition to selectively retain one of the colored state and the decolored state, and the temperature control indicator is easily discolored. On the other hand, when the ΔH value exceeds 30 ° C., even if the temperature environment around the article or its storage container changes, the temperature management indicator is less likely to change color, and it becomes difficult to appropriately control the temperature of the article or its storage container.

The compounds are specifically exemplified below for each of the components (a), (b) and (c).
The component (a) of the present invention, that is, the electron-donating color-developing organic compound, is a component that determines the color and is a compound that develops a color by donating an electron to the component (b), which is a developer.
Examples of the electron-donating color-developing organic compound include a phthalide compound, a fluoran compound, a styrinoquinoline compound, a diazarhodamine lactone compound, a pyridine compound, a quinazoline compound, and a bisquinazoline compound. Of these, a phthalide compound and a fluoran compound are preferable. ..
Examples of the phthalide compound include a diphenylmethanephthalide compound, a phenylindolylphthalide compound, an indolylphthalide compound, a diphenylmethaneazaphthalide compound, a phenylindolylazaphthalide compound, and a derivative thereof. Among them, phenylindolyl azaphthalide compounds and their derivatives are preferable.
Further, examples of the fluorane compound include an aminofluorane compound, an alkoxyfluorane compound, and derivatives thereof.
Examples of these compounds are shown below.
3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide,
3- (4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide,
3,3-bis (1-n-butyl-2-methylindol-3-yl) phthalide,
3,3-bis (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide,
3- (2-ethoxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide,
3- (2-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-propylindol-3-yl) -4-azaphthalide,
3,6-bis (diphenylamino) fluorane,
3,6-dimethoxyfluorane,
3,6-di-n-butoxyfluorane,
2-methyl-6- (N-ethyl-N-p-tolylamino) fluorane,
3-chloro-6-cyclohexylaminofluorane,
2-methyl-6-cyclohexylaminofluorane,
2- (2-chloroamino) -6-di-n-butylaminofluorane,
2- (2-chloroanilino) -6-di-n-butylaminofluorane,
2- (3-trifluoromethylanilino) -6-diethylaminofluorane,
2- (3-trifluoromethylanilino) -6-dipentylaminofluorane,
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,
1,2-benz-6-diethylaminofluorane,
1,2-benz-6- (N-ethyl-N-isobutylamino) fluorane,
1,2-benz-6- (N-ethyl-N-isoamylamino) fluorane,
2- (3-methoxy-4-dodecoxystyryl) quinoline,
2-diethylamino-8-diethylamino-4-methylspiro [5H- [1] benzopyrano [2,3-d] pyrimidin-5,1 ′ (3′H) isobenzofuran] -3′-one,
2-Di-n-butylamino-8-di-n-butylamino-4-methylspiro [5H- [1] benzopyrano [2,3-d] pyrimidine-5,1 '(3'H) isobenzofuran]- 3'-on,
2-di-n-butylamino-8-diethylamino-4-methylspiro [5H- [1] benzopyrano [2,3-d] pyrimidin-5,1 '(3'H) isobenzofuran] -3'-one,
2-Di-n-butylamino-8- (N-ethyl-N-isoamylamino) -4-methylspiro [5H- [1] benzopyrano [2,3-d] 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,
4,5,6,7-Tetrachloro-3- (4-dimethylamino-2-methoxyphenyl) -3- (1-butyl-2-methyl-1H-indol-3-yl) -1 (3H)- Isobenzofuranone,
4,5,6,7-Tetrachloro-3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methyl-1H-indol-3-yl) -1 (3H) -iso Benzofuranone,
4,5,6,7-Tetrachloro-3- (4-diethylamino-2-ethoxyphenyl) -3- (1-pentyl-2-methyl-1H-indol-3-yl) -1 (3H) -iso Benzofuranone,
4,5,6,7-Tetrachloro-3- (4-diethylamino-2-methylphenyl) -3- (1-ethyl-2-methyl-1H-indol-3-yl) -1 (3H) -iso Benzofuranone,
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 mentioned.
As the fluoranes, in addition to the compound having a substituent on the phenyl group forming a xanthene ring, a substituent on the phenyl group forming a lactone ring as well as a substituent on the phenyl group forming a xanthene ring (for example, It may be a compound which has an alkyl group such as a methyl group and a halogen atom such as a chlorine atom and exhibits blue or black.

The component (b), that is, the electron-accepting compound, is a compound that receives an electron from the component (a) and functions as a developer of the component (a).
As the electron-accepting compound, a group of compounds having active protons and derivatives thereof, a group of pseudo-acidic compounds [a group of compounds which are not acids but which act as an acid in the composition to develop the component (a)], electron vacancies There are compounds selected from the group of compounds having, and among these, compounds selected from the group of compounds having active protons are preferable.
Examples of the compound having an active proton and its derivative include a compound having a phenolic hydroxyl group, a metal salt thereof, a carboxylic acid and a metal salt thereof, preferably an aromatic carboxylic acid, an aliphatic carboxylic acid having 2 to 5 carbon atoms, and Examples thereof include metal salts thereof, acidic phosphoric acid esters and metal salts thereof, and azo compounds and derivatives thereof, 1,2,3-triazole and derivatives thereof, and among these, effective thermochromic properties are exhibited. A compound having a phenolic hydroxyl group is preferable because it can be obtained.
Compounds having a phenolic hydroxyl group are widely included from monophenol compounds to polyphenol compounds, and further include bis-type and tris-type phenols and phenol-aldehyde condensation resins. Among the compounds having a phenolic hydroxyl group, those having at least two benzene rings are preferable. Further, these compounds may have a substituent, and examples of the substituent include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, a carboxy group, and an ester or amide group thereof, a halogen atom and the like.
Examples of the metal contained in the metal salt of the compound having an active proton include sodium, potassium, calcium, zinc, zirconium, aluminum, magnesium, nickel, cobalt, tin, copper, iron, vanadium, titanium, lead, and molybdenum. Can be mentioned.

Examples of these compounds are shown below.
Phenol, o-cresol, tertiary butyl catechol, nonylphenol, n-octylphenol, n-dodecylphenol, n-stearylphenol, p-chlorophenol, p-bromophenol, o-phenylphenol, n-butyl p-hydroxybenzoate. , N-octyl p-hydroxybenzoate, resorcin, dodecyl gallate, 4,4-dihydroxydiphenylsulfone, bis (4-hydroxyphenyl) sulfide, 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- Droxyphenyl) 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-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-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane, 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) 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 (4-hydroxy-3-methylphenyl) propane, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,1-bis [2- ( 4-hydroxyphenyl) -2-propyl] benzene, bis (2-hydroxyphenyl) methane, 1,1,1-tris (4-hydroxyphenyl) ethane, 3,3-bis (3-methyl-4-hydroxyphenyl) ) Butane and the like can be mentioned.
A compound having a phenolic hydroxyl group can develop the most effective thermochromic properties, but aromatic carboxylic acids and aliphatic carboxylic acids having 2 to 5 carbon atoms, carboxylic acid metal salts, acidic phosphoric acid esters and their metals. It may be a compound selected from salts, 1,2,3-triazole and its derivatives.

The component (c) of the reaction medium that reversibly causes the electron transfer reaction by the components (a) and (b) in the specific temperature range will be described.
Examples of the component (c) include alcohols, esters, ketones, ethers and acid amides.

  Furthermore, in order to exhibit a large hysteresis characteristic with respect to the color density-temperature curve and to change the color, and to impart the color memory property depending on the temperature change, the temperature of 5 ° C. or higher and less than 50 ° C. described in JP-B-4-17154 is used. Carboxylic acid ester compound showing ΔT value (melting point-clouding point), for example, carboxylic acid ester containing substituted aromatic ring in molecule, ester of carboxylic acid containing unsubstituted aromatic ring and aliphatic alcohol having 10 or more carbon atoms A carboxylic acid ester containing a cyclohexyl group in the molecule, a fatty acid having 6 or more carbon atoms and an unsubstituted aromatic alcohol or phenol, a fatty acid having 8 or more carbon atoms and a branched aliphatic alcohol or ester, a dicarboxylic acid and an aromatic alcohol, or Esters of branched aliphatic alcohols, dibenzyl cinnamate, heptyl stearate, didecyl adipate, adipi Dilauryl, dimyristyl adipate, dicetyl adipate, distearyl adipate, trilaurin, trimyristin, tristearin, dimyristin, distearate, and the like.

Fatty acid ester compounds obtained from odd-numbered aliphatic monohydric alcohols having 9 or more carbon atoms and aliphatic carboxylic acids having even-numbered carbons, n-pentyl alcohol or n-heptyl alcohol, and even-numbered aliphatic carboxylic acids having 10 to 16 carbon atoms A fatty acid ester compound having a total carbon number of 17 to 23 obtained from an acid is also effective.
Specifically, n-pentadecyl acetate, n-tridecyl butyrate, n-pentadecyl butyrate, n-undecyl caproate, n-tridecyl caproate, n-pentadecyl caproate, n-nonyl caprylate, n-undecyl caprylate, N-Tridecyl caprylate, n-pentadecyl caprylate, n-heptyl caprate, n-nonyl caprate, n-undecyl caprate, n-tridecyl caprate, n-pentadecyl caprate, n-pentyl laurate, lauric acid n-heptyl, n-nonyl laurate, n-undecyl laurate, n-tridecyl laurate, n-pentadecyl laurate, n-pentyl myristate, n-heptyl myristate, n-nonyl myristate, n-myristate Undecyl, n-tridecyl myristate, N-pentadecyl lithinate, n-pentyl palmitate, n-heptyl palmitate, n-nonyl palmitate, n-undecyl palmitate, n-tridecyl palmitate, n-pentadecyl palmitate, n-nonyl stearate, stearic acid n-Undecyl, n-tridecyl stearate, n-pentadecyl stearate, n-nonyl eicosanate, n-undersi eicosanate, n-tridecyl eicosanate, n-pentadecyl eicosanate, n-nonyl behenate, n-behenate. Examples include undecyl, n-tridecyl behenate, and n-pentadecyl behenate.

As the ketones, aliphatic ketones having a total carbon number of 10 or more are effective, and 2-decanone, 3-decanone, 4-decanone, 2-undecanone, 3-undecanone, 4-undecanone, 5-undecanone, 2 -Dodecanone, 3-dodecanone, 4-dodecanone, 5-dodecanone, 2-tridecanone, 3-tridecanone, 2-tetradecanone, 2-pentadecanone, 8-pentadecanone, 2-hexadecanone, 3-hexadecanone, 9-heptadecane, 2-pentadecanone , 2-octadecanone, 2-nonadecanone, 10-nonadecanone, 2-eicosanone, 11-eicosanone, 2-heneicosanone, 2-docosanone, laurone, stearone and the like.
Furthermore, arylalkylketones having a total carbon number of 12 to 24, for example, n-octadecanophenone, n-heptadecanophenone, n-hexadecanophenone, n-pentadecanophenone, n-tetradeca 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-pentylacetoph Non, cyclohexyl phenyl ketone, benzyl -n- butyl ketone, 4-n-butyl acetophenone, n- hexanophenone, 4-isobutyl acetophenone, 1-acetonaphthone, 2-acetonaphthone, cyclopentyl phenyl ketone.

  As the ethers, aliphatic ethers having a total carbon number of 10 or more are effective, and dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, dinonyl ether, didecyl ether, diundecyl ether, didodecyl ether, ditridecyl ether. Decyl 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 mentioned.

  Examples of acid amides include acetamide, propionic acid amide, butyric acid amide, caproic acid amide, caprylic acid amide, capric acid amide, lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, and oleic acid amide. , Erucamide, benzamide, caproic acid anilide, caprylic acid anilide, capric acid anilide, lauric acid anilide, myristic acid anilide, palmitic acid anilide, stearic acid anilide, behenic acid anilide, oleic acid anilide, erucic acid anilide, caproic acid N -Methylamide, caprylic acid N-methylamide, capric acid N-methylamide, lauric acid N-methylamide, myristic acid N-methylamide, palmitic acid N-methylamide, stearic acid N-methylamido , Behenic acid N-methylamide, oleic acid N-methylamide, erucic acid N-methylamide, lauric acid N-ethylamide, myristic acid N-ethylamide, palmitic acid N-ethylamide, stearic acid N-ethylamide, oleic acid N-ethylamide, lauric acid Acid N-butylamide, myristic acid N-butylamide, palmitic acid N-butylamide, stearic acid N-butylamide, oleic acid N-butylamide, lauric acid N-octylamide, myristic acid N-octylamide, palmitic acid N-octylamide, Stearic acid N-octylamide, oleic acid N-octylamide, lauric acid N-dodecylamide, myristic acid N-dodecylamide, palmitic acid N-dodecylamide, stearic acid N-dodecylamide, oleic acid Acid N-dodecylamide, dilauric acid amide, dimyristic acid amide, dipalmitic acid amide, distearic acid amide, dioleic acid amide, trilauric acid amide, trimyristic acid amide, tripalmitic acid amide, tristearic acid amide, trioleic acid Amide, succinic acid amide, adipic acid amide, glutaric acid amide, malonic acid amide, azelaic acid amide, maleic acid amide, succinic acid N-methylamide, adipic acid N-methylamide, glutaric acid N-methylamide, malonic acid N-methylamide, Azelaic acid N-methylamide, succinic acid N-ethylamide, adipic acid N-ethylamide, glutaric acid N-ethylamide, malonic acid N-ethylamide, azelaic acid N-ethylamide, succinic acid N-butylamide, adipic acid N- Butylamide, glutaric acid N-butylamide, malonic acid N-butylamide, adipic acid N-octylamide, adipic acid N-dodecylamide and the like can be mentioned.

（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、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はそれぞれ水素原子、炭素数１〜４のアルキル基、メトキシ基、又はハロゲン原子を示し、ｒ及びｐはそれぞれ１〜３の整数を示す。）
式（１）で示される化合物のうち、Ｒ_１が水素原子の場合、より広いヒステリシス幅を有する可逆熱変色性組成物が得られるため好適であり、さらにＲ_１が水素原子であり、且つ、ｍが０の場合がより好適である。
なお、式（１）で示される化合物のうち、より好ましくは下記一般式（２）で示される化合物が用いられる。

式中のＲは炭素数８以上のアルキル基又はアルケニル基を示すが、好ましくは炭素数１０〜２４のアルキル基、さらに好ましくは炭素数１２〜２２のアルキル基である。
式（２）で示される化合物として具体的には、オクタン酸−４−ベンジルオキシフェニルエチル、ノナン酸−４−ベンジルオキシフェニルエチル、デカン酸−４−ベンジルオキシフェニルエチル、ウンデカン酸−４−ベンジルオキシフェニルエチル、ドデカン酸−４−ベンジルオキシフェニルエチル、トリデカン酸−４−ベンジルオキシフェニルエチル、テトラデカン酸−４−ベンジルオキシフェニルエチル、ペンタデカン酸−４−ベンジルオキシフェニルエチル、ヘキサデカン酸−４−ベンジルオキシフェニルエチル、ヘプタデカン酸−４−ベンジルオキシフェニルエチル、オクタデカン酸−４−ベンジルオキシフェニルエチルを例示できる。 Further, as the component (C), a compound represented by the following general formula (1) can also be used.

(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 an alkenyl group having 4 or more carbon atoms, Y ₁ and Y ₂ each represent a hydrogen atom, a carbon number 1 to 4 represents an alkyl group, a methoxy group, or a halogen atom, and r and p each represent an integer of 1 to 3.)
Of the compounds represented by the formula (1), when R ₁ is a hydrogen atom, a reversible thermochromic composition having a wider hysteresis width can be obtained, which is preferable, and R ₁ is a hydrogen atom, and It is more preferable that m is 0.
Among the compounds represented by the formula (1), the compound represented by the following general formula (2) is more preferably used.

R in the formula represents an alkyl group or an alkenyl group having 8 or more carbon atoms, preferably an alkyl group having 10 to 24 carbon atoms, and more preferably an alkyl group having 12 to 22 carbon atoms.
Specific examples of the compound represented by the formula (2) include 4-benzyloxyphenylethyl octanoate, 4-benzyloxyphenylethyl nonanoate, 4-benzyloxyphenylethyl decanoate, and 4-benzyl undecanoate. Oxyphenylethyl, 4-benzyloxyphenylethyl dodecanoate, 4-benzyloxyphenylethyl tridecanoate, 4-benzyloxyphenylethyl tetradecanoate, 4-benzyloxyphenylethyl pentadecanoate, 4-benzyl hexadecanoate Examples include oxyphenylethyl, 4-benzyloxyphenylethyl heptadecanoate, and 4-benzyloxyphenylethyl octadecanoate.

（式中、Ｒは炭素数８以上のアルキル基又はアルケニル基を示し、ｍ及びｎはそれぞれ１〜３の整数を示し、Ｘ及びＹはそれぞれ水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、又はハロゲン原子を示す。）
式（３）で示される化合物として具体的には、オクタン酸１,１−ジフェニルメチル、ノナン酸１,１−ジフェニルメチル、デカン酸１,１−ジフェニルメチル、ウンデカン酸１,１−ジフェニルメチル、ドデカン酸１,１−ジフェニルメチル、トリデカン酸１,１−ジフェニルメチル、テトラデカン酸１,１−ジフェニルメチル、ペンタデカン酸１,１−ジフェニルメチル、ヘキサデカン酸１,１−ジフェニルメチル、ヘプタデカン酸１,１−ジフェニルメチル、オクタデカン酸１,１−ジフェニルメチルを例示できる。 Furthermore, a compound represented by the following general formula (3) can be used as the component (C).

(In the formula, R represents an alkyl group or an alkenyl group having 8 or more carbon atoms, m and n each represent an integer of 1 to 3, and X and Y each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a carbon atom. It represents an alkoxy group of formulas 1 to 4, or a halogen atom.)
Specific examples of the compound represented by the formula (3) include 1,1-diphenylmethyl octanoate, 1,1-diphenylmethyl nonanoate, 1,1-diphenylmethyl decanoate, 1,1-diphenylmethyl undecanoate, 1,1-Diphenylmethyl dodecanoate, 1,1-Diphenylmethyl tridecanoate, 1,1-Diphenylmethyl tetradecanoate, 1,1-Diphenylmethyl pentadecanoate, 1,1-Diphenylmethyl hexadecanoate, Heptadecanoic acid 1,1 Examples thereof include diphenylmethyl and 1,1-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。）
式（４）で示される化合物として具体的には、マロン酸と２−〔４−(４−クロロベンジルオキシ）フェニル）〕エタノールとのジエステル、こはく酸と２−（４−ベンジルオキシフェニル）エタノールとのジエステル、こはく酸と２−〔４−(３−メチルベンジルオキシ）フェニル）〕エタノールとのジエステル、グルタル酸と２−（４−ベンジルオキシフェニル）エタノールとのジエステル、グルタル酸と２−〔４−(４−クロロベンジルオキシ）フェニル）〕エタノールとのジエステル、アジピン酸と２−（４−ベンジルオキシフェニル）エタノールとのジエステル、ピメリン酸と２−（４−ベンジルオキシフェニル）エタノールとのジエステル、スベリン酸と２−（４−ベンジルオキシフェニル）エタノールとのジエステル、スベリン酸と２−〔４−(３−メチルベンジルオキシ）フェニル）〕エタノールとのジエステル、スベリン酸と２−〔４−(４−クロロベンジルオキシ）フェニル）〕エタノールとのジエステル、スベリン酸と２−〔４−(２，４−ジクロロベンジルオキシ）フェニル）〕エタノールとのジエステル、アゼライン酸と２−（４−ベンジルオキシフェニル）エタノールとのジエステル、セバシン酸と２−（４−ベンジルオキシフェニル）エタノールとのジエステル、１，１０−デカンジカルボン酸と２−（４−ベンジルオキシフェニル）エタノールとのジエステル、１，１８−オクタデカンジカルボン酸と２−（４−ベンジルオキシフェニル）エタノールとのジエステル、１，１８−オクタデカンジカルボン酸と２−〔４−(２−メチルベンジルオキシ）フェニル）〕エタノールとのジエステルを例示できる。 Further, a compound represented by the following general formula (4) can be used as the component (C).

(In the formula, X represents any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, and a halogen atom, m represents an integer of 1 to 3, and n represents an integer of 1 to 20.)
Specific examples of the compound represented by the formula (4) include diesters of malonic acid and 2- [4- (4-chlorobenzyloxy) phenyl)] ethanol, succinic acid and 2- (4-benzyloxyphenyl) ethanol. , A diester of succinic acid and 2- [4- (3-methylbenzyloxy) phenyl)] ethanol, a diester of glutaric acid and 2- (4-benzyloxyphenyl) ethanol, glutaric acid and 2- [ 4- (4-chlorobenzyloxy) phenyl)] ethanol diester, adipic acid 2- (4-benzyloxyphenyl) ethanol diester, pimelic acid 2- (4-benzyloxyphenyl) ethanol diester , A diester of suberic acid with 2- (4-benzyloxyphenyl) ethanol, suberic acid 2- [4- (3-Methylbenzyloxy) phenyl)] ethanol diester, suberic acid and 2- [4- (4-chlorobenzyloxy) phenyl)] ethanol diester, suberic acid and 2- [4 -(2,4-Dichlorobenzyloxy) phenyl)] ethanol diester, azelaic acid 2- (4-benzyloxyphenyl) ethanol diester, sebacic acid 2- (4-benzyloxyphenyl) ethanol Diesters, diesters of 1,10-decanedicarboxylic acid and 2- (4-benzyloxyphenyl) ethanol, diesters of 1,18-octadecanedicarboxylic acid and 2- (4-benzyloxyphenyl) ethanol, 1,18- Octadecane dicarboxylic acid and 2- [4- (2-methylbenzyloxy) phenyl )] Can be exemplified diester of ethanol.

（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。）
式（５）で示される化合物として具体的には、１，３−ビス（２−ヒドロキシエトキシ）ベンゼンとカプリン酸とのジエステル、１，３−ビス（２−ヒドロキシエトキシ）ベンゼンとウンデカン酸とのジエステル、１，３−ビス（２−ヒドロキシエトキシ）ベンゼンとラウリン酸とのジエステル、１，３−ビス（２−ヒドロキシエトキシ）ベンゼンとミリスチン酸とのジエステル、１，４−ビス（ヒドロキシメトキシ）ベンゼンと酪酸とのジエステル、１，４−ビス（ヒドロキシメトキシ）ベンゼンとイソ吉草酸とのジエステル、１，４−ビス（２−ヒドロキシエトキシ）ベンゼンと酢酸とのジエステル、１，４−ビス（２−ヒドロキシエトキシ）ベンゼンとプロピオン酸とのジエステル、１，４−ビス（２−ヒドロキシエトキシ）ベンゼンと吉草酸とのジエステル、１，４−ビス（２−ヒドロキシエトキシ）ベンゼンとカプロン酸とのジエステル、１，４−ビス（２−ヒドロキシエトキシ）ベンゼンとカプリル酸とのジエステル、１，４−ビス（２−ヒドロキシエトキシ）ベンゼンとカプリン酸とのジエステル、１，４−ビス（２−ヒドロキシエトキシ）ベンゼンとラウリン酸とのジエステル、１，４−ビス（２−ヒドロキシエトキシ）ベンゼンとミリスチン酸とのジエステルを例示できる。 Furthermore, a compound represented by the following general formula (5) can be used as the component (C).

(In the formula, R represents an alkyl group or an alkenyl group having 1 to 21 carbon atoms, and n represents an integer of 1 to 3.)
Specific examples of the compound represented by the formula (5) include diesters of 1,3-bis (2-hydroxyethoxy) benzene and capric acid, and 1,3-bis (2-hydroxyethoxy) benzene and undecanoic acid. Diesters, diesters of 1,3-bis (2-hydroxyethoxy) benzene and lauric acid, diesters of 1,3-bis (2-hydroxyethoxy) benzene and myristic acid, 1,4-bis (hydroxymethoxy) benzene With butyric acid, 1,4-bis (hydroxymethoxy) benzene with isovaleric acid, 1,4-bis (2-hydroxyethoxy) benzene with acetic acid, 1,4-bis (2- Diester of hydroxyethoxy) benzene and propionic acid, 1,4-bis (2-hydroxyethoxy) benzene Diester with valeric acid, diester with 1,4-bis (2-hydroxyethoxy) benzene and caproic acid, diester with 1,4-bis (2-hydroxyethoxy) benzene and caprylic acid, 1,4-bis ( Diester of 2-hydroxyethoxy) benzene and capric acid, diester of 1,4-bis (2-hydroxyethoxy) benzene and lauric acid, diester of 1,4-bis (2-hydroxyethoxy) benzene and myristic acid Can be illustrated.

（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。）
式（６）で示される化合物として具体的には、こはく酸と２−フェノキシエタノールとのジエステル、スベリン酸と２−フェノキシエタノールとのジエステル、セバシン酸と２−フェノキシエタノールとのジエステル、１，１０−デカンジカルボン酸と２−フェノキシエタノールとのジエステル、１，１８−オクタデカンジカルボン酸と２−フェノキシエタノールとのジエステルを例示できる。 Further, a compound represented by the following general formula (6) can be used as the component (C).

(In the formula, X represents any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom, m represents an integer of 1 to 3, and n represents 1 to 20. Indicates the integer of.)
Specific examples of the compound represented by the formula (6) include diesters of succinic acid and 2-phenoxyethanol, diesters of suberic acid and 2-phenoxyethanol, diesters of sebacic acid and 2-phenoxyethanol, and 1,10-decanedicarboxylic acid. Examples thereof include diesters of 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の整数を示す。）
式（７）で示される化合物として具体的には、４−フェニル安息香酸デシル、４−フェニル安息香酸ラウリル、４−フェニル安息香酸ミリスチル、４−フェニル安息香酸シクロヘキシルエチル、４−ビフェニル酢酸オクチル、４−ビフェニル酢酸ノニル、４−ビフェニル酢酸デシル、４−ビフェニル酢酸ラウリル、４−ビフェニル酢酸ミリスチル、４−ビフェニル酢酸トリデシル、４−ビフェニル酢酸ペンタデシル、４−ビフェニル酢酸セチル、４−ビフェニル酢酸シクロペンチル、４−ビフェニル酢酸シクロヘキシルメチル、４−ビフェニル酢酸ヘキシル、４−ビフェニル酢酸シクロヘキシルメチルを例示できる。 Further, a compound represented by the following general formula (7) can also be used as the component (C).

(In the formula, R represents any one of an alkyl group having 4 to 22 carbon atoms, a cycloalkylalkyl group, a cycloalkyl group, and an alkenyl group having 4 to 22 carbon atoms, and X is a hydrogen atom or 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 represents an integer of 0 or 1.)
Specific examples of the compound represented by the formula (7) include decyl 4-phenylbenzoate, lauryl 4-phenylbenzoate, myristyl 4-phenylbenzoate, cyclohexylethyl 4-phenylbenzoate, octyl 4-biphenylacetate, and 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-biphenyl Examples include cyclohexylmethyl acetate, hexyl 4-biphenylacetate, and cyclohexylmethyl 4-biphenylacetate.

（式中、Ｒは炭素数３〜１８のアルキル基又は炭素数３〜１８の脂肪族アシル基を示し、Ｘは水素原子、炭素数１〜３のアルキル基、炭素数１又は２のアルコキシ基、ハロゲン原子のいずれかを示し、Ｙは水素原子又はメチル基を示し、Ｚは水素原子、炭素数１〜４のアルキル基、炭素数１又は２のアルコキシ基、ハロゲン原子のいずれかを示す。）
式（８）で示される化合物として具体的には、４−ブトキシ安息香酸フェノキシエチル、４−ペンチルオキシ安息香酸フェノキシエチル、４−テトラデシルオキシ安息香酸フェノキシエチル、４−ヒドロキシ安息香酸フェノキシエチルとドデカン酸とのエステル、バニリン酸フェノキシエチルのドデシルエーテルを例示できる。 Furthermore, a compound represented by the following general formula (8) can be used as the component (C).

(In the formula, R represents an alkyl group having 3 to 18 carbon atoms or an aliphatic acyl group having 3 to 18 carbon atoms, X represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 or 2 carbon atoms. , A halogen atom, Y represents a hydrogen atom or a methyl group, and Z represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 or 2 carbon atoms, or a halogen atom. )
Specific examples of the compound represented by the formula (8) include phenoxyethyl 4-butoxybenzoate, phenoxyethyl 4-pentyloxybenzoate, phenoxyethyl 4-tetradecyloxybenzoate, phenoxyethyl 4-hydroxybenzoate and dodecane. Examples thereof include esters with acids and dodecyl ether of phenoxyethyl vanillic acid.

（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の整数を示す。）
式（９）で示される化合物として具体的には、ｐ−ヒドロキシ安息香酸オクチルの安息香酸エステル、ｐ−ヒドロキシ安息香酸デシルの安息香酸エステル、ｐ−ヒドロキシ安息香酸ヘプチルのｐ−メトキシ安息香酸エステル、ｐ−ヒドロキシ安息香酸ドデシルのo-メトキシ安息香酸エステル、ｐ−ヒドロキシ安息香酸シクロヘキシルメチルの安息香酸エステルを例示できる。 Further, a compound represented by the following general formula (9) can also be used as the component (C).

(In the formula, R represents any one of an alkyl group having 4 to 22 carbon atoms, an alkenyl group having 4 to 22 carbon atoms, a cycloalkylalkyl group, and a cycloalkyl group, and X represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen. Represents any one of atoms, Y represents any one of a hydrogen atom, an alkyl group, an alkoxy group, and a halogen atom, and n represents an integer of 0 or 1.)
Specific examples of the compound represented by the formula (9) include benzoic acid ester of octyl p-hydroxybenzoate, benzoic acid ester of decyl p-hydroxybenzoate, p-methoxybenzoic acid ester of heptyl p-hydroxybenzoate, Examples thereof include o-methoxybenzoic acid ester of dodecyl p-hydroxybenzoate and benzoic acid ester of cyclohexylmethyl p-hydroxybenzoate.

（式中、Ｒは炭素数３〜１８のアルキル基、炭素数６〜１１のシクロアルキルアルキル基、炭素数５〜７のシクロアルキル基、炭素数３〜１８のアルケニル基のいずれかを示し、Ｘは水素原子、炭素数１〜４のアルキル基、炭素数１〜３のアルコキシ基、ハロゲン原子のいずれかを示し、Ｙは水素原子、炭素数１〜４のアルキル基、メトキシ基、エトキシ基、ハロゲン原子のいずれかを示す。）
式（１０）で示される化合物として具体的には、ｐ−ヒドロキシ安息香酸ノニルのフェノキシエチルエーテル、ｐ−ヒドロキシ安息香酸デシルのフェノキシエチルエーテル、ｐ−ヒドロキシ安息香酸ウンデシルのフェノキシエチルエーテル、バニリン酸ドデシルのフェノキシエチルエーテルを例示できる。 Furthermore, a compound represented by the following general formula (10) can be used as the component (C).

(In the formula, 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 represents any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a halogen atom, and Y represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, an ethoxy group. , Indicates one of the halogen atoms.)
Specific examples of the compound represented by the formula (10) include phenoxyethyl ether of nonyl p-hydroxybenzoate, phenoxyethyl ether of decyl p-hydroxybenzoate, phenoxyethyl ether of undecyl p-hydroxybenzoate, and dodecyl vanillate. The phenoxyethyl ether can be exemplified.

（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。）
式（１１）で示される化合物として具体的には、１，３−ビス（２−ヒドロキシエトキシ）ベンゼンとシクロヘキサンカルボン酸とのジエステル、１，４−ビス（２−ヒドロキシエトキシ）ベンゼンとシクロヘキサンプロピオン酸とのジエステル、１，３−ビス（２−ヒドロキシエトキシ）ベンゼンとシクロヘキサンプロピオン酸とのジエステルを例示できる。 Further, a compound represented by the following general formula (11) can also be used as the component (C).

(In the formula, R represents a cycloalkyl group having 3 to 8 carbon atoms or a cycloalkylalkyl group having 4 to 9 carbon atoms, and n represents an integer of 1 to 3.)
Specific examples of the compound represented by the formula (11) include diesters of 1,3-bis (2-hydroxyethoxy) benzene and cyclohexanecarboxylic acid, 1,4-bis (2-hydroxyethoxy) benzene and cyclohexanepropionic acid. And a diester of 1,3-bis (2-hydroxyethoxy) benzene and cyclohexanepropionic acid.

（式中、Ｒは炭素数３〜１７のアルキル基、炭素数３〜８のシクロアルキル基、炭素数５〜８のシクロアルキルアルキル基のいずれかを示し、Ｘは水素原子、炭素数１〜５のアルキル基、メトキシ基、エトキシ基、ハロゲン原子のいずれかを示し、ｎは１〜３の整数を示す。）
式（１２）で示される化合物として具体的には、４−フェニルフェノールエチレングリコールエーテルとシクロヘキサンカルボン酸とのジエステル、４−フェニルフェノールジエチレングリコールエーテルとラウリン酸とのジエステル、４−フェニルフェノールトリエチレングリコールエーテルとシクロヘキサンカルボン酸とのジエステル、４−フェニルフェノールエチレングリコールエーテルとオクタン酸とのジエステル、４−フェニルフェノールエチレングリコールエーテルとノナン酸とのジエステル、４−フェニルフェノールエチレングリコールエーテルとデカン酸とのジエステル、４−フェニルフェノールエチレングリコールエーテルとミリスチン酸とのジエステルを例示できる。 Further, a compound represented by the following general formula (12) can be used as the component (C).

(In the formula, R represents any one of an alkyl group having 3 to 17 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and a cycloalkylalkyl group having 5 to 8 carbon atoms, X is a hydrogen atom, 1 to 1 carbon atoms. 5 represents any one of an alkyl group, a methoxy group, an ethoxy group, and a halogen atom, and n represents an integer of 1 to 3.)
Specific examples of the compound represented by the formula (12) include a diester of 4-phenylphenol ethylene glycol ether and cyclohexanecarboxylic acid, a diester of 4-phenylphenol diethylene glycol ether and lauric acid, and 4-phenylphenol triethylene glycol ether. And cyclohexanecarboxylic acid diester, 4-phenylphenol ethylene glycol ether and octanoic acid diester, 4-phenylphenol ethylene glycol ether and nonanoic acid diester, 4-phenylphenol ethylene glycol ether and decanoic acid diester, An example is a diester of 4-phenylphenol ethylene glycol ether and myristic acid.

  Further, (b) a specific alkoxyphenol compound having a linear or side chain alkyl group having 3 to 18 carbon atoms as an electron-accepting compound (JP-A-11-129623), a specific hydroxybenzoic acid ester (JP-A-2001). It is also possible to apply a reversible thermochromic microcapsule pigment containing a heat-coloring type reversible thermochromic composition using a gallic acid ester (Japanese Patent Application Laid-Open No. 2003-253149) or the like.

  The reversible thermochromic composition is a compatible solution containing (a), (b), and (c) as essential components, and the ratio of each component depends on the concentration, the color change temperature, the color change form, and the type of each component. Although it depends on the composition, generally, the component ratio for obtaining desired characteristics is 0.1 to 100, preferably 0.1 to 50, more preferably 0.1 to 100 parts of the (b) component. 5 to 20, (c) component 5 to 200, preferably 5 to 100, more preferably 10 to 100 (the above-mentioned ratios are all parts by mass).

Microencapsulation can be carried out by known interfacial polymerization method, in situ polymerization method, liquid hardening coating method, phase separation method from aqueous solution, phase separation method from organic solvent, melt dispersion cooling method, air suspension coating method, spraying. There is a drying method or the like, which is appropriately selected depending on the application. Further, the surface of the microcapsules may be provided with a secondary resin film for imparting durability depending on the purpose, or the surface characteristics may be modified for practical use.
The reversible thermochromic microcapsule pigment preferably has a mass ratio of inclusion: wall film of 7: 1 to 1: 1 and when the mass ratio of inclusion and wall film is within the above range, the color is developed. It is possible to prevent the color density and the sharpness from deteriorating. More preferably, the mass ratio of inclusion: wall membrane is 6: 1 to 1: 1.

  The temperature control indicator of the present invention is one of the reversible thermochromic materials in which the reversible thermochromic material is in a colored state, and the other reversible thermochromic material is in a decolored state, and the temperature-controllable article or its storage container Within the proper temperature range, only the color of the reversible thermochromic material in the colored state is visually recognized (initial state).

When one of the reversible thermochromic materials is in a colored state, the temperature control indicator in the initial state is in a proper temperature range when the reversible thermochromic material in a colored state disappears when placed in a temperature environment higher than the proper temperature range. Then, the color of each reversible thermochromic material in the decolored state is visually recognized (state 1).
Cooling is required to return the reversible thermochromic material from this state to the color-developed state, but when placed under a temperature environment lower than the appropriate temperature range, each reversible thermochromic material in the decolorized state develops color together, Within the appropriate temperature range, a color in which each reversible thermochromic material is mixed in the colored state is visually recognized (state 2).
When the temperature control indicator in the initial state is placed in a temperature environment lower than the proper temperature range, the reversible thermochromic material in the decolored state develops color, and each reversible thermochromic material develops color within the proper temperature range. Colors mixed in the state are visually recognized (state 2).
Heating is required to return the reversible thermochromic material from this state to the decolorized state, but when placed in a temperature environment higher than the appropriate temperature range, each reversible thermochromic material in the colored state is decolorized together. In the appropriate temperature range, the color of each reversible thermochromic material is in the decolored state is visually recognized (state 1).
When the temperature control indicator of the present invention is placed in a temperature environment higher or lower than the appropriate temperature range from the initial state, one of the initial reversible thermochromic materials does not return to the color shown in the color-developed state, and the temperature control is performed. It is possible to determine whether or not the article requiring the above or its storage container has deviated from the proper temperature range.

In each of the reversible thermochromic materials provided in the first reversible thermochromic body and the second reversible thermochromic body constituting the temperature management indicator of the present invention, the (a), (b) and (c) components are the same. (Each reversible thermochromic material has the same composition), each reversible thermochromic material exhibits the same color in the color-developed state, and has a perfect color development temperature t ₁ , a color development start temperature t ₂ , and a decolorization start temperature. Since t ₃ and the complete decoloring temperature t ₄ are also the same, one of the reversible thermochromic materials is in a colored state and the color visually recognized in the temperature control indicator in the initial state is different from that of each reversible thermochromic material in a colored state. The color visually recognized in the temperature management indicator of the mixed state 2 is the same color, and the color visually recognized in the state 2 has a higher density than the color visually recognized in the initial state. Out of range In this case, the only visible change is the change in shade, and it may be difficult to determine whether or not the temperature has deviated from the appropriate temperature range. Therefore, it is preferable that the reversible thermochromic materials provided in the first reversible thermochromic material and the second reversible thermochromic material have the component (a), that is, the electron-donating color-developing organic compound different from each other. It is more preferable that the reversible thermochromic materials provided in the one reversible thermochromic body and the second reversible thermochromic body exhibit mutually different colors in a colored state.

  When the (a) component of each reversible thermochromic material provided in the first reversible thermochromic body and the second reversible thermochromic body is different from each other, each reversible thermochromic material shows a different color in a colored state, The color visible on the temperature control indicator in the initial state where one of the reversible thermochromic materials is in the colored state and the color seen in the temperature management indicator in the state 2 in which both of the reversible thermochromic materials are mixed in the colored state. Since the colors are different, the change visually recognized when the temperature management indicator deviates from the proper temperature range is a change in hue, and it is possible to clearly and easily determine whether or not the temperature deviates from the proper temperature range. ..

Further, the temperature control indicator of the present invention is the complete color development temperature t ₁ , the color development start temperature t ₂ , the decolorization start of each reversible thermochromic material provided in the first reversible thermochromic material and the second reversible thermochromic material. By changing the temperature t ₃ or the complete erasing temperature t ₄ , it is possible to provide a temperature management function of the article or its storage container that requires temperature management in a specific temperature range, and the temperatures t ₁ , t ₂ , T ₃ , or t ₄ are changed, at least one of the component (a), the component (b), and the component (c) constituting each reversible thermochromic material is different from each other, specifically, ( It is preferable that the (a) component is different from each other, or the (c) component is different from each other, and the (a) component and the (c) component constituting each reversible thermochromic material are different from each other, or each reversible thermochromic property. (A) component that constitutes the material, B) component, and (c) it is more preferred that all of the components are different from each other.

In the temperature control indicator of the present invention, the reversible thermochromic material in the color-developed state has a perfect coloring temperature t ₁ , a coloring start temperature t ₂ , a decoloring start temperature t ₃ , and a completely decoloring temperature t _4, and The complete color development temperature t ₁ , the color development start temperature t ₂ , the decolorization start temperature t ₃ , and the complete decolorization temperature t ₄ of the reversible thermochromic material may be “substantially the same”. The term “substantially the same” means that the temperatures t ₁ , t ₂ , t ₃ , and t ₄ of the reversible thermochromic material in the colored state and the decolored state are exactly the same, and in the present invention, , The absolute value (| ΔT |) of the temperature difference (ΔT) of the reversible thermochromic material in the colored state and the decolored state is 3 ° C. or less, specifically, | ΔT = [reversible thermochromic property in the colored state each temperature of the material _{(t 1, t 2, t} 3, t 4) ] - [the temperature of the thermochromic material decolored state _{(t 1, t 2, t} 3, t 4) ] | ≦ 3 ° C. It also includes satisfying the condition, preferably | ΔT | ≦ 2 ° C., and more preferably | ΔT | ≦ 1 ° C.

In each of the reversible thermochromic materials provided in the first reversible thermochromic material and the second reversible thermochromic material, the complete coloring temperature t ₁ of the reversible thermochromic material in the colored state and the reversible thermochromic material in the decolorized state complete coloring temperature t _1, and color development initiation temperature t ₂ of the color start temperature t ₂ and thermochromic material decolored state of the reversibly thermochromic material colored state are each substantially identical, and, the colored state of decoloration of thermochromic material start temperature t ₃ and decoloring starting temperature t ₃ of the reversible thermochromic material decolored state of it is substantially the same, complete decoloring temperature t of the thermochromic material colored state ₄ will be described color change behavior of the complete decoloring temperature t ₄ is less than the temperature control indicator reversibly thermochromic material decolored state.
In the temperature control indicator in the initial state, the reversible thermochromic material A is in a colored state and the reversible thermochromic material B is in a decolored state. In FIG. 2, the solid line indicates the reversible thermochromic material A (of the colored state). The color density-temperature curve of the reversible thermochromic material), and the broken line is the color density-temperature curve of the reversible thermochromic material B (reversible thermochromic material in the decolored state). Also, t _4A is a complete decoloring temperature t ₄ of thermochromic material A, t _4B represents the complete decoloring temperature t ₄ of thermochromic material B, respectively.

In the temperature control indicator in the initial state, the reversible thermochromic material A is in a color-developing state, and within the proper temperature range (the temperature range exceeding the temperature t ₁ and less than the temperature t _4A ), only the color of the reversible thermochromic material A is shown. When the reversible thermochromic material A is visually recognized and placed in a temperature environment higher than the appropriate temperature range, the reversible thermochromic material A in the colored state is decolored, and the reversible thermochromic material is visually decolored within the appropriate temperature range. (State 1).
Cooling is required to return the temperature management indicator to the initial state from this state, but if placed in a temperature environment lower than the appropriate temperature range, each reversible thermochromic material in the decolored state will develop color, and Within the temperature range (within the temperature range of less than the temperature t _4A ), a color in which the reversible thermochromic materials are mixed in the colored state is visually recognized (state 2).
Further, when the temperature control indicator in the initial state is placed in a temperature environment lower than the proper temperature range, the reversible thermochromic material B in the decolored state develops color, and within the proper temperature range (within the temperature range of less than the temperature t _4A ). Then, a color in which the reversible thermochromic materials are mixed in the colored state is visually recognized (state 2).
Heating is required to return the temperature management indicator from this state to the initial state, but when placed in a temperature environment of temperature t _4A or higher and lower than temperature t _4B, only the reversible thermochromic material A in the colored state is The color of the reversible thermochromic material B is erased and the color of the reversible thermochromic material B is visually _recognized within the proper temperature range (the temperature range less than the temperature t _4A ) (state 3). Further, when placed in a temperature environment of temperature t _4B or higher, the reversible thermochromic material B in the color-developed state is decolored, and each reversible thermochromic material is within the proper temperature range (temperature range exceeding temperature t ₁ ). The color in the decolored state is visually recognized (state 1).
The above temperature control indicator, when placed in a temperature environment higher or lower than the proper temperature range from the initial state, one of the reversible thermochromic materials in the initial state is in a coloring state, and what is the color of the temperature control indicator before discoloration? It is possible to easily detect whether or not the article requiring temperature control or its storage container has deviated from the appropriate temperature range without changing to a different color and returning to the initial color. In addition, in a specific temperature environment higher than the upper limit of the appropriate temperature range (in a temperature environment of temperature t _4A or higher and temperature t _4B or lower) from a state in which each reversible thermochromic material is mixed in a colored state (state 2). When placed in the appropriate temperature range, the color in the initial state and the color different from the color shown when placed in an environment where the temperature is higher or lower than the appropriate temperature range from the initial state change to a specific color. It has a temperature control function in a temperature environment.

In the temperature control indicator in the initial state, the reversible thermochromic material A is in the colored state and the reversible thermochromic material B is in the decolored state. In FIG. 3, the solid line indicates the reversible thermochromic material A (in the colored state (Reversible thermochromic material) is the color density-temperature curve, and the broken line is the color density-temperature curve of reversible thermochromic material B (the reversible thermochromic material in the decolored state), which is the reversible thermochromic property in the colored state. If decoloring starting temperature t ₃ of the material decoloring starting temperature greater than t ₃ of thermochromic material decolored state is shown. Further, the t _3A decolorization initiation temperature t ₃ of the reversible thermochromic material A, t _3B is a decoloring starting temperature t ₃ of the reversible thermochromic material B, complete disappearance of the t _4A is thermochromic material A The color temperature t ₄ and t _4B represent the complete decoloring temperature t ₄ of the reversible thermochromic material B, respectively.
In the above temperature control indicator, when the decolorization start temperature t ₃ of the reversible thermochromic material in the colored state shown in FIG. 2 is substantially the same as the decolorization start temperature t ₃ of the reversible thermochromic material in the decolored state. It exhibits the same color change behavior as the above, and can easily detect whether or not the article requiring temperature control or its storage container has deviated from the proper temperature range, and the temperature control function under a specific temperature environment. Have.

In each of the reversible thermochromic materials provided in the first reversible thermochromic material and the second reversible thermochromic material, the complete coloring temperature t ₁ of the reversible thermochromic material in the colored state and the reversible thermochromic material in the decolorized state complete coloring temperature t _1, and color development initiation temperature t ₂ of the color start temperature t ₂ and thermochromic material decolored state of the reversibly thermochromic material colored state are each substantially identical, and, the colored state of decoloring starting temperature t ₃ of the reversible thermochromic material is smaller than the decoloring starting temperature t ₃ of the reversible thermochromic material decolored state, complete decoloring temperature t ₄ of thermochromic material colored state of the anti The color change behavior of the temperature management indicator lower than the complete decoloring temperature t ₄ of the reversible thermochromic material in the color state will be described.
In the temperature control indicator in the initial state, the reversible thermochromic material A is in a colored state and the reversible thermochromic material B is in a decolored state. In FIG. 4, the solid line indicates the reversible thermochromic material A (in the colored state). The color density-temperature curve of the reversible thermochromic material), and the broken line is the color density-temperature curve of the reversible thermochromic material B (reversible thermochromic material in the decolored state). Further, the t _3A decolorization initiation temperature t ₃ of the reversible thermochromic material A, t _3B is a decoloring starting temperature t ₃ of the reversible thermochromic material B, complete disappearance of the t _4A is thermochromic material A The color temperature t ₄ and t _4B represent the complete decoloring temperature t ₄ of the reversible thermochromic material B, respectively.

In the temperature control indicator in the initial state, the reversible thermochromic material A is in a color-developing state, and within the proper temperature range (the temperature range exceeding the temperature t ₁ and less than the temperature t _4A ), only the color of the reversible thermochromic material A is shown. When the reversible thermochromic material A is visually recognized and placed in a temperature environment higher than the appropriate temperature range, the reversible thermochromic material A in the colored state is decolored, and the reversible thermochromic material is visually decolored within the appropriate temperature range. (State 1).
Cooling is required to return the temperature management indicator to the initial state from this state, but if placed in a temperature environment lower than the appropriate temperature range, each reversible thermochromic material in the decolored state will develop color, and Within the temperature range (within the temperature range of less than the temperature t _4A ), a color in which the reversible thermochromic materials are mixed in the colored state is visually recognized (state 2).
Further, when the temperature control indicator in the initial state is placed in a temperature environment lower than the proper temperature range, the reversible thermochromic material B in the decolored state develops color, and within the proper temperature range (within the temperature range of less than the temperature t _4A ). Then, a color in which the reversible thermochromic materials are mixed in the colored state is visually recognized (state 2).
Heating is required to return the temperature management indicator from this state to the initial state, but when placed in a temperature environment of temperature t _4A or higher and lower than temperature t _4B, only the reversible thermochromic material A in the colored state is The color of the reversible thermochromic material B is erased and the color of the reversible thermochromic material B is visually _recognized within the proper temperature range (the temperature range less than the temperature t _4A ) (state 3). Further, when placed in a temperature environment of temperature t _4B or higher, the reversible thermochromic material B in the color-developed state is decolored, and each reversible thermochromic material is within the proper temperature range (temperature range exceeding temperature t ₁ ). The color in the decolored state is visually recognized (state 1).
The above temperature control indicator, when placed in a temperature environment higher or lower than the proper temperature range from the initial state, one of the reversible thermochromic materials in the initial state is in a coloring state, and what is the color of the temperature control indicator before discoloration? It is possible to easily detect whether or not the article requiring temperature control or its storage container has deviated from the appropriate temperature range without changing to a different color and returning to the initial color. In addition, under a specific temperature environment higher than the upper limit of the appropriate temperature range (under a temperature environment of temperature t _4A or more and temperature t _{4B or} less) from a state (state 2) in which each reversible thermochromic material is mixed in a colored state. When placed in a proper temperature range, the color changes to a color in the initial state and to a color different from the color shown when placed in an environment in which the temperature is higher or lower than the proper temperature range from the initial state. It has a temperature control function in the area.

The temperature control indicators shown in FIG. 2 to FIG. 4 show the temperature of each reversible thermochromic material in a color-mixed state from the state where the mixed colors are visually recognized under a specific temperature environment higher than the appropriate temperature range, specifically, the temperature. When the reversible thermochromic material B is placed in a temperature environment of not less than t _{4A and} less than the temperature t _4B and kept under the temperature environment, the reversible thermochromic material B changes to a state in which the color of the colored state is visually recognized. In the temperature management indicator shown in FIG. 3, the reversible thermochromic material B has started decoloring under the above temperature environment, and the visible color of the temperature management indicator is that the reversible thermochromic material B is in a completely colored state. The color is lighter than the color, and the change from the color in which the reversible thermochromic materials are mixed in the colored state to the color of only the reversible thermochromic material B may be unclear.
On the other hand, in the temperature management indicator shown in FIG. 4, when the complete decoloring temperature t _4A of the reversible thermochromic material _A is lower than the decolorization start temperature t _{3B of the} reversible thermochromic material B, each reversible thermochromic material is When the mixed color is visually recognized in the colored state, the reversible thermochromic material B is completely colored and the reversible thermochromic material A is completely decolorized when kept in the above temperature environment. Therefore, it is clear that only the reversible thermochromic material B is changed to a color in which the reversible thermochromic materials are mixed in the colored state.
Therefore, in each of the reversible thermochromic materials provided in the first reversible thermochromic material and the second reversible thermochromic material, the complete color development temperature t ₁ of the reversible thermochromic material in the colored state and the reversible thermochromic material in the decolorized state complete coloring temperature t ₁ sexual _material, and, coloring starting temperature t ₂ of the color start temperature t ₂ and thermochromic material decolored state of the reversibly thermochromic material colored state are each substantially identical, and, The decolorization start temperature t ₃ of the reversible thermochromic material in the colored state is smaller than the decolorization start temperature t ₃ of the reversible thermochromic material in the decolored state, and the complete decolorization temperature t ₄ of the reversible thermochromic material in the colored state. Is smaller than the complete decolorization temperature t ₄ of the reversible thermochromic material in the decolorized state, and the complete decolorization temperature t _4A of the reversible thermochromic material _A is lower than the decolorization start temperature t _{3B of the} reversible thermochromic material B. It is preferably small.

In each of the reversible thermochromic materials provided in the first reversible thermochromic material and the second reversible thermochromic material, the decolorization start temperature t ₃ of the reversible thermochromic material in the colored state and the reversible thermochromic property in the decolorized state decoloring starting temperature t ₃ of the _material, and, the complete decoloring temperature t ₄ of thermochromic material complete decoloring temperature t ₄ decolored state of the reversibly thermochromic material colored state are each substantially the same, Further, the complete color development temperature t ₁ of the reversible thermochromic material in the colored state is smaller than the complete color development temperature t ₁ of the reversible thermochromic material in the decolored state, and the color development start temperature t ₂ of the reversible thermochromic material in the colored state is The color change behavior of the temperature control indicator in which the reversible thermochromic materials in the decolored state have substantially the same color development start temperatures t ₂ will be described.
In the temperature control indicator in the initial state, the reversible thermochromic material A is in the colored state and the reversible thermochromic material B is in the decolored state. In FIG. 5, the solid line indicates the reversible thermochromic material A (of the colored state). The color density-temperature curve of the reversible thermochromic material), and the broken line is the color density-temperature curve of the reversible thermochromic material B (reversible thermochromic material in the decolored state). Also, t _1A is a complete coloring temperature t ₁ of the thermochromic material A, t _1B represents the complete coloring temperature t ₁ of the thermochromic material B, respectively.
In the temperature control indicator in the initial state, the reversible thermochromic material A is in a color-developing state, and within the proper temperature range (the temperature range exceeding the temperature t _1B and less than the temperature t ₄ ), only the color of the reversible thermochromic material A is shown. When the reversible thermochromic material A is visually recognized and placed in a temperature environment higher than the appropriate temperature range, the reversible thermochromic material A in the colored state is decolored, and the reversible thermochromic material is visually decolored within the appropriate temperature range. (State 1).
Cooling is required to return the temperature management indicator from this state to the initial state, but when placed in a temperature environment of temperature t _1A or higher and temperature t _1B or lower, the reversible thermochromic material B in the decolored state B Only the color develops, and the color of the reversible thermochromic material B in the colored state is visually recognized within the proper temperature range (the temperature range lower than the temperature t ₄ ) (state 2). Further, when the reversible thermochromic material A in the decolored state develops color when placed in a temperature environment of the temperature t _1A or lower, the colors mixed in the reversible thermochromic material in the colored state are mixed within an appropriate temperature range. It is visually recognized (state 3).
The temperature control indicator in the initial state, when placed under a lower temperature environment than the appropriate temperature range, and color development reversible thermochromic material B of colorless state, in the appropriate temperature range (a temperature range of t less than ₄₎ Colors in which the reversible thermochromic materials are mixed in the colored state are visually recognized (state 3).
Heating is required to return the temperature control indicator to the initial state from this state, but when placed in a temperature environment higher than the appropriate temperature range, each reversible thermochromic material in the colored state will be decolored and In the temperature range (the temperature range exceeding the temperature t _1B ), the color of each reversible thermochromic material in the decolored state is visually recognized (state 1). Further, when placed in a temperature environment that exceeds the temperature t _1A and is equal to or lower than the temperature t _1B, only the reversible thermochromic material B in the decolored state develops color, and within the temperature range that exceeds the temperature t _1A , the reversible thermochromic material. The color in which B is in a colored state is visually recognized.
The above temperature control indicator, when placed in a temperature environment higher or lower than the proper temperature range from the initial state, one of the reversible thermochromic materials in the initial state is in a coloring state, and what is the color of the temperature control indicator before discoloration? It is possible to easily detect whether or not the article requiring temperature control or its storage container has deviated from the appropriate temperature range without changing to a different color and returning to the initial color. In addition, from the state where each reversible thermochromic material is in the decolored state (state 1), to a specific temperature environment lower than the lower limit of the appropriate temperature range (under a temperature environment that is higher than the temperature t _1A and lower than the temperature t _1B ). When placed, within the proper temperature range, the color in the initial state and from the initial state changes to a color different from the color shown when placed in a temperature environment higher or lower than the proper temperature range. It has a temperature control function.

Further, in the temperature control indicator in the initial state, the reversible thermochromic material A is in the colored state and the reversible thermochromic material B is in the decolored state. In FIG. 6, the solid line indicates the reversible thermochromic material A (color developed State of the reversible thermochromic material) and the broken line is the color density-temperature curve of the reversible thermochromic material B (the reversible thermochromic material in the decolored state) and the reversible heat of the colored state. If coloring starting temperature t ₂ of the color change material is greater than coloring starting temperature t ₂ of the thermochromic material decolored state is shown. _{Also, t 1A} is a complete coloring temperature _{t 1} of the thermochromic material _{A, t 1B} is a complete coloring temperature _{t 1} of the thermochromic material _{B, t 2A} color development initiation temperature t of the thermochromic material A ₁ and t _2B represent the color development start temperature t ₁ of the reversible thermochromic material B, respectively.
The above temperature management indicator is the same as that shown in FIG. 5 when the color development start temperature t ₂ of the reversible thermochromic material in the colored state is substantially the same as the color development start temperature t ₂ of the reversible thermochromic material in the decolored state. It exhibits a color change behavior and can easily detect whether or not an article requiring temperature control or its storage container deviates from an appropriate temperature range, and further has a temperature control function under a specific temperature environment.

In each of the reversible thermochromic materials provided in the first reversible thermochromic material and the second reversible thermochromic material, the decolorization starting temperature t ₃ of the reversible thermochromic material in the colored state and the reversible thermochromic property in the decolorized state decoloring starting temperature t ₃ of the _material, and, the complete decoloring temperature t ₄ of thermochromic material complete decoloring temperature t ₄ decolored state of the reversibly thermochromic material colored state are each substantially the same, Further, the complete color development temperature t ₁ of the reversible thermochromic material in the colored state is smaller than the complete color development temperature t ₁ of the reversible thermochromic material in the decolored state, and the color development start temperature t ₂ of the reversible thermochromic material in the colored state is The color change behavior of the temperature management indicator lower than the color development start temperature t ₂ of the reversible thermochromic material in the decolored state will be described.
In the temperature control indicator in the initial state, the reversible thermochromic material A is in a colored state and the reversible thermochromic material B is in a decolored state. In FIG. 7, the solid line indicates the reversible thermochromic material A (of the colored state). The color density-temperature curve of the reversible thermochromic material), and the broken line is the color density-temperature curve of the reversible thermochromic material B (reversible thermochromic material in the decolored state). _{Also, t 1A} is a complete coloring temperature _{t 1} of the thermochromic material _{A, t 1B} is a complete coloring temperature _{t 1} of the thermochromic material _{B, t 2A} color development initiation temperature t of the thermochromic material A ₂ and t _2B represent the color development start temperature t ₂ of the reversible thermochromic material B, respectively.

In the temperature control indicator in the initial state, the reversible thermochromic material A is in a color-developing state, and within the proper temperature range (the temperature range exceeding the temperature t _1B and less than the temperature t ₄ ), only the color of the reversible thermochromic material A is shown. When the reversible thermochromic material A is visually recognized and placed in a temperature environment higher than the appropriate temperature range, the reversible thermochromic material A in the colored state is decolored, and the reversible thermochromic material is visually decolored within the appropriate temperature range. (State 1).
Cooling is required to return the temperature management indicator from this state to the initial state, but when placed in a temperature environment of temperature t _1A or higher and temperature t _1B or lower, the reversible thermochromic material B in the decolored state B Only the color develops, and the color of the reversible thermochromic material B in the colored state is visually recognized within the proper temperature range (the temperature range lower than the temperature t ₄ ) (state 2). Further, when the reversible thermochromic material A in the decolored state develops color when placed in a temperature environment of the temperature t _1A or lower, the colors mixed in the reversible thermochromic material in the colored state are mixed within an appropriate temperature range. It is visually recognized (state 3).
The temperature control indicator in the initial state, when placed under a lower temperature environment than the appropriate temperature range, and color development reversible thermochromic material B of colorless state, in the appropriate temperature range (a temperature range of t less than ₄₎ Colors in which the reversible thermochromic materials are mixed in the colored state are visually recognized (state 3).
Heating is required to return the temperature control indicator to the initial state from this state, but when placed in a temperature environment higher than the appropriate temperature range, each reversible thermochromic material in the colored state will be decolored and In the temperature range (the temperature range exceeding the temperature t _1B ), the color of each reversible thermochromic material in the decolored state is visually recognized (state 1). Further, when placed in a temperature environment that exceeds the temperature t _1A and is equal to or lower than the temperature t _1B, only the reversible thermochromic material B in the decolored state develops color, and within the temperature range that exceeds the temperature t _1A , the reversible thermochromic material. The color in which B is in a colored state is visually recognized.
The above temperature control indicator, when placed in a temperature environment higher or lower than the proper temperature range from the initial state, one of the reversible thermochromic materials in the initial state is in a coloring state, and what is the color of the temperature control indicator before discoloration? It is possible to easily detect whether or not the article requiring temperature control or its storage container has deviated from the appropriate temperature range without changing to a different color and returning to the initial color. In addition, from the state where each reversible thermochromic material is in the decolored state (state 1), to a specific temperature environment lower than the lower limit of the appropriate temperature range (under a temperature environment that is higher than the temperature t _1A and lower than the temperature t _1B ). When placed, within the proper temperature range, the color in the initial state and from the initial state changes to a color different from the color shown when placed in a temperature environment higher or lower than the proper temperature range. It has a temperature control function.

The temperature control indicators shown in FIGS. 5 to 7 show the temperature t _1A in a specific temperature environment lower than the appropriate temperature range from the state in which the color of each reversible thermochromic material is in the decolored state is visually _recognized . When the reversible thermochromic material B is placed in an environment where the temperature exceeds the temperature t _1B and is maintained under the temperature environment, the color of the reversible thermochromic material B is visible, but the temperature management indicator shown in FIGS. In the above temperature environment, the reversible thermochromic material A has begun to develop color, and the color of the temperature control indicator visually recognized is the color of the reversible thermochromic material B in the completely colored state and the color of the completely colored state. It is a color in which the color of the reversible thermochromic material A, which is thinner than the color, is mixed, and the color of each reversible thermochromic material changes from the decolored state to the colored state of only the reversible thermochromic material B. May be unclear.
On the other hand, in the temperature management indicator shown in FIG. 7, when the color development start temperature t _2A of the reversible thermochromic material A is lower than the complete color development temperature t _1B of the reversible thermochromic material B, each reversible thermochromic material is decolorized. From the state where the color of the state is visually recognized, when kept in the above temperature environment, the reversible thermochromic material B is completely colored and the reversible thermochromic material A is completely decolorized. It is clear that only the reversible thermochromic material B is changed to a color in which the reversible thermochromic material is in the decolored state.
Therefore, in each of the reversible thermochromic materials provided in the first reversible thermochromic material and the second reversible thermochromic material, the decolorization start temperature t ₃ of the reversible thermochromic material in the colored state and the reversible heat in the decolorized state discoloration material decoloring starting temperature t _3, and, the complete decoloring temperature t ₄ of thermochromic material complete decoloring temperature t ₄ decolored state of the thermochromic material of the color states respectively substantially the same And the complete color development temperature t ₁ of the reversible thermochromic material in the colored state is smaller than the complete color development temperature t ₁ of the reversible thermochromic material in the decolored state, and the color development start temperature t of the reversible thermochromic material in the colored state ₂ is lower than the color development start temperature t ₂ of the reversible thermochromic material in the decolored state, and the color development start temperature t _2A of the reversible thermochromic material A is lower than the complete color development temperature t _{2B of the} reversible thermochromic material B. Is preferred.

The temperature control indicator of the present invention is configured by laminating a reversible thermochromic material including a reversible thermochromic material in a colored state and a reversible thermochromic material including a reversible thermochromic material in a decolored state.
When the hysteresis characteristic of the reversible thermochromic material is small, the reversible thermochromic material is easily discolored, but each reversible thermochromic material is provided in a different reversible thermochromic material, and it is necessary to use it as a temperature control indicator. The one reversible thermochromic material can be maintained in the decolored state by being heated, and the other reversible thermochromic material can be kept in the colored state by being cooled. Therefore, as a temperature control indicator in which one reversible thermochromic material of the reversible thermochromic material is in a colored state and the other reversible thermochromic material is in a decolorized state without causing a color change before the temperature control indicator is used. It is possible to effectively function for temperature control of an article having a narrow proper temperature range or its storage container.

As shown in FIG. 8, the temperature control indicator (1) of the present invention has a structure in which the first reversible thermochromic body (2) is laminated on the second reversible thermochromic body (3).
As shown in FIG. 9, the first reversible thermochromic body (2) has a structure in which a reversible thermochromic layer (4) containing a reversible thermochromic material is provided on a transparent support (5), It is also possible to adopt a constitution in which a reversible thermochromic material is contained in a transparent support. As shown in FIG. 10, the second reversible thermochromic material has a structure in which a reversible thermochromic layer (4) containing a reversible thermochromic material is provided on a support (6), and the reversible thermochromic material is reversible in the support. A configuration including a thermochromic material can also be used.

As shown in FIG. 11, the temperature control indicator (1) of the present invention has a transparency provided on a second reversible thermochromic material (3) comprising a support (6) and a reversible thermochromic material layer (4). In addition to the constitution in which the first reversible thermochromic material (2) having the reversible thermochromic layer (4) provided on the supporting material (5) is laminated, as shown in FIG. 12, it is provided on the support (6). On the second reversible thermochromic body (3) provided with the reversible thermochromic layer (4), a first reversible thermochromic body (7) containing a reversible thermochromic material in a transparent support. ) May be laminated.
As shown in FIG. 13, a reversible thermochromic layer (4) is provided on a transparent support (5) on a second reversible thermochromic material (8) containing a reversible thermochromic material in the support. ) Is provided, the first reversible thermochromic material (2) may be laminated.
Furthermore, as shown in FIG. 14, a reversible thermochromic material is contained in a transparent support on a second reversible thermochromic material (8) comprising a reversible thermochromic material in the support. The first reversible thermochromic body (7) may be laminated.

When the first reversible thermochromic material contains a reversible thermochromic material in a transparent support, the reversible thermochromic resin described above is contained in a transparent molding resin selected from thermoplastic or thermosetting resins. It can be obtained by blending and molding a color-changing microcapsule pigment or reversible thermochromic resin particles.
As the molding resin having transparency, polyethylene, polypropylene, polyisobutylene, polybutadiene, polymethylpentene, polystyrene, polyethylene terephthalate, polybutylene terephthalate, polycyclohexylene-dimethylene terephthalate, polyvinyl acetate, polyvinyl chloride, polyvinyl chloride. Vinylidene, acrylic ester resin, methacrylic ester resin, polyvinyl butyral, polyarylate, polyetherimide, polycarbonate, polysulfone, ionomer resin, ethylene-propylene copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl alcohol copolymer Resin, ethylene-acrylic acid ester copolymer resin, ethylene-methacrylic acid ester copolymer resin, acrylonitrile-styrene copolymer resin , Thermoplastic resin such as cycloolefin copolymers,
Thermosetting resins such as epoxy resin, epoxy acrylate, phenol resin, unsaturated polyester resin, urea resin, aryl resin, and silicone resin can be used.

When the second reversible thermochromic material comprises a reversible thermochromic material in the support, the reversible thermochromic microcapsule pigment or reversible thermochromic pigment in a molding resin selected from thermoplastic or thermosetting resins. It can be obtained by blending the discolorable resin particles and molding.
As the molding resin, linear low density polyethylene, low density polyethylene, medium high density polyethylene, ultra high density polyethylene, chlorinated polyethylene, polypropylene, chlorinated polypropylene, polyisobutylene, polybutadiene, polymethylpentene, polystyrene, polyethylene terephthalate, Polybutylene terephthalate, polycyclohexylene-dimethylene terephthalate, polyvinyl acetate, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, acrylic ester resin, methacrylic ester resin, polyamide, copolyamide, polyamideimide, polyacetal , Polyvinyl formal, polyvinyl butyral, polyarylate, polyetherimide, polyetheretherketone, polycarbonate, polyphenyl Ether, polyphenylene sulfide, polysulfone, fluororesin, ionomer resin, ethylene-propylene copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl alcohol copolymer resin, ethylene-acrylic ester copolymer resin, ethylene-methacrylic ester Copolymer resin, ethylene-vinyl chloride copolymer resin, vinyl chloride-propylene copolymer resin, vinyl chloride-vinylidene chloride copolymer resin, styrene-butadiene copolymer resin, acrylonitrile-vinylidene chloride copolymer resin, acrylonitrile-styrene copolymer resin , Acrylonitrile-ethylene-styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, acrylonitrile-chlorinated polyethylene-styrene copolymer resin, acrylonitrile-acryl resin Ester-styrene copolymer resin, ethylene-vinyl acetate resin-vinyl chloride graft copolymer resin, methyl methacrylate-butadiene-styrene copolymer resin, styrene-based thermoplastic elastomer, olefin-based thermoplastic elastomer, urethane-based thermoplastic elastomer , Polyester thermoplastic elastomer, 1,2-polybutadiene thermoplastic elastomer, vinyl chloride thermoplastic elastomer, petroleum hydrocarbon resin, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, nitrocellulose, low molecular weight polyethylene , Low molecular weight polypropylene, polybutene, coumarone-indene copolymer, thermoplastic resin such as phenoxy plastic,
Heat of epoxy resin, xylene resin, toluene resin, guanamine resin, epoxy acrylate, phenol resin, unsaturated polyester resin, furan resin, polyimide, poly (p-hydroxybenzoic acid), polyurethane, urea resin, melamine resin, silicone resin, etc. A curable resin may be used.

  The first reversible thermochromic body is provided with a reversible thermochromic layer on a transparent support, or the second reversible thermochromic body is provided with a reversible thermochromic layer on the support, reversible Thermochromic microcapsule pigment or reversible thermochromic resin particles, using an ink or paint dispersed in a vehicle containing a binder resin, screen printing, offset printing, gravure printing, coater, a printing method such as transfer printing, or A reversible thermochromic layer can be provided on the first reversible thermochromic support or the second reversible thermochromic support by a coating method such as spray coating.

The support of the first reversible thermochromic material is colorless and transparent, or colored and transparent, and is not particularly limited as long as the pattern, characters, and color change of the second reversible thermochromic material are visible. Examples of the support for the first reversible thermochromic material include plastics, elastomers, rubbers, and the like, and the form is preferably flat, sheet-like, or film-like.
The support for the second reversible thermochromic material is not particularly limited, but is a cloth such as paper, synthetic paper, knitted cloth, woven cloth, and non-woven cloth, synthetic leather, leather, plastic, glass, elastomer, rubber. , Porcelain, metal, wood, stone, and the like, and the form is preferably flat, sheet-like, or film-like.

  The binder resin is not particularly limited as long as it does not affect color development, decolorization, discoloration, etc. of the reversible thermochromic material, and a general-purpose resin, for example, an ionomer resin, isobutylene-maleic anhydride copolymer resin, acrylonitrile- Acrylic styrene copolymer resin, acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, acrylonitrile chlorinated polyethylene-styrene copolymer resin, ethylene-vinyl chloride copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene- Vinyl acetate-vinyl chloride graft copolymer resin, vinylidene chloride resin, vinyl chloride resin, chlorinated vinyl chloride resin, vinyl chloride-vinylidene chloride copolymer resin, chlorinated polyethylene resin, chlorinated polypropylene resin, polyamide resin, polyethylene tere Talate resin, polybutylene terephthalate resin, polycarbonate resin, polystyrene resin, high-impact polystyrene resin, polypropylene resin, polymethylstyrene resin, polyacrylic ester resin, polymethylmethacrylate resin, epoxy acrylate resin, alkylphenol resin, rosin-modified phenol resin, Rosin modified alkyd resin, phenolic resin modified alkyd resin, epoxy resin modified alkyd resin, styrene modified alkyd resin, acrylic modified alkyd resin, amino alkyd resin, vinyl chloride-vinyl acetate resin, styrene-butadiene resin, epoxy resin, unsaturated polyester resin , Saturated polyester resin, polyurethane resin, alkyd resin, natural rubber, polyisobutylene, butyl rubber, polyvinyl alkyl ether Resin, rosin, rosin ester, rosin derivative, polyterpene resin, oil-soluble phenol resin, petroleum hydrocarbon resin, shellac, cyclized rubber, vinyl acetate emulsion resin, styrene-butadiene emulsion resin, acrylic ester emulsion resin, Examples thereof include water-soluble alkyd resin, water-soluble melamine resin, water-soluble urea resin, water-soluble phenol resin, water-soluble epoxy resin, water-soluble polybutadiene resin, cellulose acetate, cellulose nitrate and ethyl cellulose.

When the reversible thermochromic material is provided with a reversible thermochromic layer containing a reversible thermochromic material, a transparent protective layer is provided on the reversible thermochromic layer to impart scratch resistance or a light stabilizer layer. Can be provided to impart light resistance.
As the light stabilizer layer, a light stabilizer selected from an ultraviolet absorber, an antioxidant, an antioxidant, a singlet oxygen quencher, a superoxide anion quencher, an ozone quencher, a visible light absorber, an infrared absorber, etc. And a layer in which is fixed in a dispersed state.

The temperature control indicator of the present invention can bring about an alternating color change from colored (1) to colored (2) by using a reversible thermochromic material and a non-thermochromic coloring agent together.
As shown in FIG. 15, a non-thermochromic layer (9) containing a non-thermochromic colorant is provided between the second reversible thermochromic support (6) and the reversible thermochromic layer (4). In addition to the configuration, the reversible thermochromic layer of the second reversible thermochromic material may contain a non-thermochromic colorant.
Further, the second reversible thermochromic support may be a colored support.
A general pigment or dye is used as the non-thermochromic colorant.

The temperature control indicator of the present invention comprises a first reversible thermochromic body, a first adhesive layer provided on the surface in contact with the second reversible thermochromic body, wherein the second reversible thermochromic body has the first reversible thermochromic body. The discolored body can be attached and laminated on an article that requires temperature control or its storage container for use.
In addition, a second adhesive layer is provided on the surface of the second reversible thermochromic material on the side opposite to the side on which the first reversible thermochromic material is provided, and the second reversible thermosensitive material is provided on the article or its storage container requiring temperature control. A thermochromic material may be attached and the first reversible thermochromic material may be laminated on the second reversible thermochromic material for use.
Furthermore, a first adhesive layer is provided on the surface of the first reversible thermochromic material that contacts the second reversible thermochromic material, and the first reversible thermochromic material of the second reversible thermochromic material is A second adhesive layer is provided on the opposite surface provided, and the second reversible thermochromic material is attached to an article or its storage container that requires temperature control. A reversible thermochromic material can be attached and used.

The pressure-sensitive adhesive used for the first pressure-sensitive adhesive layer does not affect the coloring, decoloration, discoloration, etc. of the reversible thermochromic material provided in the first reversible thermochromic material, and the pattern of the second reversible thermochromic material. There is no particular limitation as long as it can be visually recognized, a character and a color change and can be attached to the second reversible thermochromic material. Further, as the second adhesive layer, an article or its storage container that does not affect the coloring, decoloration, discoloration, etc. of the reversible thermochromic material provided in the second reversible thermochromic material and that requires temperature control. There is no particular limitation as long as it can be attached to.
Examples of the pressure-sensitive adhesive used in the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer include acrylic resin, polyurethane-based resin, ethylene vinyl acetate-based resin, rubber-based resin, silicone-based resin, epoxy resin and the like.

In the temperature control indicator of the present invention, the support of the first reversible thermochromic material is a transparent tamper-proof member provided with an adhesive layer, and the first reversible thermochromic material is used as the second reversible thermochromic material. By sticking the body and stacking it on an article requiring temperature control or its storage container, replacement of the reversible thermochromic material when the article requiring temperature control or its storage vessel deviates from the proper temperature range or It is possible to prevent tampering by removing one of the reversible thermochromic materials, heating or cooling again, and then re-pasting.
The second reversible thermochromic support is used as a tamper-proof member provided with an adhesive layer, and the second reversible thermochromic material is attached to an article or a storage container thereof that requires temperature control. Tampering can also be prevented by stacking the first reversible thermochromic material on the reversible thermochromic material.
Further, the first reversible thermochromic support is used as a transparent tamper-proof member provided with an adhesive layer, and the second reversible thermochromic support is provided with an adhesive layer to prevent tampering. As a member, by sticking the second reversible thermochromic body to the article or its storage container that requires temperature management, by sticking the first reversible thermochromic body to the second reversible thermochromic body, Tampering can be prevented further.

The tampering prevention member exhibits a tampering prevention function by providing an adhesive layer on the outermost layer of the laminated structure member.
As the tampering prevention member, a tampering prevention label, a tape, a seal, or the like can be used. An example of a tampering prevention member having a tampering prevention function of a type that is transferred to a body is cited.
In addition, when it is peeled off after being attached to an adherend, separation occurs at the interface of the laminated structure, the residue does not remain on the adherend due to the deformation of the layer, and characters are raised on the tamper-proof member or a base of a fragile material. Examples of the tamper-proof member having tamper-proof property include a type in which the base material is destroyed when the material is attached to an adherend and then peeled off, and a trace of peeling remains on the adherend.

The temperature control indicator in the present invention can be used as follows, for example.
In order to bring the first reversible thermochromic material into the color-developed state, it is cooled at a temperature lower than the appropriate temperature range of the article requiring temperature control or its storage container to maintain the color-developed state. Then, in order to bring the second reversible thermochromic material into the decolored state, it is heated at a temperature higher than the appropriate temperature range to maintain the decolored state. Stop heating or cooling the reversible thermochromic material, and under the temperature environment within the proper temperature range, stack the first reversible thermochromic material in the colored state on the second reversible thermochromic material in the decolored state, and control the temperature. Make an indicator. When the temperature management indicator is stacked on an article that requires temperature control or its storage container to make it possible to detect temperature changes, the temperature of the above-mentioned article or its storage container will be affected by the change in the color of the temperature management indicator. It is possible to irreversibly confirm whether or not the range is deviated.
If the temperature control indicator is mistakenly placed in a temperature environment higher than the proper temperature range before use and both reversible thermochromic materials are in the decolored state, the first reversible thermochromic change from the temperature control indicator. Remove the body and store it again while keeping the color development state by cooling at a temperature lower than the appropriate temperature range. Initialize the temperature control indicator by stopping the cooling of the first reversible thermochromic material and again stacking the first reversible thermochromic material on the second reversible thermochromic material under the temperature environment within the proper temperature range. It can be returned to the state and used.
Also, if the temperature control indicator is accidentally placed in a temperature environment lower than the appropriate temperature range before use and both reversible thermochromic materials become colored, the temperature control indicator will cause the second reversible heat Remove the discolored body and heat it again at a temperature higher than the appropriate temperature range to maintain the decolored state and store it. By stopping the heating of the second reversible thermochromic material and again stacking the first reversible thermochromic material on the second reversible thermochromic material under the temperature environment within the proper holding temperature range, the temperature control indicator Can be returned to the initial state and used.
When an adhesive layer is provided on at least one of the first reversible thermochromic body or the second reversible thermochromic body, the same reversible thermochromic body or the above-mentioned article or a storage container thereof is adhered to Can be used in any way.

  Examples will be 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 reversible thermochromic microcapsule pigment A 2.5 parts of 1,3-dimethyl-6-diethylaminofluorane as component (a) and 2,2-bis (4-hydroxyphenyl) as component (b) Reversible thermochromic composition composed of 5.0 parts of hexafluoropropane, 3.0 parts of 1,1-bis (4-hydroxyphenyl) n-decane, and 50.0 parts of decyl myristate as the component (c). The product was encapsulated in microcapsules by an interfacial polymerization method to obtain a microcapsule suspension. The suspension was centrifuged to isolate heat-decolorizable reversible thermochromic microcapsule pigment A.
The reversible thermochromic microcapsule pigment A has a particle diameter of 2.5 μm, a complete color development temperature t ₁ of 15 ° C., a color development start temperature t ₂ of 17 ° C., a decolorization start temperature t ₃ of 20 ° C., and a complete decolorization. The temperature t ₄ was 22 ° C., the hysteresis width ΔH was 5 ° C., and the temperature changed reversibly from orange to colorless.
Preparation of reversible thermochromic microcapsule pigment B 1.0 part of 3,3-bis (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide as component (a) and 1,1 as component (b) A reversible thermochromic composition comprising 8.0 parts of -bis (4-hydroxyphenyl) n-decane and 50.0 parts of decyl myristate as a component (c) was encapsulated in microcapsules by an interfacial polymerization method. , A microcapsule suspension was obtained. The suspension was centrifuged to isolate heat-decolorizable reversible thermochromic microcapsule pigment B.
The reversible thermochromic microcapsule pigment B has a particle size of 2.5 μm, a complete color development temperature t ₁ of 15 ° C., a color development start temperature t ₂ of 16 ° C., a decolorization start temperature t ₃ of 19 ° C., and a complete decolorization. The temperature t ₄ was 22 ° C., the hysteresis width ΔH was 5 ° C., and the color changed reversibly from bluish green to colorless.

Preparation of temperature control indicator (see Fig. 11)
As a transparent support (5), on a transparent polyester film having a thickness of 25 μm, 30 parts of reversible thermochromic microcapsule pigment A, 62 parts of urethane emulsion, 2 parts of thickening agent, 0.5 part of leveling agent, A reversible thermochromic ink obtained by uniformly dispersing 0.5 parts of a defoaming agent and 5 parts of a crosslinking agent is solid-printed using a 120 mesh screen plate, and dried and cured to form a reversible thermochromic layer (4). It provided and the 1st reversible thermochromic body (2) was obtained.
Then, on a white synthetic paper as a support (6), 30 parts of reversible thermochromic microcapsule pigment B, 62 parts of urethane emulsion, 2 parts of thickener, 0.5 part of leveling agent, 0.5 part of defoaming agent, The reversible thermochromic ink in which 5 parts of the cross-linking agent is uniformly dispersed is solid-printed using a 120-mesh screen plate, and dried and cured to form the reversible thermochromic layer (4). A color change product (3) was obtained.
The first reversible thermochromic material was cooled to 15 [deg.] C. or lower to maintain the colored state, and the second reversible thermochromic material was heated to 22 [deg.] C. or higher to retain the decolored state and stored.
The cooling of the first reversible thermochromic material and the heating of the second reversible thermochromic material are stopped, and the first reversible thermochromic material is laminated on the second reversible thermochromic material to produce the temperature management indicator (1). However, since the first reversible thermochromic material in the color-developed state was decolored because it was produced in a temperature environment of 25 ° C, the first reversible thermochromic material was removed from the temperature control indicator, and the first reversible thermochromic material was removed. The reversible thermochromic material was cooled again to 15 ° C. or lower and kept in the colored state and stored.
When the cooling of the first reversible thermochromic substance is stopped and the first reversible thermochromic substance is laminated on the second reversible thermochromic substance under a temperature environment of 18 ° C., a desired temperature control indicator is produced. I was able to.

Checking the temperature during the distribution and storage of chocolate (determine whether the temperature exceeds 15 ° C and less than 22 ° C)
Under a temperature environment of 18 ° C, when a temperature control indicator is stacked on a packaging container that contains chocolate with an appropriate temperature range exceeding 15 ° C and less than 22 ° C, an orange color due to the first reversible thermochromic material is visually recognized. Was done (initial state). As long as the packaging container was within the proper temperature range, the orange temperature control indicator was only visible.
When the temperature control indicator in the initial state reaches a temperature of 22 ° C. or higher, the reversible thermochromic microcapsule pigment A provided in the first reversible thermochromic material is decolored and becomes colorless, and the second reversible thermochromic material causes White color was visually recognized (state 1), and only white color was visually recognized in a temperature range exceeding 15 ° C.
When the temperature control indicator in the state 1 reaches a temperature of 15 ° C. or lower, the reversible thermochromic microcapsule pigment A provided in the first reversible thermochromic body and the reversible thermochromic microcapsule provided in the second reversible thermochromic body Pigment B was colored together, and a brown color in which an orange color due to the first reversible thermochromic substance and a blue-green color due to the second reversible thermochromic substance were mixed was observed (state 2), and brown in the temperature range below 22 ° C. Was only visible.
Further, when the temperature control indicator in the initial state reaches a temperature of 15 ° C. or lower, the reversible thermochromic microcapsule pigment B provided in the second reversible thermochromic substance develops a color, and the first reversible thermochromic substance causes an orange color. A brown color, which was a mixture of blue-green color due to the second reversible thermochromic material, was visually recognized (state 2), and only a brown color was visually recognized in a temperature range of less than 22 ° C.
When the temperature control indicator in the state 2 reaches a temperature of 22 ° C. or higher, the reversible thermochromic microcapsule pigment A provided in the first reversible thermochromic body and the reversible thermochromic microcapsule provided in the second reversible thermochromic body Both the pigments B were decolored and became colorless, and white due to the second reversible thermochromic material was visually recognized (state 1).
Therefore, the packaging container containing chocolate discolors when placed in a temperature environment outside the proper temperature range, and then it cannot be returned to the initial state, and it is irreversibly confirmed that the packaging container deviates from the proper temperature range. I was able to do it.

Example 2
Preparation of Reversible Thermochromic Microcapsule Pigment C As component (a), 4,5,6,7-tetrachloro-3- (4-diethylamino-2-methylphenyl) -3- (1-ethyl-2-methyl) 2.0 parts of -1H-indol-3-yl) -1 (3H) isobenzofuranone, 8.0 parts of 2,2-bis (4-hydroxyphenyl) propane as the component (b), and (c) A reversible thermochromic composition containing 50.0 parts of neopentyl stearate as a component was encapsulated in microcapsules by an interfacial polymerization method to obtain a microcapsule suspension. The suspension was centrifuged to isolate heat-decolorizable reversible thermochromic microcapsule pigment C.
The reversible thermochromic microcapsule pigment C has a particle diameter of 2.5 μm, a complete color development temperature t ₁ of 5 ° C., a color development start temperature t ₂ of 10 ° C., a decolorization start temperature t ₃ of 30 ° C., and a complete decolorization. The temperature t ₄ was 35 ° C., the hysteresis width ΔH was 25 ° C., and the temperature changed reversibly from blue to colorless.
Preparation of reversible thermochromic microcapsule pigment D As component (a), 2-di-n-butylamino-8-di-n-pentylamino-4-methyl-spiro [5H- [1] benzopyrano [2,3] -D] pyrimidine] -5,1 '(3'H) isobenzofuran] -3'-one and 1.0 part of 2,2-bis (4-hydroxyphenyl) propane as the (b) component. Part and 50.0 parts of neopentyl stearate as a component (c), a reversible thermochromic composition was encapsulated in a microcapsule by an interfacial polymerization method to obtain a microcapsule suspension. The suspension was centrifuged to isolate heat-decolorizable reversible thermochromic microcapsule pigment D.
The reversible thermochromic microcapsule pigment D has a particle diameter of 2.5 μm, a complete color development temperature t ₁ of 5 ° C., a color development start temperature t ₂ of 10 ° C., a decolorization start temperature t ₃ of 28 ° C., and a complete decolorization. The temperature t ₄ was 35 ° C. and the hysteresis width ΔH was 24 ° C. The temperature changed reversibly from pink to colorless.

Fabrication of temperature control indicator (see Figure 12)
10 parts of the reversible thermochromic microcapsule pigment C, 1 part of the dispersant, and 89 parts of polypropylene homopolymer were melt-mixed at 180 ° C. in an extruder to obtain reversible thermochromic pellets.
A first reversible thermochromic material containing a reversible thermochromic material in a transparent support, which is molded into a plate shape using an injection molding machine at a cylinder temperature of 180 ° C. using the reversible thermochromic pellet ( 7) was obtained.
Then, on a white synthetic paper as a support (6), 30 parts of reversible thermochromic microcapsule pigment D, 62 parts of urethane emulsion, 2 parts of thickener, 0.5 part of leveling agent, 0.5 part of defoaming agent, The reversible thermochromic ink obtained by uniformly dispersing 5 parts of the crosslinking agent is solid-printed using a 120 mesh screen plate, dried and cured to form the reversible thermochromic layer (4), and the second reversible thermochromic ink is provided. A color change product (3) was obtained.
The first reversible thermochromic material was heated to 35 ° C. or higher to maintain the decolored state, and the second reversible thermochromic material was cooled to 5 ° C. or lower to retain the colored state and stored.
The heating of the first reversible thermochromic material and the cooling of the second reversible thermochromic material are stopped, and the first reversible thermochromic material is laminated on the second reversible thermochromic material under a temperature environment of 25 ° C. A temperature control indicator (1) was prepared.

Temperature check of distribution and storage processes in the normal temperature range [The normal temperature is 20 ° C ± 15 ° C (5-35 ° C) specified in JIS Z 8703, and the normal temperature range is higher than 5 ° C and lower than 35 ° C. Area)
Under the temperature environment of 25 ° C., a pink color due to the second reversible thermochromic material was visually recognized on the temperature management indicator (initial state). As long as the temperature control indicator was in the normal temperature range, only a pink color was visually recognized.
When the temperature control indicator in the initial state reaches a temperature of 35 ° C. or higher, the reversible thermochromic microcapsule pigment D provided in the second reversible thermochromic material is decolored and becomes colorless, and the second reversible thermochromic material causes White was visually recognized (state 1), and white was only visually recognized in a temperature range of higher than 5 ° C.
When the temperature control indicator in the state 1 reaches a temperature of 5 ° C. or lower, the reversible thermochromic microcapsule pigment C provided in the first reversible thermochromic body and the reversible thermochromic microcapsule provided in the second reversible thermochromic body Pigment D was colored together, and a purple color in which blue color due to the first reversible thermochromic substance and pink color due to the second reversible thermochromic substance were mixed was observed (state 2), and purple was observed in the temperature range of less than 35 ° C. It was only visible.
Further, when the temperature control indicator in the initial state reaches a temperature of 5 ° C. or lower, the reversible thermochromic microcapsule pigment C provided in the first reversible thermochromic body develops a color, resulting in a blue color due to the first reversible thermochromic body. Purple in which the pink color was mixed by the second reversible thermochromic material was visually recognized (state 2), and only purple was visually recognized in the temperature range of less than 35 ° C.
When the temperature control indicator in the state 2 reaches a temperature of 35 ° C. or higher, the reversible thermochromic microcapsule pigment C provided in the first reversible thermochromic body and the reversible thermochromic microcapsule provided in the second reversible thermochromic body Both of the pigments D were decolored and became colorless, and white due to the second reversible thermochromic material was visually recognized (state 1).
Therefore, the temperature control indicator changed color when placed in a temperature environment outside the normal temperature range, and it was not possible to return to the initial state thereafter, and it was possible to irreversibly confirm that the temperature control indicator deviated from the normal temperature range.

Example 3
Fabrication of temperature control indicator (see Figure 16)
As a transparent support (5), on a transparent polyester film having a thickness of 25 μm, 30 parts of the above reversible thermochromic microcapsule pigment C, 62 parts of urethane emulsion, 2 parts of thickener, 0.5 part of leveling agent. A reversible thermochromic ink obtained by uniformly dispersing 0.5 parts of a defoaming agent and 5 parts of a crosslinking agent was subjected to solid printing using a 120-mesh screen plate, dried and cured, and the reversible thermochromic layer (4). Was provided to obtain a first reversible thermochromic material (2).
Then, on a white synthetic paper as a support (6), 0.5 parts of a yellow general pigment, 91.5 parts of a urethane emulsion, 2 parts of a thickener, 0.5 part of a leveling agent, 0.5 part of a defoaming agent. The non-thermochromic ink obtained by uniformly dispersing 5 parts of the cross-linking agent was subjected to solid printing using a 120 mesh screen plate and dried and cured to form the non-thermochromic layer (9).
On the non-thermochromic layer, 30 parts of the reversible thermochromic microcapsule pigment D, 62 parts of urethane emulsion, 2 parts of thickener, 0.5 part of leveling agent, 0.5 part of defoaming agent, 5 parts of crosslinking agent. The reversible thermochromic ink obtained by uniformly dispersing is subjected to solid printing using a 120 mesh screen plate, dried and cured to provide a reversible thermochromic layer (4), and a second reversible thermochromic material (3 ) Got.
The first reversible thermochromic material was cooled to 5 ° C. or lower to maintain the colored state, and the second reversible thermochromic material was heated to 35 ° C. or higher to retain the decolored state and stored.
The cooling of the first reversible thermochromic body and the heating of the second reversible thermochromic body are stopped, and the first reversible thermochromic body is laminated on the second reversible thermochromic body under a temperature environment of 25 ° C. A temperature control indicator (1) was prepared.

Temperature check of distribution and storage processes in the normal temperature range [The normal temperature is 20 ° C ± 15 ° C (5-35 ° C) specified in JIS Z 8703, and the normal temperature range is higher than 5 ° C and lower than 35 ° C. Area)
Under a temperature environment of 25 ° C., the temperature management indicator visually recognized a green color, which was a mixture of blue due to the first reversible thermochromic substance and yellow due to the non-thermochromic layer of the second reversible thermochromic substance (initial state). ). As long as the temperature control indicator was in the normal temperature range, only green was visually recognized.
When the temperature control indicator in the initial state reaches a temperature of 35 ° C. or higher, the reversible thermochromic microcapsule pigment C provided in the first reversible thermochromic material is decolored and becomes colorless, and the second reversible thermochromic material causes Yellow was visible (state 1), and only yellow was visible in the temperature range of higher than 5 ° C.
When the temperature control indicator in the state 1 reaches a temperature of 5 ° C. or lower, the reversible thermochromic microcapsule pigment C provided in the first reversible thermochromic body and the reversible thermochromic microcapsule provided in the second reversible thermochromic body Pigment D was colored together, and a brown color in which a blue color due to the first reversible thermochromic substance and a pink color due to the reversible thermochromic substance layer of the second reversible thermochromic substance and a yellow color due to the non-thermochromic substance layer were mixed was visually recognized (state 2), brown was only visually recognized in the temperature range of less than 35 ° C.
Further, when the temperature control indicator in the initial state reaches a temperature of 5 ° C. or lower, the reversible thermochromic microcapsule pigment D provided in the second reversible thermochromic substance develops a color, and the first reversible thermochromic substance causes a blue color. In the second reversible thermochromic material, brown, which is a mixed color of pink due to the reversible thermochromic layer and yellow due to the non-thermochromic layer, is visible (state 2), and brown is only visible in the temperature range of less than 35 ° C. It was
When the temperature control indicator in the state 2 reaches a temperature of 35 ° C. or higher, the reversible thermochromic microcapsule pigment C provided in the first reversible thermochromic body and the reversible thermochromic microcapsule provided in the second reversible thermochromic body Both the pigments D were decolored and became colorless, and yellow due to the second reversible thermochromic material was visually recognized (state 1).
Therefore, the temperature control indicator changed color when placed in a temperature environment outside the normal temperature range, and it was not possible to return to the initial state thereafter, and it was possible to irreversibly confirm that the temperature control indicator deviated from the normal temperature range.

Example 4
Preparation of reversible thermochromic microcapsule pigment E 1.0) 1,2-benz-6- (N-ethyl-N-isoamylamino) fluorane as component (a) and 1,2 as component (b) A reversible thermochromic composition comprising 8.0 parts of -bis (4-hydroxyphenyl) n-decane and 5.0 parts of n-butyl palmitate as the component (c) was formed into microcapsules by an interfacial polymerization method. Encapsulation was performed to obtain a microcapsule suspension. The suspension was centrifuged to isolate heat-decolorizable reversible thermochromic microcapsule pigment E.
The reversible thermochromic microcapsule pigment E has a particle size of 2.5 μm, a complete color development temperature t ₁ of 0 ° C., a color development start temperature t ₂ of 3 ° C., a decolorization start temperature t ₃ of 8 ° C., and a complete decolorization. The temperature t ₄ was 10 ° C., the hysteresis width ΔH was 8 ° C., and the color changed reversibly from red to colorless due to the temperature change.
Preparation of Reversible Thermochromic Microcapsule Pigment F (A) As a component, 2.0 parts of 2- (2-chloroamino) -6-di-n-butylaminofluorane, and as a (B) component, 1,1 A reversible thermochromic composition comprising 8.0 parts of -bis (4-hydroxyphenyl) n-decane and 50.0 parts of n-butyl palmitate as the component (c) was formed into microcapsules by an interfacial polymerization method. Encapsulation was performed to obtain a microcapsule suspension. The suspension was centrifuged to isolate a heat-decolorizable reversible thermochromic microcapsule pigment F.
The reversible thermochromic microcapsule pigment F has a particle size of 2.5 μm, a complete color development temperature t ₁ of 0 ° C., a color development start temperature t ₂ of 3 ° C., a decolorization start temperature t ₃ of 7 ° C., and a complete decolorization. The temperature t ₄ was 10 ° C., the hysteresis width ΔH was 7 ° C., and the temperature changed reversibly from black to colorless.

Fabrication of temperature control indicator with adhesive layer (see Fig. 17)
As a transparent support (5), 30 parts of reversible thermochromic microcapsule pigment E is provided on the surface of the transparent polyester film having a thickness of 25 μm provided with the first adhesive layer (10) on the side opposite to the adhesive layer. , A reversible thermochromic ink of 120 mesh with a uniform dispersion of 62 parts of urethane emulsion, 2 parts of thickening agent, 0.5 parts of leveling agent, 0.5 parts of defoaming agent and 5 parts of crosslinking agent. Solid printing was carried out using, and dried and cured to provide a reversible thermochromic layer (4), and a first reversible thermochromic body (2) was obtained.
Then, as a support (6), a reversible thermochromic microcapsule pigment F30 part and urethane were formed on the surface of the white polyester film having a thickness of 25 μm provided with the second adhesive layer (11) on the side opposite to the adhesive layer. A reversible thermochromic ink obtained by uniformly dispersing 62 parts of a system emulsion, 2 parts of a thickener, 0.5 part of a leveling agent, 0.5 part of a defoaming agent, and 5 parts of a crosslinking agent using a 120 mesh screen plate. Solid printing was performed, followed by drying and curing to provide a reversible thermochromic layer (4) to obtain a second reversible thermochromic material (3).
The first reversible thermochromic material was cooled to 0 ° C. or lower to retain the colored state, and the second reversible thermochromic material was heated to 10 ° C. or higher to retain the decolored state and stored.
Stop the cooling of the first reversible thermochromic material and the heating of the second reversible thermochromic material, and attach the first reversible thermochromic material to the second reversible thermochromic material under a temperature environment of 5 ° C. A temperature control indicator (1) was prepared.

Milk temperature distribution and storage process temperature check (determine whether the temperature exceeds the appropriate temperature range above 0 ℃ and below 10 ℃)
When a temperature control indicator is attached to a packaging container filled with milk whose temperature range is more than 0 ° C and less than 10 ° C under the temperature environment of 5 ° C, the red color due to the first reversible thermochromic substance is generated. Visually recognized (initial state). As long as the packaging was within the proper temperature range, the red temperature control indicator was only visible.
When the temperature control indicator in the initial state reaches a temperature of 10 ° C. or higher, the reversible thermochromic microcapsule pigment E provided in the first reversible thermochromic substance is decolored and becomes colorless, and the second reversible thermochromic substance causes White color was visually recognized (state 1), and only white color was visually recognized in a temperature range exceeding 0 ° C.
When the temperature control indicator in the state 1 reaches a temperature of 0 ° C. or lower, the reversible thermochromic microcapsule pigment E provided in the first reversible thermochromic body and the reversible thermochromic microcapsule provided in the second reversible thermochromic body A red-brown color, in which both the pigment F and the red color produced by the first reversible thermochromic material and the black color produced by the second reversible thermochromic material were mixed, was visually recognized (state 2), and red was observed in a temperature range of less than 10 ° C. Only brown was visible.
Further, when the temperature control indicator in the initial state reaches a temperature of 0 ° C. or lower, the reversible thermochromic microcapsule pigment F provided in the second reversible thermochromic body develops a color, resulting in a red color due to the first reversible thermochromic body. A reddish brown color in which black was mixed with the second reversible thermochromic material was visually recognized (state 2), and a reddish brown color was only visually recognized in a temperature range of less than 10 ° C.
When the temperature control indicator in the state 2 reaches a temperature of 10 ° C. or higher, the reversible thermochromic microcapsule pigment E provided in the first reversible thermochromic body and the reversible colorant microcapsule pigment provided in the second reversible thermochromic body Both F were decolored and became colorless, and white due to the second reversible thermochromic material was visually recognized (state 1).
Therefore, the packaging container filled with milk discolors when placed in a temperature environment outside the proper temperature range and cannot be returned to the initial state thereafter, and it is irreversibly confirmed that the packaging container deviates from the proper temperature range. I was able to do it.

Example 5
Fabrication of temperature control indicator with tampering prevention function (see Figure 18)
As the tampering prevention member (12), a tampering prevention label [TP seal C (M) Kaifu made by Lintec Co., Ltd.] having a thickness of 38 μm and made of a transparent polyester film is provided on the surface opposite to the adhesive surface. Reversible thermochromic microcapsule pigment E 30 parts, urethane emulsion 62 parts, thickener 2 parts, leveling agent 0.5 part, defoaming agent 0.5 part, crosslinking agent 5 parts reversible heat uniformly dispersed The color-changing ink was subjected to solid printing using a 120-mesh screen plate, dried and cured to provide a reversible thermochromic layer (4), and a first reversible thermochromic body (2) was obtained.
Then, on a white polyester film having a thickness of 25 μm as a support (6), 30 parts of the reversible thermochromic microcapsule pigment F, 62 parts of a urethane emulsion, 2 parts of a thickening agent, 0.5 part of a leveling agent, and A reversible thermochromic ink obtained by uniformly dispersing 0.5 part of a foaming agent and 5 parts of a crosslinking agent is solid-printed using a 120 mesh screen plate, and dried and cured to form a reversible thermochromic layer (4). Thus, a second reversible thermochromic material (3) was obtained.
The first reversible thermochromic material was cooled to 0 ° C. or lower to maintain the colored state, and the second reversible thermochromic material was heated to 10 ° C. or higher to retain the decolored state and stored.
Stop the cooling of the first reversible thermochromic material and the heating of the second reversible thermochromic material, and attach the first reversible thermochromic material to the second reversible thermochromic material under a temperature environment of 5 ° C. A temperature control indicator (1) was prepared.

Milk temperature distribution and storage process temperature check (determine whether the temperature exceeds the appropriate temperature range above 0 ℃ and below 10 ℃)
When a temperature control indicator is attached to a packaging container filled with milk whose temperature range is more than 0 ° C and less than 10 ° C under the temperature environment of 5 ° C, the red color due to the first reversible thermochromic substance is generated. Visually recognized (initial state). As long as the packaging was within the proper temperature range, the red temperature control indicator was only visible.
When the temperature control indicator in the initial state reaches a temperature of 10 ° C. or higher, the reversible thermochromic microcapsule pigment E provided in the first reversible thermochromic substance is decolored and becomes colorless, and the second reversible thermochromic substance causes White color was visually recognized (state 1), and only white color was visually recognized in a temperature range exceeding 0 ° C.
When the temperature control indicator in the state 1 reaches a temperature of 0 ° C. or lower, the reversible thermochromic microcapsule pigment E provided in the first reversible thermochromic body and the reversible thermochromic microcapsule provided in the second reversible thermochromic body A red-brown color, in which both the pigment F and the red color produced by the first reversible thermochromic material and the black color produced by the second reversible thermochromic material were mixed, was visually recognized (state 2), and red was observed in a temperature range of less than 10 ° C. Only brown was visible.
Further, when the temperature control indicator in the initial state reaches a temperature of 0 ° C. or lower, the reversible thermochromic microcapsule pigment F provided in the second reversible thermochromic body develops a color, resulting in a red color due to the first reversible thermochromic body. A reddish brown color in which black was mixed with the second reversible thermochromic material was visually recognized (state 2), and a reddish brown color was only visually recognized in a temperature range of less than 10 ° C.
When the temperature control indicator in state 2 reaches a temperature of 10 ° C. or higher, the reversible thermochromic microcapsule pigment E provided in the first reversible thermochromic body and the reversible thermochromic microcapsule provided in the second reversible thermochromic body Both of the pigments F were decolored to become colorless, and white due to the second reversible thermochromic material was visually recognized (state 1).
Therefore, the packaging container filled with milk discolors when placed in a temperature environment outside the proper temperature range and cannot be returned to the initial state thereafter, and it is irreversibly confirmed that the packaging container deviates from the proper temperature range. I was able to do it.
The first reversible thermochromic substance was peeled off in order to replace it with another first reversible thermochromic substance in a different coloring state so as not to leave a history of raising and lowering the temperature of milk. The adhesive of the body tampering prevention label remained on the second reversible thermochromic material, and the word "opened" was transferred. An attempt was made to re-attach the peeled first reversible thermochromic material to the second reversible thermochromic material, but the characters remaining on the second reversible thermochromic material and the first reversible thermochromic material The missing characters on the tampering prevention label did not exactly overlap.
Therefore, the above-mentioned temperature management indicator has a function of preventing falsification such as replacement or reattachment.

Example 6
Preparation of reversible thermochromic microcapsule pigment G As component (a), 4,5,6,7-tetrachloro-3- (4-diethylamino-2-methylphenyl) -3- (1-ethyl-2-methyl) 2.0 parts of -1H-indol-3-yl) -1 (3H) isobenzofuranone, 8.0 parts of 2,2-bis (4-hydroxyphenyl) propane as the component (b), and (c) As a component, a reversible thermochromic composition consisting of 40.0 parts of n-butyl palmitate and 10.0 parts of myristyl alcohol is dissolved by heating and encapsulated in microcapsules by an interfacial polymerization method to prepare a microcapsule suspension. Got The suspension was centrifuged to isolate heat-decolorizable reversible thermochromic microcapsule pigment G.
The reversible thermochromic microcapsule pigment G has a particle size of 2.5 μm, a complete color development temperature t ₁ of 2 ° C., a color development start temperature t ₂ of 3 ° C., a decolorization start temperature t ₃ of 7 ° C., and a complete decolorization. The temperature t ₄ was 8 ° C., the hysteresis width ΔH was 5 ° C., and the temperature changed reversibly from blue to colorless.
Preparation of Reversible Thermochromic Microcapsule Pigment H As component (a), 2-di-n-butylamino-8-di-n-pentylamino-4-methyl-spiro [5H- [1] benzopyrano [2,3] -D] pyrimidine] -5,1 '(3'H) isobenzofuran] -3'-one and 1.0 part of 2,2-bis (4-hydroxyphenyl) propane as the (b) component. Part, and (c) as a component, 40.0 parts of n-butyl palmitate, and 10.0 parts of myristyl alcohol are reversibly thermochromic dissolved by heating and encapsulated in microcapsules by an interfacial polymerization method. , A microcapsule suspension was obtained. The suspension was centrifuged to isolate heat-decolorizable reversible thermochromic microcapsule pigment H.
The reversible thermochromic microcapsule pigment H has a particle diameter of 2.5 μm, a complete color development temperature t ₁ of 2 ° C., a color development start temperature t ₂ of 3 ° C., a decolorization start temperature t ₃ of 7 ° C., and a complete decolorization. The temperature t ₄ was 8 ° C., the hysteresis width ΔH was 5 ° C., and the temperature changed reversibly from pink to colorless.

Fabrication of temperature control indicator with tampering prevention function (see Fig. 19)
As a transparent support (5), 30 parts of reversible thermochromic microcapsule pigment G is provided on the surface of the transparent polyester film having a thickness of 25 μm provided with the first adhesive layer (10) on the side opposite to the adhesive layer. , A reversible thermochromic ink of 120 mesh with a uniform dispersion of 62 parts of urethane emulsion, 2 parts of thickening agent, 0.5 parts of leveling agent, 0.5 parts of defoaming agent and 5 parts of crosslinking agent. Solid printing was carried out using, and dried and cured to provide a reversible thermochromic layer (4), and a first reversible thermochromic body (2) was obtained.
Next, a reversible thermochromic property was formed on the surface opposite to the adhesive surface of the tamperproof label [FP1102B PAT1 11HL manufactured by Lintec Co., Ltd.] having a thickness of 50 μm and made of a white vinyl chloride film as the tamperproof member (12). A reversible thermochromic ink obtained by uniformly dispersing 30 parts of microcapsule pigment H, 62 parts of urethane emulsion, 2 parts of thickener, 0.5 part of leveling agent, 0.5 part of defoaming agent, and 5 parts of crosslinking agent. Solid printing was performed using a 120 mesh screen plate, dried and cured to provide a reversible thermochromic layer (4), and a second reversible thermochromic body (3) was obtained.
The first reversible thermochromic material was heated to 8 ° C or higher to maintain the decolored state, and the second reversible thermochromic material was cooled to 2 ° C or lower to retain the colored state and stored.
The heating of the first reversible thermochromic material and the cooling of the second reversible thermochromic material are stopped, and the first reversible thermochromic material is attached to the second reversible thermochromic material under a temperature environment of 5 ° C. A temperature control indicator (1) was prepared.

Temperature check during distribution and storage of pharmaceuticals (determine whether or not the temperature exceeds the appropriate temperature range above 2 ° C and below 8 ° C)
In a temperature environment of 5 ° C, when a temperature control indicator is affixed to a storage container that contains a pharmaceutical product having an appropriate temperature range of 2 ° C or higher and 8 ° C or lower, the second reversible thermochromic substance in a colored state. The pink color was visually recognized (initial state). As long as the storage container was within the proper temperature range, the pink temperature control indicator was only visible.
When the temperature control indicator in the initial state reaches a temperature of 8 ° C. or higher, the reversible thermochromic microcapsule pigment H provided in the second reversible thermochromic material is decolored and becomes colorless, which is caused by the second reversible thermochromic material. White color was visually recognized (state 1), and white color was only visually recognized in a temperature range exceeding 2 ° C.
When the temperature control indicator in the state 1 reaches a temperature of 2 ° C. or lower, the reversible thermochromic microcapsule pigment G provided in the first reversible thermochromic body and the reversible thermochromic microcapsule provided in the second reversible thermochromic body Pigment H was colored together, and a purple color, which was a mixture of blue color due to the first reversible thermochromic substance and pink color due to the second reversible thermochromic substance, was visually recognized (state 2). It was only visible.
When the temperature control indicator in the initial state reaches a temperature of 2 ° C. or lower, the reversible thermochromic microcapsule pigment G provided in the first reversible thermochromic body develops a color, and the first reversible thermochromic body produces a blue color. Purple in which a pink color was mixed by the second reversible thermochromic material was visually recognized (state 2), and only purple was visually recognized in a temperature range of less than 8 ° C.
When the temperature control indicator in the state 2 reaches a temperature of 8 ° C. or higher, the reversible thermochromic microcapsule pigment G provided in the first reversible thermochromic body and the reversible thermochromic microcapsule provided in the second reversible thermochromic body Both of the pigments H were decolored to become colorless, and white due to the second reversible thermochromic material was visually recognized (state 1).
Therefore, the storage container in which the medicine is packed changes color when placed in a temperature environment outside the proper temperature range and cannot be returned to the initial state thereafter, and it is irreversibly confirmed that the storage container has deviated from the proper temperature range. I was able to.
The second reversible thermochromic substance was peeled off in order to replace it with another second reversible thermochromic substance in a different coloring state so as not to leave a history of increasing and decreasing the temperature of the drug product. The surface base material of the body tampering prevention label was destroyed, and traces of peeling remained on the storage container.
Therefore, the temperature management indicator has a function of preventing falsification such as replacement or re-sticking.

Example 7
Preparation of Reversible Thermochromic Microcapsule Pigment I As component (a), 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethylmethylindol-3-yl) -4-azaphthalide 1.0 part As a component (b), 5.0 parts of 4,4 '-(2-methylpropane-1,1-diyl) diphenol, as a component (c) 5.0 parts of cetyl alcohol, and myristyl alcohol 20. A reversible thermochromic composition comprising 0.0 parts and 25.0 parts of decyl myristate was dissolved by heating and encapsulated in microcapsules by an interfacial polymerization method to obtain a microcapsule suspension. The suspension was centrifuged to isolate heat-decolorizable reversible thermochromic microcapsule pigment I.
The reversible thermochromic microcapsule pigment I has a particle size of 6.0 μm, a complete color development temperature t ₁ of 11 ° C., a color development start temperature t ₂ of 13 ° C., a decolorization start temperature t ₃ of 20 ° C., and a complete decolorization temperature. t ₄ was 22 ° C., the hysteresis width ΔH was 9 ° C., and the color changed reversibly from blue to colorless due to the temperature change.

Fabrication of temperature control indicator with tampering prevention function (see Figure 18)
As the tampering prevention member (12), a reversible heat treatment was applied to the surface opposite to the adhesive surface of the tampering prevention label [TP seal C (M) Kaifu manufactured by Lintec Co., Ltd.] having a thickness of 38 μm and made of a transparent polyester film. Reversible thermochromic property obtained by uniformly dispersing 30 parts of color-changing microcapsule pigment I, 62 parts of urethane emulsion, 2 parts of thickener, 0.5 part of leveling agent, 0.5 part of defoaming agent, and 5 parts of crosslinking agent. The ink was subjected to solid printing using a 120 mesh screen plate, dried and cured to provide a reversible thermochromic layer (4), and thus a first reversible thermochromic body (2) was obtained.
Then, on a white polyester film having a thickness of 25 μm as a support (6), 30 parts of the above-mentioned reversible thermochromic microcapsule pigment A, 62 parts of a urethane-based emulsion, 2 parts of a thickening agent, 0.5 part of a leveling agent, and a decoloring agent. Reversible thermochromic ink obtained by uniformly dispersing 0.5 parts of a foaming agent and 5 parts of a crosslinking agent is solid-printed using a 120 mesh screen plate and dried and cured to form a reversible thermochromic layer (4). Thus, a second reversible thermochromic material (3) was obtained.
The first reversible thermochromic material was cooled to 11 ° C. or lower to maintain the colored state, and the second reversible thermochromic material was heated to 22 ° C. or higher to retain the decolored state and stored.
Stop the cooling of the first reversible thermochromic material and the heating of the second reversible thermochromic material, and attach the first reversible thermochromic material to the second reversible thermochromic material under a temperature environment of 17 ° C. A temperature control indicator (1) was prepared.

Temperature check during distribution and storage of chocolate (determine whether the temperature exceeds 15 ° C and less than 22 ° C) (see Fig. 7)
In a temperature environment of 17 ° C, when a temperature control indicator is attached to a packaging container containing chocolate, which has an appropriate temperature range exceeding 15 ° C and less than 22 ° C, the first reversible thermochromic material produces blue color. Visually recognized (initial state). As long as the packaging container was within the proper temperature range, only blue color was visible.
When the temperature control indicator in the initial state reaches a temperature of 22 ° C. or higher, the reversible thermochromic microcapsule pigment I provided in the first reversible thermochromic material is decolored and becomes colorless, and the second reversible thermochromic material causes White color was visually recognized (state 1), and only white color was visually recognized in a temperature range exceeding 15 ° C.
When the temperature control indicator in the state 1 exceeds 11 ° C. and reaches a temperature of 15 ° C. or less, the reversible thermochromic microcapsule pigment A provided in the second reversible thermochromic substance develops a color to give the second reversible thermochromic substance. Was visually recognized (state 2), and only orange was visually recognized in the temperature range higher than 11 ° C. and lower than 22 ° C. Further, when the temperature control indicator in the state 2 reaches a temperature of 11 ° C. or lower, the reversible thermochromic microcapsule pigment I provided in the first reversible thermochromic body develops color, resulting in a blue color due to the first reversible thermochromic body. Black-brown in which orange was mixed with the second reversible thermochromic material was visually recognized (state 3), and only black-brown was visually recognized in a temperature range of less than 22 ° C.
Further, when the temperature control indicator in the state 1 reaches a temperature of 11 ° C. or lower, the reversible thermochromic microcapsule pigment I provided in the first reversible thermochromic substance and the reversible thermochromic property provided in the second reversible thermochromic substance. A black brown color, in which both the microcapsule pigment A and the blue color due to the first reversible thermochromic substance and the orange color due to the second reversible thermochromic substance were mixed, was visually recognized (state 3), and the temperature range was lower than 22 ° C. Only black-brown was visible.
When the temperature control indicator in the state 3 reaches a temperature of 22 ° C. or higher, the reversible thermochromic microcapsule pigment I provided in the first reversible thermochromic body and the reversible thermochromic microcapsule provided in the second reversible thermochromic body Both of the pigments A were decolored to become colorless, white color due to the second reversible thermochromic material was visually recognized (state 1), and only white color was visually recognized in a temperature range of higher than 15 ° C.
Further, when the temperature control indicator in the initial state reaches a temperature of 15 ° C. or lower, the reversible thermochromic microcapsule pigment A provided in the second reversible thermochromic substance develops a color, and the first reversible thermochromic substance causes a blue color. Black-brown in which orange was mixed with the second reversible thermochromic material was visually recognized (state 3), and only black-brown was visually recognized in a temperature range of less than 22 ° C.
When the temperature control indicator in the state 3 reaches a temperature of 22 ° C. or higher, the reversible thermochromic microcapsule pigment I provided in the first reversible thermochromic body and the reversible thermochromic microcapsule provided in the second reversible thermochromic body Both of the pigments A were decolored to become colorless, white color due to the second reversible thermochromic material was visually recognized (state 1), and only white color was visually recognized in a temperature range of higher than 15 ° C.
When the temperature control indicator in the state 1 exceeds 11 ° C. and reaches a temperature of 15 ° C. or lower, the reversible thermochromic microcapsule pigment A provided in the second reversible thermochromic substance develops a color to give the second reversible thermochromic substance. Was visually recognized (state 2), and only orange was visually recognized in the temperature range higher than 11 ° C. and lower than 22 ° C. Further, when the temperature control indicator in the state 2 reaches a temperature of 11 ° C. or lower, the reversible thermochromic microcapsule pigment I provided in the first reversible thermochromic body develops color, resulting in a blue color due to the first reversible thermochromic body. Black-brown in which orange was mixed with the second reversible thermochromic material was visually recognized (state 3), and only black-brown was visually recognized in a temperature range of less than 22 ° C.
Further, when the temperature control indicator in the state 1 reaches a temperature of 11 ° C. or lower, the reversible thermochromic microcapsule pigment I provided in the first reversible thermochromic substance and the reversible thermochromic property provided in the second reversible thermochromic substance. A black brown color, in which both the microcapsule pigment A and the blue color due to the first reversible thermochromic substance and the orange color due to the second reversible thermochromic substance were mixed, was visually recognized (state 3), and the temperature range was lower than 22 ° C. Only black-brown was visible.
Therefore, the packaging container containing chocolate discolors when placed in a temperature environment outside the proper temperature range, and then it cannot be returned to the initial state, and it is irreversibly confirmed that the packaging container deviates from the proper temperature range. I was able to do it. Furthermore, the temperature control indicator once placed in a temperature environment higher than the proper temperature range indicates that the temperature control indicator is placed in a temperature range of more than 11 ° C. and 15 ° C. or less in a temperature environment lower than the proper temperature range. It changed to a different color when placed in a temperature range of ℃ or less, and had a temperature control function in a specific temperature range.
Further, the above temperature control indicator shows that the color development start temperature t ₂ of the reversible thermochromic material in the color developed state (the reversible thermochromic microcapsule pigment I provided in the first reversible thermochromic material) is the reversible heat in the decolored state. The reversible thermochromic microcapsule pigment provided in each reversible thermochromic material is smaller than the complete decoloring temperature t _{1 of the} color-changing material (reversible thermochromic microcapsule pigment A provided in the second reversible thermochromic material). From I and the color of the reversible thermochromic microcapsule pigment A in the decolored state (state 1), only the reversible thermochromic microcapsule pigment A provided in the second reversible thermochromic body is in the colored state (state 2) The change to was clear.
Furthermore, the first reversible thermochromic substance was peeled off in an attempt to replace it with a first reversible thermochromic substance in a different coloring state so as not to leave a history of increasing and decreasing the temperature of the chocolate. The adhesive of the tamperproof label of the thermochromic body remained on the second reversible thermochromic body, and the characters "opened" were transferred. An attempt was made to re-attach the peeled first reversible thermochromic material to the second reversible thermochromic material, but the characters remaining on the second reversible thermochromic material and the first reversible thermochromic material The missing characters on the tampering prevention label did not exactly overlap.
Therefore, the above-mentioned temperature management indicator has a function of preventing falsification such as replacement or reattachment.

Example 8
Preparation of Reversible Thermochromic Microcapsule Pigment J (A) As components, {4- [2,6-bis (2,4-diethoxyphenyl) pyridin-4-yl] phenyl} dimethylamine 1.0 part, A reversible thermochromic composition comprising 5.0 parts of 2,2-bis (4-hydroxyphenyl) hexafluoropropane as the component (b) and 50.0 parts of cyclohexylmethyl stearate as the component (c). It was dissolved by heating and encapsulated in microcapsules by an interfacial polymerization method to obtain a microcapsule suspension. The suspension was centrifuged to isolate the heat-decolorizable reversible thermochromic microcapsule pigment J.
The reversible thermochromic microcapsule pigment J has a particle diameter of 2.5 μm, a complete color development temperature t ₁ of 15 ° C., a color development start temperature t ₂ of 21 ° C., a decolorization start temperature t ₃ of 33 ° C., and a complete decolorization. The temperature t ₄ was 39 ° C., the hysteresis width ΔH was 18 ° C., and the temperature changed reversibly from yellow to colorless.
Preparation of Reversible Thermochromic Microcapsule Pigment K 2.0 parts of 1,2-benz-6-diethylaminofluorane as component (a) and 4,4- (2-methylpropylidene) as component (b) A reversible thermochromic composition comprising 6.0 parts of bisphenol and 50.0 parts of neopentyl stearate as a component (c) is dissolved by heating and encapsulated in microcapsules by an interfacial polymerization method to prepare a microcapsule suspension. Got The suspension was centrifuged to isolate heat-decolorizable reversible thermochromic microcapsule pigment K.
The reversible thermochromic microcapsule pigment K has a particle diameter of 2.5 μm, a complete color development temperature t ₁ of 15 ° C., a color development start temperature t ₂ of 21 ° C., a decolorization start temperature t ₃ of 26 ° C., and a complete decolorization. The temperature t ₄ was 32 ° C., the hysteresis width ΔH was 18 ° C., and the color changed reversibly from pink to colorless due to the temperature change.

Fabrication of temperature control indicator with tampering prevention function (see Fig. 19)
As a support (5) having transparency, 30 parts of reversible thermochromic microcapsule pigment J is provided on the surface of the transparent polyester film having a thickness of 25 μm provided with the first adhesive layer (10) on the side opposite to the adhesive layer. , A reversible thermochromic ink of 120 mesh with a uniform dispersion of 62 parts of urethane emulsion, 2 parts of thickening agent, 0.5 parts of leveling agent, 0.5 parts of defoaming agent and 5 parts of crosslinking agent. Solid printing was carried out using, and dried and cured to provide a reversible thermochromic layer (4), to obtain a first reversible thermochromic material (2).
Next, as a tamper-proof member (12), a 50 μm-thick tamper-proof label [FP1102B PAT1 11HL manufactured by Lintec Co., Ltd.] having a thickness of 50 μm was formed on the surface opposite to the adhesive surface by reversible thermochromism. A reversible thermochromic ink obtained by uniformly dispersing 30 parts of microcapsule pigment K, 62 parts of urethane emulsion, 2 parts of thickener, 0.5 part of leveling agent, 0.5 part of defoaming agent, and 5 parts of crosslinking agent. Solid printing was performed using a 120 mesh screen plate, dried and cured to provide a reversible thermochromic layer (4), and a second reversible thermochromic body (3) was obtained.
The first reversible thermochromic material was heated to 32 ° C. or higher to maintain the decolored state, and the second reversible thermochromic material was cooled to 15 ° C. or lower to retain the colored state and stored.
The heating of the first reversible thermochromic material and the cooling of the second reversible thermochromic material are stopped, and the first reversible thermochromic material is attached to the second reversible thermochromic material under a temperature environment of 18 ° C. A temperature control indicator (1) was prepared.

Temperature check during distribution and storage of seasonings (determine whether the temperature exceeds 15 ° C and less than 32 ° C) (see Fig. 4)
In a temperature environment of 18 ° C, if a temperature control indicator is attached to a storage container containing a seasoning that has an appropriate temperature range of more than 15 ° C and less than 32 ° C, the second reversible thermochromic material causes pink color. Was visually recognized (initial state). As long as the storage container was within the proper temperature range, only pink was visible.
When the temperature control indicator in the initial state reaches a temperature of 32 ° C. or higher, the reversible thermochromic microcapsule pigment K provided in the second reversible thermochromic material is decolored and becomes colorless, which is caused by the second reversible thermochromic material. White color was visually recognized (state 1), and only white color was visually recognized in a temperature range exceeding 15 ° C.
When the temperature control indicator in the state 1 reaches a temperature of 15 ° C. or lower, the reversible thermochromic microcapsule pigment J provided in the first reversible thermochromic body and the reversible thermochromic microcapsule provided in the second reversible thermochromic body Pigment K was colored together, and an orange color, which was a mixture of yellow color due to the first reversible thermochromic substance and pink color due to the second reversible thermochromic substance, was visually recognized (state 2), and orange was observed in the temperature range of less than 32 ° C. It was only visible.
When the temperature control indicator in the state 2 reaches a temperature of 32 ° C. or higher and lower than 39 ° C., the reversible thermochromic microcapsule pigment K provided in the second reversible thermochromic material is decolored to give the first reversible thermochromic material. The yellow color was visually recognized (state 3), and the yellow color was only visually recognized in a temperature range of higher than 15 ° C and lower than 39 ° C. Furthermore, when the temperature control indicator in the state 3 reaches a temperature of 39 ° C. or higher, the reversible thermochromic microcapsule pigment J provided in the first reversible thermochromic material is decolored and becomes colorless, and the second reversible thermochromic material is used. White by the body was visually recognized (state 1), and white by the second reversible thermochromic material was visually recognized in the temperature range of higher than 15 ° C.
When the temperature control indicator in the state 2 reaches a temperature of 39 ° C. or higher, the reversible thermochromic microcapsule pigment J provided in the first reversible thermochromic substance and the reversible thermochromic property provided in the second reversible thermochromic substance. Both of the microcapsule pigments K are discolored and become colorless, and the white color due to the second reversible thermochromic substance is visually recognized (state 1), and the white color due to the second reversible thermochromic substance is visually recognized in a temperature range of over 15 ° C. It was
Further, when the temperature control indicator in the initial state reaches a temperature of 15 ° C. or lower, the reversible thermochromic microcapsule pigment J provided in the first reversible thermochromic body develops a color and becomes yellow due to the first reversible thermochromic body. An orange color in which a pink color was mixed by the second reversible thermochromic material was visually recognized (state 2), and only an orange color was visually recognized in a temperature range of less than 32 ° C.
When the temperature control indicator in the state 2 reaches a temperature of 32 ° C. or higher and lower than 39 ° C., the reversible thermochromic microcapsule pigment K provided in the second reversible thermochromic material is decolored to give the first reversible thermochromic material. The yellow color was visually recognized (state 3), and the yellow color was only visually recognized in a temperature range of higher than 15 ° C and lower than 39 ° C. Further, when the temperature control indicator in the state 3 reaches a temperature of 39 ° C. or higher, the reversible thermochromic microcapsule pigment J contained in the first reversible thermochromic material is decolored and becomes colorless, and the second reversible thermochromic pigment is used. White was visually recognized by the body (state 1), and white was only visually recognized in a temperature range of higher than 15 ° C.
When the temperature control indicator in the state 2 reaches a temperature of 39 ° C. or higher, the reversible thermochromic microcapsule pigment J provided in the first reversible thermochromic substance and the reversible thermochromic property provided in the second reversible thermochromic substance. Both of the microcapsule pigments K are discolored and become colorless, and the white color due to the second reversible thermochromic substance is visually recognized (state 1), and the white color due to the second reversible thermochromic substance is visually recognized in a temperature range of over 15 ° C. It was
When the temperature control indicator in the state 1 reaches a temperature of 15 ° C. or lower, the reversible thermochromic material J provided in the first reversible thermochromic body and the reversible thermochromic microcapsule pigment K provided in the second reversible thermochromic body And the yellow color due to the first reversible thermochromic substance and the pink color due to the second reversible thermochromic substance are mixed to form an orange color (state 2), and an orange color is visually recognized in a temperature range of less than 32 ° C. It was only
Therefore, the storage container containing the seasoning discolors when placed in a temperature environment outside the proper temperature range, and then it cannot be returned to the initial state, and it is irreversibly confirmed that the storage container has deviated from the proper temperature range. We were able to. Furthermore, the temperature control indicator once placed in a temperature environment lower than the proper temperature range indicates that the temperature management indicator is placed in a temperature environment of 32 ° C. or higher and lower than 39 ° C. in a temperature environment higher than the proper temperature range. It changed to a different color when placed in a temperature environment above ℃ and had a temperature control function in a specific temperature range.
Further, the above temperature control indicator shows that the complete decoloring temperature t ₄ of the reversible thermochromic material in the colored state (the reversible thermochromic microcapsule pigment K provided in the first reversible thermochromic material) is the reversible state in the decolorized state. The reversible thermochromic microcapsules provided in each reversible thermochromic material are smaller than the decolorization start temperature t _{3 of the} thermochromic material (reversible thermochromic microcapsule pigment J provided in the second reversible thermochromic material). From the color development state (state 2) of the pigment J and the reversible thermochromic microcapsule pigment K, only the color of the reversible thermochromic microcapsule pigment K provided in the second reversible thermochromic substance is in the decolorized state (state 3). The change was clear.
The second reversible thermochromic substance was peeled off in an attempt to replace it with a second reversible thermochromic substance in another coloring state so as not to leave a history of increasing and decreasing the temperature of the seasoning. The surface substrate of the tamperproof label of the color change body was destroyed, and a trace of peeling remained on the storage container.
Therefore, the temperature management indicator has a function of preventing falsification such as replacement or re-sticking.

Example 9
Preparation of Reversible Thermochromic Microcapsule Pigment L As component (a), 3- [2-ethoxy-4- (N-ethylanilino) phenyl] -3- (1-ethyl-2-methyl-indol-3-yl) was used. 2.0 parts of -4-azaphthalide, 6.0 parts of 1,1-bis (4-hydroxyphenyl) hexafluoropropane as the component (b), and 50.0 parts of nonyl palmitate as the component (c). The reversible thermochromic composition consisting of was dissolved under heating and encapsulated in microcapsules by an interfacial polymerization method to obtain a microcapsule suspension. The suspension was centrifuged to isolate heat-decolorizable reversible thermochromic microcapsule pigment L.
The reversible thermochromic microcapsule pigment L has a particle diameter of 8.0 μm, a complete color development temperature t ₁ of 16 ° C., a color development start temperature t ₂ of 19 ° C., a decolorization start temperature t ₃ of 27 ° C., and a complete decolorization. The temperature t ₄ was 32 ° C., the hysteresis width ΔH was 12 ° C., and the temperature changed reversibly from blue to colorless.
Preparation of Reversible Thermochromic Microcapsule Pigment M As component (a), 2.0 parts of 1,2-benz-6- (N-ethyl-N-isobutylamino) fluorane, and as component (b), 1,1 -A reversible thermochromic composition comprising 6.0 parts of bis (4-hydroxyphenyl) hexafluoropropane and 50.0 parts of nonyl palmitate as a component (c) was dissolved by heating and micro-structured by an interfacial polymerization method. It was encapsulated in a capsule to obtain a microcapsule suspension. The suspension was centrifuged to isolate the heat-decolorizable reversible thermochromic microcapsule pigment M.
The reversible thermochromic microcapsule pigment M has a particle size of 3.0 μm, a complete color development temperature t ₁ of 4 ° C., a color development start temperature t ₂ of 18 ° C., a decolorization start temperature t ₃ of 27 ° C., and a complete decolorization. The temperature t ₄ was 32 ° C., the hysteresis width ΔH was 19 ° C., and the color changed reversibly from pink to colorless due to the temperature change.

Fabrication of temperature control indicator with adhesive layer (see Fig. 17)
As a transparent support (5), 30 parts of reversible thermochromic microcapsule pigment L is provided on the surface of the transparent polyester film having a thickness of 25 μm provided with the first adhesive layer (10) on the side opposite to the adhesive layer. , A reversible thermochromic ink of 120 mesh with a uniform dispersion of 62 parts of urethane emulsion, 2 parts of thickening agent, 0.5 parts of leveling agent, 0.5 parts of defoaming agent and 5 parts of crosslinking agent. Solid printing was carried out using, and dried and cured to provide a reversible thermochromic layer (4), and a first reversible thermochromic body (2) was obtained.
Then, as a support (6), a reversible thermochromic microcapsule pigment M30 parts and urethane were formed on the surface of the white polyester film having a thickness of 25 μm provided with the second adhesive layer (11) on the side opposite to the adhesive layer. A reversible thermochromic ink obtained by uniformly dispersing 62 parts of a system emulsion, 2 parts of a thickener, 0.5 part of a leveling agent, 0.5 part of a defoaming agent, and 5 parts of a crosslinking agent using a 120 mesh screen plate. Solid printing was performed, followed by drying and curing to provide a reversible thermochromic layer (4) to obtain a second reversible thermochromic material (3).
The first reversible thermochromic material was heated to 32 ° C. or higher to maintain the decolored state, and the second reversible thermochromic material was cooled to 4 ° C. or less to retain the colored state and stored.
The heating of the first reversible thermochromic material and the cooling of the second reversible thermochromic material are stopped, and the first reversible thermochromic material is attached to the second reversible thermochromic material under a temperature environment of 20 ° C. A temperature control indicator (1) was prepared.

Temperature check during distribution and storage of vegetables (determine whether or not the temperature exceeds 16 ° C and less than 32 ° C) (see Fig. 5)
In a temperature environment of 20 ° C, when a temperature control indicator is affixed to a packaging container that contains vegetables whose proper temperature range is over 16 ° C and under 32 ° C, a pink color due to the second reversible thermochromic material is generated. Visually recognized (initial state). As long as the packaging container was within the proper temperature range, only pink was visible.
When the temperature control indicator in the initial state reaches a temperature of 32 ° C. or higher, the reversible thermochromic microcapsule pigment M provided in the second reversible thermochromic material is decolored and becomes colorless, which is caused by the second reversible thermochromic material. White color was visually recognized (state 1), and only white color was visually recognized in a temperature range exceeding 16 ° C.
When the temperature control indicator in the state 1 exceeds 4 ° C. and reaches a temperature of 16 ° C. or less, the reversible thermochromic microcapsule pigment L provided in the first reversible thermochromic substance develops a color to produce the first reversible thermochromic substance. The blue color was visually recognized (state 2), and the blue color was only visually recognized in the temperature range of more than 4 ° C and less than 32 ° C. Furthermore, when the temperature control indicator in the state 2 reaches a temperature of 4 ° C. or lower, the reversible thermochromic microcapsule pigment M contained in the second reversible thermochromic substance develops a color, resulting in a blue color due to the first reversible thermochromic substance. Purple in which the pink color was mixed with the second reversible thermochromic material was visually recognized (state 3), and only purple was visible in the temperature range of less than 32 ° C.
Further, when the temperature control indicator in the state 1 reaches a temperature of 4 ° C. or lower, the reversible thermochromic microcapsule pigment M provided in the first reversible thermochromic substance and the reversible thermochromic property provided in the second reversible thermochromic substance. Both the microcapsule pigment L developed a color, and a purple color in which a blue color due to the first reversible thermochromic substance and a pink color due to the second reversible thermochromic substance were mixed (state 3) was visually recognized. Only purple was visible.
When the temperature control indicator in the state 3 reaches a temperature of 32 ° C. or higher, the reversible thermochromic microcapsule pigment L provided in the first reversible thermochromic body and the reversible thermochromic microcapsule provided in the second reversible thermochromic body Both the pigments M were decolored to become colorless, white color due to the second reversible thermochromic material was visually recognized (state 1), and only white color was visually recognized in a temperature range exceeding 16 ° C.
Further, when the temperature control indicator in the initial state reaches a temperature of 16 ° C. or lower, the reversible thermochromic microcapsule pigment L provided in the first reversible thermochromic body develops a color, resulting in a blue color due to the first reversible thermochromic body. Purple in which the pink color was mixed with the second reversible thermochromic material was visually recognized (state 3), and only purple was visible in the temperature range of less than 32 ° C.
When the temperature control indicator in the state 3 reaches a temperature of 32 ° C. or higher, the reversible thermochromic microcapsule pigment L provided in the first reversible thermochromic body and the reversible thermochromic microcapsule provided in the second reversible thermochromic body Both the pigments M were decolored to become colorless, white color due to the second reversible thermochromic material was visually recognized (state 1), and only white color was visually recognized in a temperature range exceeding 16 ° C.
When the temperature control indicator in the state 1 exceeds 4 ° C. and reaches a temperature of 16 ° C. or less, the reversible thermochromic microcapsule pigment L provided in the first reversible thermochromic substance develops a color to produce the first reversible thermochromic substance. The blue color was visually recognized (state 2), and the blue color was only visually recognized in the temperature range of more than 4 ° C and less than 32 ° C. Furthermore, when the temperature control indicator in the state 2 reaches a temperature of 4 ° C. or lower, the reversible thermochromic microcapsule pigment M contained in the second reversible thermochromic substance develops a color, resulting in a blue color due to the first reversible thermochromic substance. Purple in which the pink color was mixed with the second reversible thermochromic material was visually recognized (state 3), and only purple was visible in the temperature range of less than 32 ° C.
Further, when the temperature control indicator in the state 1 reaches a temperature of 4 ° C. or lower, the reversible thermochromic microcapsule pigment M provided in the first reversible thermochromic substance and the reversible thermochromic property provided in the second reversible thermochromic substance. Both the microcapsule pigment L developed a color, and a purple color in which a blue color due to the first reversible thermochromic substance and a pink color due to the second reversible thermochromic substance were mixed (state 3) was visually recognized. Only purple was visible.
Therefore, the packaging container containing vegetables discolors when placed in a temperature environment outside the proper temperature range and cannot be returned to the initial state thereafter, and it is irreversibly confirmed that the packaging container has deviated from the proper temperature range. I was able to do it. Further, the temperature control indicator once placed in a temperature environment higher than the proper temperature range has a temperature environment lower than the proper temperature range and is placed in a temperature environment of more than 4 ° C. and 16 ° C. or less, The color changed to a different color when placed in a temperature environment of 4 ° C. or less, and had a temperature management function in a specific temperature range.

Example 10
Preparation of reversible thermochromic microcapsule pigment N As component (a), 4,5,6,7-tetrachloro-3- (4-diethylamino-2-methylphenyl) -3- (1-ethyl-2-methyl) 2.0 parts of -1H-indol-3-yl) -1 (3H) isobenzofuranone, 8.0 parts of 2,2-bis (4-hydroxyphenyl) propane as the component (b), and (c) As a component, a reversible thermochromic composition composed of 35.0 parts of stearyl caprate and 15.0 parts of cetyl caprate was dissolved by heating and encapsulated in microcapsules by an interfacial polymerization method to prepare a microcapsule suspension. Obtained. The suspension was centrifuged to isolate heat-decolorizable reversible thermochromic microcapsule pigment N.
The reversible thermochromic microcapsule pigment N has a particle size of 3.0 μm, a complete color development temperature t ₁ of 8 ° C., a color development start temperature t ₂ of 28 ° C., a decolorization start temperature t ₃ of 25 ° C., and a complete decolorization. The temperature t ₄ was 34 ° C., the hysteresis width ΔH was 11.5 ° C., and the temperature changed reversibly from blue to colorless.

Fabrication of temperature control indicator (see Figure 16)
As a transparent support (5), a reversible thermochromic microcapsule pigment N30 parts, urethane emulsion 62 parts, thickener 2 parts, leveling agent 0.5 part, on a transparent polyester film having a thickness of 25 μm, A reversible thermochromic ink obtained by uniformly dispersing 0.5 parts of a defoaming agent and 5 parts of a crosslinking agent is solid-printed using a 120 mesh screen plate, and dried and cured to form a reversible thermochromic layer (4). It provided and the 1st reversible thermochromic body (2) was obtained.
Then, on a white synthetic paper as a support (6), 30 parts of the above-mentioned reversible thermochromic microcapsule pigment K, 62 parts of urethane emulsion, 2 parts of thickener, 0.5 part of leveling agent, 0.5 part of defoaming agent. Part and 5 parts of the cross-linking agent are uniformly dispersed to perform solid printing using a 120-mesh screen plate and dry cure to form a reversible thermochromic layer (4). A reversible thermochromic material (3) was obtained.
The first reversible thermochromic material was cooled to 8 ° C. or lower to maintain the colored state, and the second reversible thermochromic material was heated to 32 ° C. or higher to retain the decolored state and stored.
The cooling of the first reversible thermochromic material and the heating of the second reversible thermochromic material are stopped, and the first reversible thermochromic material is laminated on the second reversible thermochromic material to produce the temperature management indicator (1). did.

Temperature check during distribution and storage of vegetables (determine whether the temperature exceeds 15 ° C and less than 32 ° C) (see Figure 6)
Under a temperature environment of 20 ° C, when a temperature control indicator is stacked on a packaging container that contains vegetables whose proper temperature range is over 15 ° C and under 32 ° C, blue color due to the first reversible thermochromic material is visually recognized. Was done (initial state). As long as the packaging container was within the proper temperature range, only blue color was visible.
When the temperature control indicator in the initial state reaches a temperature of 34 ° C. or higher, the reversible thermochromic microcapsule pigment N provided in the first reversible thermochromic substance is decolored and becomes colorless, and the second reversible thermochromic substance causes White color was visually recognized (state 1), and only white color was visually recognized in a temperature range exceeding 15 ° C.
When the temperature control indicator in the state 1 exceeds 8 ° C. and reaches a temperature of 15 ° C. or less, the reversible thermochromic microcapsule pigment K provided in the second reversible thermochromic substance develops a color to give the second reversible thermochromic substance. The peach color was visually recognized (state 2), and only the blue color was visually recognized in the temperature range of higher than 8 ° C and lower than 34 ° C. Further, when the temperature control indicator in the state 2 reaches a temperature of 8 ° C. or lower, the reversible thermochromic microcapsule pigment N contained in the first reversible thermochromic substance develops color, and a blue color due to the first reversible thermochromic substance is generated. Purple in which the pink color was mixed by the second reversible thermochromic material was visually recognized (state 3), and only purple was visually recognized in the temperature range of less than 32 ° C.
Further, when the temperature control indicator in the state 1 reaches a temperature of 8 ° C. or lower, the reversible thermochromic microcapsule pigment N provided in the first reversible thermochromic substance and the reversible thermochromic property provided in the second reversible thermochromic substance. The microcapsule pigment K was colored together, and a purple color, which was a mixture of blue color due to the first reversible thermochromic substance and pink color due to the second reversible thermochromic substance, was visually recognized (state 3), and in the temperature range below 32 ° C. Only purple was visible.
When the temperature control indicator in the state 3 reaches a temperature of 34 ° C. or higher, the reversible thermochromic microcapsule pigment N provided in the first reversible thermochromic body and the reversible thermochromic microcapsule provided in the second reversible thermochromic body Both the pigments K were decolored to become colorless, white due to the second reversible thermochromic material was visually recognized (state 1), and only white was visually recognized in the temperature range exceeding 15 ° C.
When the temperature control indicator in the initial state reaches a temperature of 15 ° C. or lower, the reversible thermochromic microcapsule pigment K provided in the second reversible thermochromic body develops a color, and the first reversible thermochromic body produces a blue color. Purple in which the pink color was mixed by the second reversible thermochromic material was visually recognized (state 3), and only purple was visually recognized in the temperature range of less than 32 ° C.
When the temperature control indicator in the state 3 reaches a temperature of 34 ° C. or higher, the reversible thermochromic microcapsule pigment N provided in the first reversible thermochromic body and the reversible thermochromic microcapsule provided in the second reversible thermochromic body Both the pigments K were decolored to become colorless, white due to the second reversible thermochromic material was visually recognized (state 1), and only white was visually recognized in the temperature range exceeding 15 ° C.
When the temperature control indicator in the state 1 exceeds 8 ° C. and reaches a temperature of 15 ° C. or less, the reversible thermochromic microcapsule pigment K provided in the second reversible thermochromic substance develops a color to give the second reversible thermochromic substance. The peach color was visually recognized (state 2), and only the peach color was visually recognized in a temperature range of higher than 8 ° C and lower than 32 ° C. Furthermore, when the temperature control indicator in the state 2 reaches a temperature of 8 ° C. or lower, the reversible thermochromic microcapsule pigment N contained in the first reversible thermochromic substance develops a color, resulting in a blue color due to the first reversible thermochromic substance. Purple in which the pink color was mixed by the second reversible thermochromic material was visually recognized (state 3), and only purple was visually recognized in the temperature range of less than 32 ° C.
Further, when the temperature control indicator in the state 1 reaches a temperature of 8 ° C. or lower, the reversible thermochromic microcapsule pigment N provided in the first reversible thermochromic substance and the reversible thermochromic property provided in the second reversible thermochromic substance. The microcapsule pigment K was colored together, and a purple color, which was a mixture of blue color due to the first reversible thermochromic substance and pink color due to the second reversible thermochromic substance, was visually recognized (state 3), and in the temperature range below 32 ° C. Only purple was visible.
Therefore, the packaging container containing vegetables discolors when placed in a temperature environment outside the proper temperature range and cannot be returned to the initial state thereafter, and it is irreversibly confirmed that the packaging container has deviated from the proper temperature range. I was able to do it. Further, the temperature control indicator once placed in a temperature environment higher than the proper temperature range has a temperature environment of lower than the proper temperature range, in which the temperature control indicator exceeds 8 ° C. and is 15 ° C. or less. The color changed to a different color when placed in a temperature environment of 8 ° C. or less, and had a temperature management function in a specific temperature range.

Example 11
Preparation of Reversible Thermochromic Microcapsule Pigment O As component (a), 2-di-n-butylamino-8-di-n-pentylamino-4-methyl-spiro [5H- [1] benzopyrano [2,3] -D] pyrimidine] -5,1 '(3'H) isobenzofuran] -3'-one 1.0 part and (2-) component 2,2-bis (4'-hydroxyphenyl) propane 8. A reversible thermochromic composition comprising 0 part and 50.0 parts of cetyl caprate as a component (c) was dissolved by heating and encapsulated in a microcapsule by an interfacial polymerization method to obtain a microcapsule suspension. . The suspension was centrifuged to isolate heat-decolorizable reversible thermochromic microcapsule pigment O.
The reversible thermochromic microcapsule pigment O has a particle size of 6.0 μm, a complete color development temperature t ₁ of 25 ° C., a color development start temperature t ₂ of 27 ° C., a decolorization start temperature t ₃ of 29 ° C., and a complete decolorization. The temperature t ₄ was 33 ° C., the hysteresis width ΔH was 5 ° C., and the color changed reversibly from pink to colorless due to the temperature change.
Preparation of reversible thermochromic microcapsule pigment P As component (a), 3- (2-ethoxy-4-diethylaminophenyl) -3- (1-pentyl-2-methylindol-3-yl) -4,5, 2.0 parts of 6,7-tetrachlorophthalide, 18.0 parts of dodecyl gallate as the (b) component, 35.0 parts of lauryl alcohol and 15.0 of stearyl laurate as the (c) component. The reversible thermochromic composition consisting of 1 part and 2 parts was dissolved by heating and encapsulated in microcapsules by an interfacial polymerization method to obtain a microcapsule suspension. The suspension was centrifuged to isolate heat-decolorizable reversible thermochromic microcapsule pigment P.
The reversible thermochromic microcapsule pigment P has a particle size of 6.0 μm, a complete color development temperature t ₁ of 23 ° C., a color development start temperature t ₂ of 28 ° C., a decolorization start temperature t ₃ of 30 ° C., and a complete decolorization. The temperature t ₄ was 38 ° C., the hysteresis width ΔH was 8.5 ° C., and the color changed reversibly from blue to colorless due to the temperature change.

Fabrication of temperature control indicator with adhesive layer (see Fig. 17)
As a support (5) having transparency, 30 parts of reversible thermochromic microcapsule pigment O is provided on the surface of the transparent polyester film having a thickness of 25 μm provided with the first adhesive layer (10) on the side opposite to the adhesive layer. , A reversible thermochromic ink of 120 mesh with a uniform dispersion of 62 parts of urethane emulsion, 2 parts of thickening agent, 0.5 parts of leveling agent, 0.5 parts of defoaming agent and 5 parts of crosslinking agent. Solid printing was carried out using, and the reversible thermochromic layer (4) was provided by drying and curing to obtain a first reversible thermochromic material (2).
Then, as a support (6), on a surface of the white polyester film having a thickness of 25 μm provided with the second adhesive layer (11) on the side opposite to the adhesive layer, 30 parts of reversible thermochromic microcapsule pigment P, urethane A reversible thermochromic ink obtained by uniformly dispersing 62 parts of a system emulsion, 2 parts of a thickener, 0.5 part of a leveling agent, 0.5 part of a defoaming agent, and 5 parts of a crosslinking agent using a 120 mesh screen plate. Solid printing was performed, followed by drying and curing to provide a reversible thermochromic layer (4) to obtain a second reversible thermochromic material (3).
The first reversible thermochromic material was cooled to 25 ° C. or lower to retain the colored state, and the second reversible thermochromic material was heated to 38 ° C. or higher to retain the decolored state and stored.
Stop cooling of the first reversible thermochromic material and heating of the second reversible thermochromic material, and attach the first reversible thermochromic material to the second reversible thermochromic material under a temperature environment of 27 ° C. A temperature control indicator (1) was prepared.

Temperature check during distribution and storage of seasonings (determine whether or not the temperature has exceeded the proper temperature range of over 25 ° C and under 33 ° C) (see Fig. 2)
In a temperature environment of 27 ° C, when a temperature control indicator is attached to a storage container containing a seasoning whose temperature range is above 25 ° C and below 33 ° C, the first reversible thermal discoloration in the colored state. A pink color was visually recognized by the body (initial state). As long as the storage container was within the proper temperature range, only pink was visible.
When the temperature control indicator in the initial state reaches a temperature of 33 ° C. or higher, the reversible thermochromic microcapsule pigment P provided in the first reversible thermochromic material is decolored and becomes colorless, and the second reversible thermochromic material causes White color was visually recognized (state 1), and only white color was visually recognized in a temperature range exceeding 25 ° C.
When the temperature control indicator in the state 1 reaches a temperature of 25 ° C. or lower, the reversible thermochromic microcapsule pigment O provided in the first reversible thermochromic body and the reversible thermochromic microcapsule provided in the second reversible thermochromic body Pigment P is colored together, and a purple color, in which a pink color due to the first reversible thermochromic material and a blue color due to the second reversible thermochromic material are mixed, is visually recognized (state 2), and an orange color is obtained in a temperature range of less than 33 ° C. It was only visible.
When the temperature control indicator in the state 2 reaches a temperature of 33 ° C. or higher and lower than 38 ° C., the reversible thermochromic microcapsule pigment O provided in the first reversible thermochromic material is decolored to give the second reversible thermochromic material. The blue color was visually recognized (state 3), and the blue color was only visually recognized in a temperature range of higher than 25 ° C and lower than 38 ° C. Further, when the temperature control indicator in the state 3 reaches a temperature of 38 ° C. or higher, the reversible thermochromic microcapsule pigment P provided in the second reversible thermochromic material is decolored and becomes colorless, and the second reversible thermochromic material is used. White by the body was visually recognized (state 1), and white by the second reversible thermochromic body was visually recognized in the temperature range of more than 25 ° C.
Further, when the temperature control indicator in the state 2 reaches a temperature of 38 ° C. or higher, the reversible thermochromic microcapsule pigment O provided in the first reversible thermochromic body and the reversible thermochromic property provided in the second reversible thermochromic body. The microcapsule pigments P both disappear and become colorless, and the white color due to the second reversible thermochromic substance is visually recognized (state 1), and the white color due to the second reversible thermochromic substance is visually recognized in the temperature range of over 25 ° C. It was
Further, when the temperature control indicator in the initial state reaches a temperature of 23 ° C. or lower, the reversible thermochromic microcapsule pigment P provided in the second reversible thermochromic body develops color and becomes a pink color due to the first reversible thermochromic body. A purple color, which was a mixture of blue color due to the second reversible thermochromic material, was visually recognized (state 2), and only an orange color was visually recognized in a temperature range of less than 33 ° C.
When the temperature control indicator in the state 2 reaches a temperature of 33 ° C. or higher and lower than 38 ° C., the reversible thermochromic microcapsule pigment O provided in the first reversible thermochromic material is decolored to give the first reversible thermochromic material. The blue color was visually recognized (state 3), and the blue color was only visually recognized in a temperature range of higher than 25 ° C and lower than 38 ° C. Further, when the temperature control indicator in the state 3 reaches a temperature of 38 ° C. or higher, the reversible thermochromic microcapsule pigment P contained in the second reversible thermochromic material is decolored and becomes colorless, and the second reversible thermochromic White was visually recognized by the body (state 1), and white was only visually recognized in the temperature range of more than 25 ° C.
Further, when the temperature control indicator in the state 2 reaches a temperature of 38 ° C. or higher, the reversible thermochromic microcapsule pigment O provided in the first reversible thermochromic body and the reversible thermochromic property provided in the second reversible thermochromic body. The microcapsule pigments P both disappear and become colorless, and the white color due to the second reversible thermochromic substance is visually recognized (state 1), and the white color due to the second reversible thermochromic substance is visually recognized in the temperature range of over 25 ° C. It was
When the temperature control indicator in the state 1 reaches a temperature of 23 ° C. or lower, the reversible thermochromic material O included in the first reversible thermochromic material and the reversible thermochromic microcapsule pigment P included in the second reversible thermochromic material. , And a purple color in which a pink color due to the first reversible thermochromic substance and a blue color due to the second reversible thermochromic substance are mixed is observed (state 2), and a purple color is observed in a temperature range of less than 33 ° C. It was only

t ₁ complete color development temperature t ₂ color development start temperature t ₃ decolorization start temperature t ₄ complete decolorization temperature ΔH hysteresis width t _1A complete color development temperature of reversible thermochromic material in color development state t _1B reversible thermochromic material in decolorization state Complete color development temperature t _2A Color development start temperature of the reversible thermochromic material in the color development state t _2B Color development start temperature of the reversible thermochromic material in the color removal state t _3A Color removal start temperature of the reversible thermochromic material in the color development state t _3B Decoloring start temperature of reversible thermochromic material in decolored state t _4A Complete decoloring temperature of reversible thermochromic material in colored state t _4B Complete decoloring temperature of reversible thermochromic material in decolored state 1 Temperature control indicator 2 First reversible thermochromic body 3 Second reversible thermochromic body 4 Reversible thermochromic layer 5 Transparent support 6 Support 7 First reversible material containing a reversible thermochromic material in a transparent support Thermochromic body 8 Reversible in support Second reversible thermochromic body containing thermochromic material 9 Non-thermochromic layer 10 First adhesive layer 11 Second adhesive layer 12 Tamperproof member

Claims (15)

A temperature control indicator comprising a first reversible thermochromic material having transparency and a reversible thermochromic material, and a second reversible thermochromic material having a reversible thermochromic material. The thermochromic material comprises (a) an electron-donating color-developing organic compound, (b) an electron-accepting compound, and (c) a reaction medium for controlling the color reaction of the above (a) and (b). A reversible thermochromic microcapsule pigment containing at least a reversible thermochromic composition, or reversible thermochromic resin particles in which the reversible thermochromic composition is dispersed in a thermoplastic or thermosetting resin, concentration - shows the hysteresis characteristic exhibits photochromic coloring state and decolorizing state with respect to temperature curve, in the course of temperature increase from the colored state, begins decolorized to reach decoloring starting temperature t _3, the temperature t ₃ high complete decoloring temperature _{t 4} or more Become completely decolorized state at a temperature range, in the course of temperature from decolorized state is lowered, begins to color to reach coloring initiation temperature t _2, completely at low complete coloring temperature t ₁ the following temperature range than the temperature t ₂ The reversible thermochromic material exhibits a hysteresis characteristic of being in a color-developing state, exhibits a hysteresis width (ΔH) of 5 to 30 ° C. with respect to a color density-temperature curve, and one of the reversible thermochromic materials is in a color-developing state, and the other is in a color-developing state. The reversible thermochromic material is in a decolored state, and the first reversible thermochromic material is laminated on the second reversible thermochromic material.   2. The temperature management indicator according to claim 1, wherein the reversible thermochromic materials provided in the first reversible thermochromic material and the second reversible thermochromic material have different (a) electron donating color-developing organic compounds from each other.   The temperature management indicator according to claim 2, wherein the reversible thermochromic materials provided in the first reversible thermochromic body and the second reversible thermochromic body exhibit mutually different colors in a colored state.   Claims (c) of the reversible thermochromic materials provided in the first reversible thermochromic material and the second reversible thermochromic material have different reaction media for controlling the color reaction of (a) and (b). The temperature control indicator according to any one of items 1 to 3. Each of the reversible thermochromic materials provided in the first reversible thermochromic material and the second reversible thermochromic material has a complete color development temperature t ₁ of the reversible thermochromic material in the color-developed state and a reversible thermochromic property in the decolorized state. complete coloring temperature t ₁ of the _material, and, coloring starting temperature t ₂ of the thermochromic material of colorless state with a color start temperature t ₂ of the reversibly thermochromic material colored state are each substantially identical, and, coloring The decolorization start temperature t ₃ of the reversible thermochromic material in the colored state and the decolorization start temperature t ₃ of the reversible thermochromic material in the decolored state are substantially the same, and the complete decolorization temperature of the reversible thermochromic material in the colored state t ₄ is temperature control indicator according to any one of the complete decoloring temperature t ₄ is less than claims 2 to 4 of the thermochromic material decolored state. Each of the reversible thermochromic materials provided in the first reversible thermochromic material and the second reversible thermochromic material has a complete color development temperature t ₁ of the reversible thermochromic material in the color-developed state and a reversible thermochromic property in the decolorized state. complete coloring temperature t ₁ of the _material, and, coloring starting temperature t ₂ of the thermochromic material of colorless state with a color start temperature t ₂ of the reversibly thermochromic material colored state are each substantially identical, and, coloring The decolorization start temperature t ₃ of the reversible thermochromic material in the decolored state is smaller than the decolorization start temperature t ₃ of the reversible thermochromic material in the decolored state, or the decolorization start temperature of the reversible thermochromic material in the decolored state greater than t _3, the complete decoloring temperature t ₄ is any one of the complete decoloring temperature t ₄ is less than claims 2 to 4 of the thermochromic material decolored state of the thermochromic material colored state Temperature control indicator as described. Each of the reversible thermochromic materials provided in the first reversible thermochromic material and the second reversible thermochromic material has a decolorization starting temperature t ₃ of the reversible thermochromic material in a colored state and a reversible thermochromic material in a decolorized state. decoloring starting temperature t ₃ sexual _material, and, the complete decoloring temperature t ₄ of thermochromic material complete decoloring temperature t ₄ decolored state of the thermochromic material of the color states are each substantially the same Further, the complete coloring temperature t ₁ of the reversible thermochromic material in the colored state is smaller than the complete coloring temperature t ₁ of the reversible thermochromic material in the decolored state, and the coloring start temperature t ₂ of the reversible thermochromic material in the colored state 5. The temperature control indicator according to claim ₂ , wherein the color development start temperatures t ₂ of the reversible thermochromic material in the decolored state are substantially the same. Each of the reversible thermochromic materials provided in the first reversible thermochromic material and the second reversible thermochromic material has a decolorization starting temperature t ₃ of the reversible thermochromic material in a colored state and a reversible thermochromic material in a decolorized state. decoloring starting temperature t ₃ sexual _material, and, the complete decoloring temperature t ₄ of thermochromic material complete decoloring temperature t ₄ decolored state of the thermochromic material of the color states are each substantially the same Further, the complete coloring temperature t ₁ of the reversible thermochromic material A in the colored state is smaller than the perfect coloring temperature t ₁ of the reversible thermochromic material in the decolored state, and the coloring start temperature t of the reversible thermochromic material in the colored state is t 5. ₂ is lower than the color development start temperature t ₂ of the reversible thermochromic material in the decolored state, or higher than the color development start temperature t ₂ of the reversible thermochromic material in the decolored state. Thermal control indicator as described.   The first reversible thermochromic body is a reversible thermochromic body in which a reversible thermochromic layer containing a reversible thermochromic material is provided on a transparent support, and the second reversible thermochromic body The temperature control indicator according to any one of claims 1 to 8, which is a reversible thermochromic material comprising a reversible thermochromic layer containing a reversible thermochromic material on a support.   10. The temperature management indicator according to claim 9, wherein a non-thermochromic layer containing a non-thermochromic colorant is provided between the support of the second reversible thermochromic material and the reversible thermochromic layer.   The temperature management indicator according to any one of claims 1 to 10, wherein a first adhesive layer is provided on a surface of the first reversible thermochromic material that is in contact with the second reversible thermochromic material.   The temperature control according to any one of claims 1 to 11, wherein a second adhesive layer is provided on a surface of the second reversible thermochromic material opposite to the surface on which the first reversible thermochromic material is provided. indicator.   The support for the first reversible thermochromic material is a transparent tamper-proof member provided with an adhesive layer, which can be discriminated as being peeled off after being adhered to an adherend and then peeled off. Thermal control indicator as described.   The temperature control according to claim 9 or 10, wherein the second reversible thermochromic support is a tamper-proof member provided with an adhesive layer, which can be discriminated as being peeled off after being adhered to an adherend and then peeled off. indicator.   A method for using a temperature control indicator, comprising: providing the temperature control indicator according to any one of claims 1 to 14 on an article requiring temperature control or a storage container thereof.

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