JP2020001167A - Thermochromic printed matter and thermochromic printed matter set using the same - Google Patents

Abstract

To provide a convenient thermochromic printed matter and a thermochromic printed matter set using the same, capable of facilitating management of dates and days of the week when carrying out schedule management.SOLUTION: The thermochromic printed matter set comprises a thermochromic printed matter 1 and a friction body. The thermochromic printed matter 1 is a printed matter provided with a thermochromic image 3, selected from among the dates and/or days of the week, on both front and rear faces of a printing medium 2, in which the thermochromic image is an image that irreversibly changes color from a color containing a thermochromic material to a different color, and the thermochromic image provided on the front face and the thermochromic image provided on the rear face of the printing medium do not overlap each other.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a thermochromic print and a thermochromic print set using the same. More specifically, the present invention relates to a thermochromic print and a thermochromic print set on which thermochromic dates are printed.

  2. Description of the Related Art Conventionally, there have been various types of printed materials such as notebooks and calendars on which a schedule table is printed, widely used in schedule management, and used for schedule management (for example, see Patent Documents 1 and 2).

JP-A-11-42872 Japanese Utility Model Publication No. 7-15357

  SUMMARY OF THE INVENTION An object of the present invention is to provide a thermochromic print in which the date and the day of the week in such a print can be easily managed.

The present invention is a printed matter provided with a thermochromic image selected from a date and / or a day of the week on both sides of a print medium, wherein the thermochromic image is irreversible from a color containing a thermochromic material to a color having a different color. A thermochromic printed matter which does not overlap the thermochromic image provided on the front surface of the printing medium and the thermochromic image provided on the back surface of the printing medium is required.
Further, the thermochromic material controls (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a color-forming reaction of (a) and (b). A reversible thermochromic microcapsule pigment enclosing at least a reversible thermochromic composition comprising a reaction medium, wherein the microcapsule pigment exhibits a large hysteresis characteristic with respect to a color density-temperature curve and alternates between a colored state and a colorless state. exhibit modified, holding the temperature range where both states can coexist are pigments in the normal temperature range, the pigment is the process of temperature increase from the colored state, it begins decolorized to reach the temperature T _3, higher than the temperature T ₃ become completely colorless state at a temperature T ₄ or more temperature range, the process temperature is lowered from colorless state, begins to color to reach temperature T ₂ lower than the temperature T _3, a low temperature T ₁ of a temperature below than the temperature T ₂ In the area Become completely colored state, the temperature T ₂ and shows the hysteresis characteristic colored state and a colorless state can coexist in a temperature range between the temperature T _3, temperatures T ₁ is in the range of -30～10 ° C., a temperature the T ₄ is in the range of 30 to 80 ° C., the printing medium to be paper print medium, said schedule printed material, notebook, notebook sheets, notes, and requirements etc. be selected from the calendar.
Further, a thermochromic print set comprising the thermochromic print and a friction body, and a thermochromic print set comprising the thermochromic print and a writing implement having a friction member are required.

  ADVANTAGE OF THE INVENTION This invention can provide the thermochromic print which is easy to manage the date and the day of the week, and the thermochromic print set using the same, which makes the management of the date and the day easy.

It is a front view showing one example of a thermochromic printed matter of the present invention. It is a front view showing one example of a thermochromic printed matter set of the present invention. It is a front view showing other examples of the thermochromic print set of the present invention. It is a graph explaining the hysteresis characteristic in the color density-temperature curve of a reversible thermochromic composition.

The thermochromic printed matter is a printed matter in which a thermochromic image consisting of a date and / or a day of the week is formed on a printing medium such as paper, synthetic paper, or fabric.
As the print medium, a paper print medium is preferably used.
As the thermochromic printed matter, a date book having pages printed on both front and back, the date and day used for the loose-leaf type system notebook, a notebook sheet printed on both front and back, the date and day are front and back. Examples include notebooks and booklets printed on both sides, calendars printed with dates and days of the week on both sides.
The printed matter may have a configuration in which the date and the day of the week are printed, or a configuration in which the month is printed.
Furthermore, if desired, a ruled line such as a front ruled line, a reverse ruled line, a wave ruled line, a sewing ruled line, a horizontal ruled line, a vertical ruled line, and a frame line may be printed and provided. Any of these may be used.

  The thermochromic image is an image that irreversibly changes color from a color containing a thermochromic material to a different color from a color containing a thermochromic material. Schedule management can be facilitated by facilitating schedule management or changing colors of holidays such as Saturday and Sunday.

Examples of the thermochromic material contained in the thermochromic image include (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) determining the temperature at which a color reaction occurs between the two. A microcapsule pigment in which a reversible thermochromic composition containing at least three essential components of a reaction medium and decolored by heating is included in a microcapsule is effective.
Examples of the reversible thermochromic composition include JP-B-4-17154, JP-A-7-179777, JP-A-7-33997, JP-A-8-39936, and JP-A-2005-1369. Shows a large hysteresis characteristic (ΔH = 8 to 70 ° C.), and the shape of the curve plotting the change in the coloring density due to the temperature change is opposite to the case where the temperature is increased from a lower temperature side than the color change temperature range. Color memorization that discolors along a route that is significantly different from the case of descending from the higher temperature side than the discoloration temperature range, and can maintain the color development state in the low temperature range or the decoloration state in the high temperature range in the specific temperature range A reversible thermochromic composition having the formula (irreversible reversible thermochromic composition) is preferably used.

The hysteresis characteristics of the reversible thermochromic composition in a color density-temperature curve will be described.
In FIG. 4, the vertical axis represents color density, and the horizontal axis represents temperature. The change in color density due to the temperature change proceeds along the arrow. Here, A is a point indicating the density at a temperature T ₄ (hereinafter, referred to as a complete decoloring temperature) at which a complete decoloring state is reached, and B is a temperature T ₃ at which decoloring starts (hereinafter, a decoloring start temperature and a decoloring start temperature) C) is a point indicating the density at a temperature T ₂ at which color development starts (hereinafter, referred to as a color development start temperature), and D is a temperature T ₁ (hereinafter, complete) at which a full color development state is reached. (Referred to as a coloring temperature).
Discoloration temperature region is a temperature region between the T ₁ and T _4, both states of the colored state and the decolored state can coexist, a temperature range between T ₂ and T ₃ is a large area of the difference in color density It is a substantial discoloration temperature range.
Further, the length of the line segment EF is a scale indicating the contrast of the discoloration, and the length of the line segment HG passing through the middle point of the line segment EF is a temperature width (hereinafter, referred to as a hysteresis width ΔH) indicating a degree of hysteresis. If this ΔH value is small, only one specific state can exist in the normal temperature range between the two states before and after the color change. When the ΔH value is large, it is easy to maintain each state before and after discoloration.

The specifically as a reversible thermochromic composition having color-memory property, complete coloring temperature T ₁ of the freezing compartment, a temperature obtained only in a cold region or the like, i.e. -30～10 ° C., preferably -30 to 0 ° C., more preferably -30 to-10 ° C., and, complete decoloring temperature _{T 4} to a temperature obtained from the familiar heating body such as a friction heat by the friction body, i.e. 30 to 90 ° C., preferably 36-80 ° C., More preferably, it is specified in the range of 50 to 80 ° C, more preferably, 60 to 80 ° C, and by specifying the ΔH value in the range of 40 to 60 ° C, it is effective for maintaining the color exhibited in a normal state (daily living temperature range). Can function.
The thermochromic material applied in the present invention is preferably configured such that the thermochromic image does not easily change color by touch or the like, and the discolored image does not change color again at room temperature (room temperature). Is preferred.
Accordingly, the temperature setting of the T ₁ and T ₄ described above is an important requirement.

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-forming organic compound is a component that determines a color and is a compound that gives an electron to the component (b) as a color developer and develops a color.
Examples of the electron-donating color-forming 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. preferable.
Examples of the phthalide compound include diphenylmethane phthalide compound, phenylindolyl phthalide compound, indolyl phthalide compound, diphenylmethane azaphthalide compound, phenyl indolyl azaphthalide compound, and derivatives thereof, and the like. Especially, a phenyl indolyl azaphthalide compound and a derivative thereof are preferable.
In addition, examples of the fluoran compound include an aminofluoran compound, an alkoxyfluoran compound, and a derivative thereof.
Hereinafter, these compounds will be exemplified.
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) fluoran,
3,6-dimethoxyfluoran,
3,6-di-n-butoxyfluoran,
2-methyl-6- (N-ethyl-Np-tolylamino) fluoran,
3-chloro-6-cyclohexylaminofluoran,
2-methyl-6-cyclohexylaminofluoran,
2- (2-chloroamino) -6-dibutylaminofluoran,
2- (2-chloroanilino) -6-di-n-butylaminofluoran,
2- (3-trifluoromethylanilino) -6-diethylaminofluoran,
2- (3-trifluoromethylanilino) -6-dipentylaminofluoran,
2- (dibenzylamino) -6-diethylaminofluoran,
2- (N-methylanilino) -6- (N-ethyl-Np-tolylamino) fluoran,
1,3-dimethyl-6-diethylaminofluoran,
2-chloro-3-methyl-6-diethylaminofluoran,
2-anilino-3-methyl-6-diethylaminofluoran,
2-anilino-3-methoxy-6-diethylaminofluoran,
2-anilino-3-methyl-6-di-n-butylaminofluoran,
2-anilino-3-methoxy-6-di-n-butylaminofluoran,
2-xyridino-3-methyl-6-diethylaminofluoran,
2-anilino-3-methyl-6- (N-ethyl-N-p-tolylamino) fluoran,
1,2-benz-6-diethylaminofluoran,
1,2-benz-6- (N-ethyl-N-isobutylamino) fluoran,
1,2-benz-6- (N-ethyl-N-isoamylamino) fluoran,
2- (3-methoxy-4-dodecoxystyryl) quinoline,
Spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5,1 '(3'H) isobenzofuran] -3'-one, 2- (diethylamino) -8- (diethylamino) -4-methyl ,
Spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5,1 '(3'H) isobenzofuran] -3'-one, 2- (di-n-butylamino) -8- (di -N-butylamino) -4-methyl,
Spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5,1 '(3'H) isobenzofuran] -3'-one, 2- (di-n-butylamino) -8- (diethylamino ) -4-methyl,
Spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5,1 '(3'H) isobenzofuran] -3'-one, 2- (di-n-butylamino) -8- (N -Ethyl-Ni-amylamino) -4-methyl,
Spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5,1 '(3'H) isobenzofuran] -3'-one, 2- (dibutylamino) -8- (dipentylamino) -4 -Methyl,
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) -Isobenzofuranone,
4,5,6,7-tetrachloro-3- [4- (diethylamino) -2-ethoxyphenyl] -3- (1-pentyl-2-methyl-1H-indol-3-yl) -1 (3H) -Isobenzofuranone,
4,5,6,7-tetrachloro-3- [4- (diethylamino) -2-methylphenyl] -3- (1-ethyl-2-methyl-1H-indol-3-yl) -1 (3H) -Isobenzofuranone,
3 ', 6'-bis [phenyl (2-methylphenyl) amino] -spiro [isobenzofuran-1 (3H), 9'-[9H] xanthen] -3-one,
3 ', 6'-bis [phenyl (3-methylphenyl) amino] -spiro [isobenzofuran-1 (3H), 9'-[9H] xanthen] -3-one,
3 ', 6'-bis [phenyl (3-ethylphenyl) amino] -spiro [isobenzofuran-1 (3H), 9'-[9H] xanthen] -3-one,
2,6-bis (2'-ethyloxyphenyl) -4- (4'-dimethylaminophenyl) pyridine,
2,6-bis (2 ', 4'-diethyloxyphenyl) -4- (4'-dimethylaminophenyl) pyridine,
2- (4'-dimethylaminophenyl) -4-methoxy-quinazoline,
4,4 '-(ethylenedioxy) -bis [2- (4-diethylaminophenyl) quinazoline]
And the like.
In addition, as the fluorans, in addition to the compounds having a substituent on the phenyl group forming the xanthene ring, the phenyl groups having the substituent on the phenyl group forming the xanthene ring and the phenyl group forming the lactone ring also have a substituent (for example, , An alkyl group such as a methyl group, and a halogen atom such as a chloro group).

The component (b), that is, the electron-accepting compound, is a compound that receives electrons from the component (a) and functions as a color developer of the component (a).
Examples of the electron-accepting compound include a compound group having an active proton and a derivative thereof, a pseudo-acid compound group (not an acid, but a compound group which acts as an acid in the composition to form the component (a) to form a color), There are compounds selected from a group of compounds having pores and the like, and among these, a compound selected from a group of compounds having an active proton is preferable.
Examples of the compound having an active proton and a derivative thereof include a compound having a phenolic hydroxyl group and 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 Metal salts, acidic phosphoric acid esters and metal salts thereof, and azole compounds and derivatives thereof, 1,2,3-triazole and derivatives thereof, and among these, effective thermochromic properties are exhibited. Thus, a compound having a phenolic hydroxyl group is preferable.
The compounds having a phenolic hydroxyl group are widely included from monophenol compounds to polyphenol compounds, and further include bis-type, tris-type phenols, and phenol-aldehyde condensation resins. Among the compounds having a phenolic hydroxyl group, those having at least two benzene rings are preferred. 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, and a halogen group.
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

Specific examples are described below.
Phenol, o-cresol, tert-butylcatechol, nonylphenol, n-octylphenol, n-dodecylphenol, n-stearylphenol, p-chlorophenol, p-bromophenol, o-phenylphenol, n-butyl p-hydroxybenzoate N-octyl p-hydroxybenzoate, resorcinol, 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, 1,1-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.
The compound having a phenolic hydroxyl group can exhibit the most effective thermochromic properties. However, aromatic carboxylic acids and aliphatic carboxylic acids having 2 to 5 carbon atoms, carboxylic acid metal salts, acidic phosphoric acid esters and the like thereof It may be a compound selected from metal salts, 1,2,3-triazole and derivatives thereof, and the like.

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

  Further, in order to exhibit a large hysteresis characteristic with respect to the color density-temperature curve to change the color and to provide a color storage property depending on the temperature change, a temperature of 5 ° C. or more and less than 50 ° C. Carboxylic acid ester compounds exhibiting a ΔT value (melting point−cloud point), for example, a carboxylic acid ester containing a substituted aromatic ring in the molecule, an ester of a carboxylic acid containing an unsubstituted aromatic ring and an aliphatic alcohol having 10 or more carbon atoms A carboxylic acid ester containing a cyclohexyl group in the molecule, an ester of 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, adipine Dilauryl, dimyristyl adipate, dicetyl adipate, distearyl adipate, trilaurin, trimyristin, tristearin, dimyristin, distearate, and the like.

A fatty acid ester compound obtained from an odd aliphatic monohydric alcohol having 9 or more carbon atoms and an aliphatic carboxylic acid having an even carbon number, n-pentyl alcohol or n-heptyl alcohol, and an even aliphatic carboxylic acid having 10 to 16 carbon atoms Fatty acid ester compounds having a total of 17 to 23 carbon atoms obtained from acids are 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 listinate, 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 eicosanoate, n-undersi eicosanoate, n-tridecyl eicosanoate, n-pentadecyl eicosanoate, n-nonyl behenate, n-behenate Undecyl, n-tridecyl behenate, n-pentadecyl behenate and the like can be mentioned.

As 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, 5-undecanone, -Dodecanone, 3-dodecanone, 4-dodecanone, 5-dodecanone, 2-tridecanone, 3-tridecanone, 2-tetradecanone, 2-pentadecanone, 8-pentadecanone, 2-hexadecanone, 3-hexadecanone, 9-heptadecanone, 2-pentadecanone , 2-octadecanone, 2-nonadecanone, 10-nonadecanone, 2-eicosanone, 11-eicosanone, 2-heneicosanone, 2-docosanone, laurone, stearone, and the like.
Further, arylalkyl ketones having a total carbon number of 12 to 24, for example, n-octadecanophenone, n-heptadecanophenone, n-hexadecanophenone, n-pentadecanophenone, n-tetradecano Nophenone, 4-n-dodecaacetophenone, n-tridecanophenone, 4-n-undecanoacetophenone, n-laurophenone, 4-n-decanoacetophenone, n-undecanophenone, 4-n-nonylacetophenone, n-decanophenone, 4-n-octyl acetophenone, n-nonanophenone, 4-n-heptyl acetophenone, n-octanophenone, 4-n-hexyl acetophenone, 4-n-cyclohexyl acetophenone, 4-tert-butyl propiophenone , N-heptaphenone, 4-n-pentylacetop 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, ditriethyl 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. No.

  Examples of acid amides include acetamide, propionamide, butyric amide, caproic amide, caprylic amide, capric amide, lauric amide, myristic amide, palmitic amide, stearic amide, behenic amide, and oleic amide. , Erucamide, benzamide, caproic anilide, caprylic anilide, capric anilide, lauric anilide, myristic anilide, palmitic anilide, stearic anilide, behenic anilide, oleic anilide, erucic 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-methylamide , Behenic acid N-methylamide, oleic acid N-methylamide, erucic acid N-methylamide, lauric acid N-ethylamide, myristic acid N-ethylamide, palmitic acid N-ethylamide, stearic acid N-ethylamide, oleic acid N-ethylamide, laurin 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, N-octylamide stearate, N-octylamide oleate, N-dodecylamide laurate, N-dodecylamide myristic, N-dodecylamide palmitate, N-dodecylamide stearate, Olay Acid N-dodecylamide, dilauric amide, dimyristic amide, dipalmitic amide, distearic amide, dioleic amide, trilauric amide, trimyristic amide, tripalmitic amide, tristearic amide, trioleic acid Amide, succinamide, adipic amide, glutaric amide, malonamide, azelaic amide, maleic amide, succinic N-methylamide, adipic N-methylamide, glutaric N-methylamide, malonic 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 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、ハロゲンを示し、ｒ及びｐは１〜３の整数を示す。〕
前記式（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、更に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、更に好ましくは炭素数１２〜２２のアルキル基である。
前記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.

[Wherein, 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 represents — (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 represent a hydrogen atom and 1 to 4 carbon atoms. Represents an alkyl group, a methoxy group, or a halogen, and r and p represent an integer of 1 to 3. ]
Among the compounds represented by the formula (1), when R ₁ is a hydrogen atom, a reversible thermochromic composition having a wider hysteresis width is preferably obtained, and further, R ₁ is a hydrogen atom; , M is more preferably 0.
In addition, among the compounds represented by the formula (1), a 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 include 4-benzyloxyphenylethyl octanoate, 4-benzyloxyphenylethyl nonanoate, 4-benzyloxyphenylethyl decanoate, 4-benzyloxyphenylethyl undecanoate, dodecanoic acid -4-benzyloxyphenylethyl, 4-benzyloxyphenylethyl tridecanoate, 4-benzyloxyphenylethyl tetradecanoate, 4-benzyloxyphenylethyl pentadecanoate, 4-benzyloxyphenylethyl hexadecanoate, heptadecanoic acid Examples thereof include 4-benzyloxyphenylethyl 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、ハロゲンを示す。）
前記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。 Further, as the component (c), a compound represented by the following general formula (3) can also be used.

(Wherein, R represents an alkyl group or alkenyl group having 8 or more carbon atoms, m and n each represent an integer of 1 to 3, X and Y each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, It represents an alkoxy group of formulas 1 to 4 and halogen.)
Specific examples of the compound include 1,1-diphenylmethyl octanoate, 1,1-diphenylmethyl nonanoate, 1,1-diphenylmethyl decanoate, 1,1-diphenylmethyl undecanoate, and 1,1-dodecanoate. Diphenylmethyl, 1,1-diphenylmethyl tridecanoate, 1,1-diphenylmethyl tetradecanoate, 1,1-diphenylmethyl pentadecanoate, 1,1-diphenylmethyl hexadecanoate, 1,1-diphenylmethyl heptadecanoate, octadecanoic acid 1,1-diphenylmethyl can be exemplified.

（式中、Ｘは水素原子、炭素数１乃至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乃至３の整数を示し、ｎは１乃至２０の整数を示す。）
前記化合物としては、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 a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, or a halogen atom, m represents an integer of 1 to 3, and n represents an integer of 1 to 20.)
Examples of the compound include diesters of malonic acid and 2- [4- (4-chlorobenzyloxy) phenyl)] ethanol, diesters of succinic acid and 2- (4-benzyloxyphenyl) ethanol, and succinic acid and 2- (4-benzyloxyphenyl) ethanol. [4- (3-methylbenzyloxy) phenyl)] diester with ethanol, diester with glutaric acid and 2- (4-benzyloxyphenyl) ethanol, glutaric acid and 2- [4- (4-chlorobenzyloxy) Phenyl)] ethanol, diester of adipic acid and 2- (4-benzyloxyphenyl) ethanol, diester of pimelic acid and 2- (4-benzyloxyphenyl) ethanol, and suberic acid and 2- (4- Diester with benzyloxyphenyl) ethanol, suberic acid with 2- [4- (3-methyl Benzyloxy) phenyl)] diester with ethanol, diester of suberic acid with 2- [4- (4-chlorobenzyloxy) phenyl)] ethanol, suberic acid with 2- [4- (2,4-dichlorobenzyloxy) ) Phenyl)] diester with ethanol, diester of azelaic acid with 2- (4-benzyloxyphenyl) ethanol, diester of sebacic acid with 2- (4-benzyloxyphenyl) ethanol, 1,10-decanedicarboxylic acid Diester of 1,18-octadecanedicarboxylic acid with 2- (4-benzyloxyphenyl) ethanol, 1,18-octadecanedicarboxylic acid with 2- [4- (2-methylbenzyloxy) phenyl)] It can be exemplified ether.

（式中、Ｒは炭素数１乃至２１のアルキル基又はアルケニル基を示し、ｎは１乃至３の整数を示す。）
前記化合物としては、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。 Further, 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 alkenyl group having 1 to 21 carbon atoms, and n represents an integer of 1 to 3.)
Examples of the compound include diesters of 1,3-bis (2-hydroxyethoxy) benzene and capric acid, diesters of 1,3-bis (2-hydroxyethoxy) benzene and undecanoic acid, and 1,3-bis (2 Diesters of -hydroxyethoxy) benzene and lauric acid, diesters of 1,3-bis (2-hydroxyethoxy) benzene and myristic acid, diesters of 1,4-bis (hydroxymethoxy) benzene and butyric acid, 1,4 Diesters of bis (hydroxymethoxy) benzene and isovaleric acid, diesters of 1,4-bis (2-hydroxyethoxy) benzene and acetic acid, and diesters of 1,4-bis (2-hydroxyethoxy) benzene and propionic acid Diester, diester of 1,4-bis (2-hydroxyethoxy) benzene and valeric acid Diester of 1,4-bis (2-hydroxyethoxy) benzene and caproic acid, diester of 1,4-bis (2-hydroxyethoxy) benzene and caprylic acid, 1,4-bis (2-hydroxyethoxy) benzene And diesters of capric acid, 1,4-bis (2-hydroxyethoxy) benzene and lauric acid, and diesters of 1,4-bis (2-hydroxyethoxy) benzene and myristic acid.

（式中、Ｘは水素原子、炭素数１乃至４のアルキル基、炭素数１乃至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乃至３の整数を示し、ｎは１乃至２０の整数を示す。）
前記化合物としては、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. Represents an integer.)
As the compound, diesters of succinic acid and 2-phenoxyethanol, diesters of suberic acid and 2-phenoxyethanol, diesters of sebacic acid and 2-phenoxyethanol, diesters of 1,10-decanedicarboxylic acid and 2-phenoxyethanol, A diester of 1,18-octadecanedicarboxylic acid and 2-phenoxyethanol can be exemplified.

（式中、Ｒは炭素数４乃至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乃至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乃至４のアルキル基、炭素数１乃至４のアルコキシ基、ハロゲン原子のいずれかを示し、ｎは０又は１を示す。）
前記化合物としては、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 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 represents a hydrogen atom, an alkyl having 1 to 4 carbon atoms. Group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and n represents 0 or 1.)
Examples of the compound include decyl 4-phenylbenzoate, lauryl 4-phenylbenzoate, myristyl 4-phenylbenzoate, cyclohexylethyl 4-phenylbenzoate, octyl 4-biphenylacetate, nonyl 4-biphenylacetate, and 4-biphenylacetic acid. Decyl, 4-biphenyl acetate lauryl, 4-biphenyl acetate myristyl, 4-biphenyl acetate tridecyl, 4-biphenyl acetate pentadecyl, 4-biphenyl acetate cetyl, 4-biphenyl acetate cyclopentyl, 4-biphenyl acetate cyclohexylmethyl, 4-biphenyl acetate hexyl And cyclohexylmethyl 4-biphenylacetate.

（式中、Ｒは炭素数３乃至１８のアルキル基、炭素数３乃至１８の脂肪族アシル基のいずれかを示し、Ｘは水素原子、炭素数１乃至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、メチル基のいずれかを示し、Ｚは水素原子、炭素数１乃至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。）
前記化合物としては、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。 Further, a compound represented by the following general formula (8) can be used as the component (c).

(Wherein, R represents any of an alkyl group having 3 to 18 carbon atoms and an aliphatic acyl group having 3 to 18 carbon atoms, and X represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and 1 or 2 carbon atoms. 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. One of the following.)
Examples of the compound include phenoxyethyl 4-butoxybenzoate, phenoxyethyl 4-pentyloxybenzoate, phenoxyethyl 4-tetradecyloxybenzoate, esters of phenoxyethyl 4-hydroxybenzoate with dodecanoic acid, and phenoxyethyl vanillate. Can be exemplified.

（式中、Ｒは炭素数４乃至２２のアルキル基、炭素数４乃至２２のアルケニル基、シクロアルキルアルキル基、シクロアルキル基のいずれかを示し、Ｘは水素原子、アルキル基、アルコキシ基、ハロゲン原子のいずれかを示し、Ｙは水素原子、アルキル基、アルコキシ基、ハロゲン原子のいずれかを示し、ｎは０又は１を示す。）
前記化合物としては、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 be used as the component (c).

(Wherein, R represents any 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 atom, Y represents one of a hydrogen atom, an alkyl group, an alkoxy group, and a halogen atom, and n represents 0 or 1.)
Examples of the compound include benzoic acid ester of octyl p-hydroxybenzoate, benzoic acid ester of decyl p-hydroxybenzoate, p-methoxybenzoic acid ester of heptyl p-hydroxybenzoate, and o- Examples thereof include methoxy benzoate and benzoate of cyclohexylmethyl p-hydroxybenzoate.

（式中、（式中、Ｒは炭素数３乃至１８のアルキル基、炭素数６乃至１１のシクロアルキルアルキル基、炭素数５乃至７のシクロアルキル基、炭素数３乃至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乃至４のアルキル基、炭素数１乃至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乃至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。）
前記化合物としては、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。 Further, a compound represented by the following general formula (10) can be used as the component (c).

(Wherein, R is any one of an alkyl group having 3 to 18 carbon atoms, a cycloalkylalkyl group having 6 to 11 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, and an alkenyl group having 3 to 18 carbon atoms) X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a halogen atom, and Y represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or methoxy. Group, an ethoxy group, or a halogen atom.)
Examples of the compound include phenoxyethyl ether of nonyl p-hydroxybenzoate, phenoxyethyl ether of decyl p-hydroxybenzoate, phenoxyethyl ether of undecyl p-hydroxybenzoate, and phenoxyethyl ether of dodecyl vanillate.

（式中、Ｒは炭素数３乃至８のシクロアルキル基又は炭素数４乃至９のシクロアルキルアルキル基を示し、ｎは１乃至３の整数を示す。）
前記化合物としては、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 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.)
Examples of the compound include diesters of 1,3-bis (2-hydroxyethoxy) benzene and cyclohexanecarboxylic acid, diesters of 1,4-bis (2-hydroxyethoxy) benzene and cyclohexanepropionic acid, and 1,3-bis A diester of (2-hydroxyethoxy) benzene and cyclohexanepropionic acid can be exemplified.

（式中、Ｒは炭素数３乃至１７のアルキル基、炭素数３乃至８のシクロアルキル基、炭素数５乃至８のシクロアルキルアルキル基を示し、Ｘは水素原子、炭素数１乃至５のアルキル基、メトキシ基、エトキシ基、ハロゲン原子を示し、ｎは１乃至３の整数を示す。）
前記化合物としては、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).

(Wherein, R represents an alkyl group having 3 to 17 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a cycloalkylalkyl group having 5 to 8 carbon atoms, and X represents a hydrogen atom, an alkyl having 1 to 5 carbon atoms. A methoxy group, an ethoxy group, or a halogen atom, and n represents an integer of 1 to 3.)
Examples of the compound include a diester of 4-phenylphenol ethylene glycol ether and cyclohexanecarboxylic acid, a diester of 4-phenylphenol diethylene glycol ether and lauric acid, a diester of 4-phenylphenol triethylene glycol ether and cyclohexanecarboxylic acid. -Diesters of phenylphenol ethylene glycol ether and octanoic acid, diesters of 4-phenylphenol ethylene glycol ether and nonanoic acid, diesters of 4-phenylphenol ethylene glycol ether and decanoic acid, 4-phenylphenol ethylene glycol ether and myristin Examples include diesters with acids.

  Further, (b) a specific alkoxyphenol compound having a straight-chain 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 -105732), a reversible thermochromic microcapsule pigment containing a heat-colorable reversible thermochromic composition using gallic acid ester (Japanese Patent Application Laid-Open No. 2003-253149) or the like can also be applied.

  The reversible thermochromic composition is a compatibilizer containing the above components (a), (b), and (c) as essential components, and the ratio of each component is determined by the concentration, the color change temperature, the color change form, and the type of each component. In general, the component ratio at which desired properties can be obtained is 0.1 to 100, preferably 0.1 to 50, and more preferably 0 to 100 for component (a) and component (b). 0.5 to 20, (c) component 5 to 200, preferably 5 to 100, more preferably 10 to 100 (all of the above ratios are parts by mass).

The reversible thermochromic composition is used as a reversible thermochromic pigment by being dispersed in a thermoplastic resin or a thermosetting resin, or by being encapsulated in microcapsules.
The microencapsulation is performed by a known interfacial polymerization method, in situ polymerization method, in-liquid curing coating method, phase separation method from an aqueous solution, phase separation method from an organic solvent, melt dispersion cooling method, air suspension coating method. And a spray drying method, etc., which are appropriately selected according to the application. Furthermore, a secondary resin film may be further provided on the surface of the microcapsules according to the purpose to impart durability, or the surface characteristics may be modified for practical use.
The microcapsule pigment preferably includes inclusions / wall film in a range of 7/1 to 1/1 (mass ratio). When the ratio of the wall film is within the above range, the color density and the color density at the time of color development are improved. It is possible to prevent a decrease in sharpness, and it is more preferable that the inclusion / wall film is 6/1 to 1/1 (mass ratio).

By using the thermochromic material that changes color from colorless to colorless and the non-thermochromic material together, a thermochromic material that changes color from color to a different color can be obtained.
As the non-thermochromic material, a general pigment or dye is used.

  The thermochromic material and the non-thermochromic material are dispersed in a vehicle containing water and / or an organic solvent and, if necessary, various additives, and are used as printing inks for screen printing, offset printing, process printing, gravure printing, and the like. By preparing and printing an inkjet ink, a thermochromic image can be formed on a print medium.

The thermochromic image provided on the front surface of the print medium and the thermochromic image provided on the back surface are formed so as not to overlap with each other.
Since the thermochromic images provided on the front and back sides do not overlap, when the thermochromic image on the front surface is discolored, heat is not transmitted to the thermochromic image on the back surface and discoloration occurs, thus realizing accurate schedule management. can do. Further, when the thermochromic image on the back surface is discolored, heat is not transmitted to the thermochromic image on the front surface and the color is not changed, so that accurate schedule management can be similarly realized.

The thermochromic image can be changed from colored to colored by applying friction with a finger, a friction body, or a heating discoloring tool.
Examples of the heating tool include an application of a heating color changing tool equipped with a resistance heating element, a heating color changing tool filled with hot water, and the like.However, since it is a means capable of changing color by a simple method, a friction body is used. Is preferred.
As the friction body, an elastic body that is rich in elasticity and can generate frictional heat by generating appropriate friction at the time of friction, such as a plastic foam, is preferable, but a plastic molded body, stone, wood, It may be metal or cloth.
In addition, it is possible to perform friction by using an eraser. However, an eraser is generated at the time of friction. Therefore, the above-described friction body is preferably used.
Examples of the material of the friction body include silicone resin, SBS resin (styrene-butadiene-styrene copolymer), and SEBS resin (styrene-ethylene-butylene-styrene block copolymer).
By combining the thermochromic print and the friction body, a thermochromic print set excellent in portability can be obtained.
In addition, since writing can be performed on a printed material by using a writing instrument provided with a friction member, convenience can be improved.
The location to which the friction member is fixed may be a cap tip (top), a barrel end (a portion not provided with a writing tip), or the like.
Furthermore, a small protrusion of any shape may be provided on a part of the cap or a part of the shaft cylinder to serve as a friction member.
The ink contained in the writing instrument may be a non-thermochromic ink, but by using an ink that can be erased by heating, repeated writing is possible and the convenience can be improved.
As the colorant contained in the ink which can be decolored by heating, the above-described thermochromic material can be used.
Further, the writing implement may be a solid writing implement such as a pencil or a crayon.
By combining the thermochromic printed matter with a writing instrument provided with a friction member, a thermochromic printed matter set excellent in portability can be obtained.

Examples are shown below, but the present invention is not limited to these examples.
Parts in Examples are parts by mass.
Example 1 (see FIG. 1)
Preparation of thermochromic printed matter 4.5 parts of 2- (2-chloroanilino) -6-di-n-butylaminofluoran as component (a) and 4,4 '-(2-methylpropylidene as component (b) ) A color memory consisting of 4.5 parts of bisphenol, 7.5 parts of 2,2-bis (4'-hydroxyphenyl) hexafluoropropane and 50.0 parts of 4-benzyloxyphenylethyl caprate as a component (c). (T ₁ : −20 ° C., T ₂ : −9 ° C., T ₃ : 40 ° C., T ₄ : 57 ° C., ΔH: 63 ° C., average particle diameter: 2) 0.5 μm, reversible thermochromic composition / wall film = 2.6 / 1.0, changes color from black to colorless) 30 parts, red dye 5 parts,
A reversible thermochromic offset ink was prepared by uniformly dispersing and mixing in 65.0 parts of a linseed oil-based offset ink vehicle.
Offset printing was performed on both the front and back surfaces of high-quality paper as the print medium 2 using the offset ink, followed by drying and curing to form a date (thermochromic image 3).
Note that the thermochromic images on the front and back surfaces are formed so as not to overlap.
Next, offset printing was performed using a non-color-change black ink, and dried and cured to form a frame line (non-color-change image 4) to obtain a thermochromic print.

The thermochromic printed matter is initially a notebook-shaped printed matter in which black dates are formed, but becomes red due to frictional heat generated by rubbing a thermochromic image of an arbitrary part of the surface using a friction body. It can be discolored, and the discolored state can be maintained at room temperature, which is useful for holiday schedule management.
In addition, on the date provided on the back surface of the discolored portion, when the thermochromic image on the front surface is discolored, heat is not transmitted and discolored, so that accurate schedule management could be performed.

Example 2
Preparation of thermochromic print set (see Fig. 2)
A thermochromic print set 8 was obtained by combining the thermochromic print of Example 1 with the cylindrical friction body 5 having a convex portion at one end.
The thermochromic printed matter set is initially a notebook-shaped printed matter in which a black date is formed, but is red due to frictional heat generated by rubbing a thermochromic image of an arbitrary part of the surface using a friction body. It was useful for holiday schedule management because the discolored state could be maintained at room temperature.
In addition, on the date provided on the back surface of the discolored portion, when the thermochromic image on the front surface is discolored, heat is not transmitted and discolored, so that accurate schedule management could be performed.

Example 3
Production of writing implements (see Fig. 3)
(I) 4,5,6,7-tetrachloro-3- [4- (diethylamino) -2-ethoxyphenyl] -3- [1-ethyl-2-methyl-1Hindol-3-yl]-as a component 1.5 parts of 1 (3H) -isobenzofuranone, 5.0 parts of 2,2-bis (4′-hydroxyphenyl) hexafluoropropane as the component (b), 4,4 ′-(2-methylpropylidene) A microcapsule pigment (T ₁ : −18 ° C.) containing a reversible thermochromic composition having a color memory comprising 3.0 parts of bisphenol and 50.0 parts of 4-benzyloxyphenylethyl caprate as a component (c). , T ₂ : −9 ° C., T ₃ : 42 ° C., T ₄ : 63 ° C., average particle size: 2.5 μm, reversible thermochromic composition / wall film = 2.8 / 1.0, blue to colorless 25.7 parts, succino Lican (shear-thinning agent) 0.2 parts, urea 5.5 parts, glycerin 7.5 parts, nonionic-type penetrant 0.03 parts, modified silicone-type defoamer 0.15 parts, fungicide A reversible thermochromic ink comprising 0.1 part, 0.5 part of a lubricant, 0.5 part of triethanolamine and 59.82 parts of water was prepared.
The ink (cooled in advance to −18 ° C. or less to cause the microcapsule pigment to develop a blue color and then allowed to stand at room temperature) is suction-filled into a polypropylene pipe (ink storage tube) having an inner diameter of 4.4 mm, and is made of resin. It was connected to a ballpoint pen tip via a holder.
Next, a viscoelastic ink backflow preventer (liquid stopper) containing polybutene as a main component was filled from the rear part of the polypropylene pipe, and a tail plug was fitted to the rear part of the pipe to form a refill. Further, the refill was incorporated into a barrel (consisting of a front barrel and a rear barrel), and after fitting a cap, deaeration was performed by centrifugation to obtain a writing instrument 6 (reversible thermochromic ballpoint pen). .
In addition, the ball-point pen tip is formed by holding a stainless steel ball having a diameter of 0.38 mm at the tip of the tip formed by pressing and deforming the vicinity of the tip of the metal pipe inward from the outer surface, and the ball is a spring. The body was urged forward.
In addition, an SEBS resin member having a convex curved top as a friction member 7 is attached to the end of the rear barrel.

Preparation of thermochromic print set The thermochromic print set of Example 1 and the writing implement 6 were combined to obtain a thermochromic print set.
The thermochromic printed matter set is initially a notebook-shaped printed matter in which black dates are formed, but frictional heat generated by rubbing a thermochromic image of an arbitrary portion of the surface using a friction member of a writing instrument. Thus, the discolored state can be maintained at room temperature, which is useful for holiday schedule management.
In addition, on the date provided on the back surface of the discolored portion, when the thermochromic image on the front surface is discolored, heat is not transmitted and discolored, so that accurate schedule management could be performed.
Furthermore, when the schedule is written using the writing instrument and the schedule is changed, the handwriting can be erased by friction using a friction member, and this state can be maintained at room temperature. I was able to write a new appointment.

Example 4
Preparation of thermochromic printed matter (A) 4,5,6,7-tetrachloro-3- [4- (diethylamino) -2-ethoxyphenyl] -3- [1-ethyl-2-methyl-1H indole 1.5 parts of -2-yl] -1 (3H) -isobenzofuranone, 5.0 parts of 2,2-bis (4'-hydroxyphenyl) hexafluoropropane as component (ii), 4,4 '-( A microcapsule pigment containing 3.0 parts of 2-methylpropylidene) bisphenol and a reversible thermochromic composition having color memory comprising 50.0 parts of 4-benzyloxyphenylethyl caprate as a component (c) ( T ₁ : −18 ° C., T ₂ : −9 ° C., T ₃ : 42 ° C., T ₄ : 63 ° C., average particle size: 2.5 μm, reversible thermochromic composition / wall film = 2.8 / 1. 0, color changes from blue to colorless) 0 parts of red dye, 5 parts were uniformly dispersed and mixed in linseed oil-based offset ink vehicle 65.0 parts, was prepared a reversible thermochromic offset ink.
Offset printing was performed on the front and back surfaces of high quality paper as a printing medium using the offset ink, and the ink was dried and cured to form a day of the week (thermochromic image) to obtain a thermochromic print.
Next, offset printing was performed using a non-discolorable black ink, and the ink was dried and cured to form ruled lines, dates and months.
Note that the thermochromic images on the front and back surfaces are formed so as not to overlap.

The thermochromic printed matter is initially a calendar-shaped printed matter in which purple days of the week are formed, but turns red due to frictional heat generated by rubbing a thermochromic image of any part of the surface using a friction body. Since the discoloration can be performed and the discolored state can be maintained at room temperature, it is useful for schedule management of learning.
Further, on the day of the week provided on the back surface of the discolored portion, when the thermochromic image on the front surface is discolored, heat is not transmitted and discolored, so that accurate schedule management could be performed.

Example 5
Preparation of Thermochromic Print Set A thermochromic print set was obtained by combining the thermochromic print of Example 4 with a friction body.
The thermochromic printed matter set is initially a calendar-shaped printed matter in which purple days of the week are formed, but is red due to frictional heat generated by rubbing a thermochromic image of an arbitrary portion of the surface with a friction body. Since the discolored state can be maintained at room temperature, it was useful for schedule management of learning.
Further, on the day of the week provided on the back surface of the discolored portion, when the thermochromic image on the front surface is discolored, heat is not transmitted and discolored, so that accurate schedule management could be performed.

Example 6
Preparation of writing implement (A) 4,5,6,7-tetrachloro-3- [4- (diethylamino) -2-ethoxyphenyl] -3- [1-ethyl-2-methyl-1H indole-3- Yl] -1 (3H) -isobenzofuranone 1.5 parts, (2) component 2,2-bis (4'-hydroxyphenyl) hexafluoropropane 5.0 parts, 4,4 '-(2-methyl Microcapsule pigment (T ₁₎ containing a reversible thermochromic composition having a color memory comprising 3.0 parts of propylidene) bisphenol and 50.0 parts of 4-benzyloxyphenylethyl caprate as a component (c): _{-18 ℃, T 2: -9 ℃} , T 3: 42 ℃, T 4: 63 ℃, average particle size: 2.5 [mu] m, the reversible thermochromic composition / wall membrane = 2.8 / 1.0, blue To colorless) 25.7 0.2 parts of succinoglycan (shear-thinning agent), 5.5 parts of urea, 7.5 parts of glycerin, 0.03 part of nonionic penetrant, 0.15 part of modified silicone defoamer, A reversible thermochromic ink comprising 0.1 part of an antifungal agent, 0.5 part of a lubricant, 0.5 part of triethanolamine, and 59.82 parts of water was prepared.
The ink (cooled in advance to −18 ° C. or less to cause the microcapsule pigment to develop a blue color and then allowed to stand at room temperature) is suction-filled into a polypropylene pipe (ink storage tube) having an inner diameter of 4.4 mm, and is made of resin. It was connected to a ballpoint pen tip via a holder.
Next, a viscoelastic ink backflow preventer (liquid stopper) containing polybutene as a main component was filled from the rear part of the polypropylene pipe, and a tail plug was fitted to the rear part of the pipe to form a refill. Further, the refill was assembled in a barrel (consisting of a front barrel and a rear barrel), fitted with a cap, and then deaerated by centrifugation to obtain a writing instrument (reversible thermochromic ballpoint pen).
The ball-point pen tip is formed by holding a stainless steel ball having a diameter of 0.7 mm at the tip of a tip formed by pressing and deforming the vicinity of the tip of a metal pipe inward from the outer surface, and the ball is a spring. The body was urged forward.
Also, an SEBS resin member having a convex curved top is mounted as a friction member at the end of the rear barrel.

Preparation of Thermochromic Print Set A thermochromic print set was obtained by combining the thermochromic print of Example 4 with a writing instrument.
The thermochromic printed material set is a calendar-shaped printed material in which purple days of the week are initially formed, but frictional heat generated by rubbing a thermochromic image of an arbitrary portion of the surface using a friction member of a writing instrument. The color can be changed to red, and the discolored state can be maintained at room temperature, which is useful for schedule management of learning.
Further, on the day of the week provided on the back surface of the discolored portion, when the thermochromic image on the front surface is discolored, heat is not transmitted and discolored, so that accurate schedule management could be performed.
Furthermore, when the schedule is written using the writing instrument and the schedule is changed, the handwriting can be erased by friction using a friction member, and this state can be maintained at room temperature. I was able to write a new appointment.

Example 7
Preparation of thermochromic printed matter 4.5 parts of 2- (2-chloroanilino) -6-di-n-butylaminofluoran as component (a) and 4,4 '-(2-methylpropylidene as component (b) ) A color memory consisting of 4.5 parts of bisphenol, 7.5 parts of 2,2-bis (4'-hydroxyphenyl) hexafluoropropane and 50.0 parts of 4-benzyloxyphenylethyl caprate as a component (c). (T ₁ : −20 ° C., T ₂ : −9 ° C., T ₃ : 40 ° C., T ₄ : 57 ° C., ΔH: 63 ° C., average particle diameter: 2) 0.5 μm, reversible thermochromic composition / wall film = 2.6 / 1.0, changes color from black to colorless) 30 parts, blue dye 5 parts,
A reversible thermochromic offset ink was prepared by uniformly dispersing and mixing in 65.0 parts of a linseed oil-based offset ink vehicle.
Offset printing was performed on both sides of high-quality paper as a printing medium using the offset ink, and dried and cured to form a date (thermochromic image) and a day of the week (thermochromic image) to obtain a thermochromic print.
Note that the thermochromic images on the front and back surfaces are formed so as not to overlap.

The thermochromic printed matter is a printed matter used in a loose-leaf type system notebook in which black dates are initially formed, but is generated by rubbing a thermochromic image at an arbitrary position on the surface using a friction body. The color changed to blue by frictional heat, and the discolored state could be maintained at room temperature, which was useful for the schedule management of holidays and hospital visits.
In addition, on the date provided on the back surface of the discolored portion, when the thermochromic image on the front surface is discolored, heat is not transmitted and discolored, so that accurate schedule management could be performed.

Example 8
Preparation of Thermochromic Print Set A thermochromic print set was obtained by combining the thermochromic print of Example 7 and an electric heating tool.
The thermochromic printed matter set is initially a notebook-shaped printed matter in which black dates are formed, but the color of the thermochromic image at an arbitrary position on the surface is changed to blue by heating using an electric heating tool. It was possible to maintain the discolored state at room temperature, which was useful for holiday and outpatient schedule management.
In addition, on the date provided on the back surface of the discolored portion, when the thermochromic image on the front surface is discolored, heat is not transmitted and discolored, so that accurate schedule management could be performed.

Example 9
Preparation of thermochromic printed matter 4.5 parts of 2- (2-chloroanilino) -6-di-n-butylaminofluoran as component (a) and 4,4 '-(2-methylpropylidene as component (b) ) A color memory consisting of 4.5 parts of bisphenol, 7.5 parts of 2,2-bis (4'-hydroxyphenyl) hexafluoropropane and 50.0 parts of 4-benzyloxyphenylethyl caprate as a component (c). (T ₁ : −20 ° C., T ₂ : −9 ° C., T ₃ : 40 ° C., T ₄ : 57 ° C., ΔH: 63 ° C., average particle diameter: 2) 0.5 μm, reversible thermochromic composition / wall film = 2.6 / 1.0, changes color from black to colorless) 30 parts, red dye 5 parts,
A reversible thermochromic offset ink was prepared by uniformly dispersing and mixing in 65.0 parts of a linseed oil-based offset ink vehicle.
Offset printing was performed on the front and back surfaces of high-quality paper as a print medium using the offset ink, and dried and cured to form a date (thermochromic image) and a day of the week (thermochromic image).
Next, offset printing was performed using a non-color-change black ink, and dried and cured to form ruled lines, thereby obtaining a thermo-color-change print.
Note that the thermochromic images on the front and back surfaces are formed so as not to overlap.

The thermochromic printed matter is a notebook-shaped printed matter in which black dates and days of the week are initially formed, but due to frictional heat generated by rubbing a thermochromic image of an arbitrary part of the surface using a friction body. Since the color can be changed to red and the discolored state can be maintained at room temperature, it was useful for schedule management.
In addition, the date and the day of the week provided on the back surface of the discolored portion did not dissipate heat when the thermochromic image on the front surface was discolored, so that accurate schedule management could be performed.

Example 10
Preparation of Thermochromic Print Set A thermochromic print set was obtained by combining the thermochromic print of Example 9 with a friction body.
The thermochromic printed matter set is initially a notebook-shaped printed matter in which black dates and days of the week are formed, but frictional heat generated by rubbing a thermochromic image of an arbitrary part of the surface using a friction body. Thus, the color changed to red, and the discolored state could be maintained at room temperature, which was useful for schedule management.
In addition, the date and the day of the week provided on the back surface of the discolored portion did not dissipate heat when the thermochromic image on the front surface was discolored, so that accurate schedule management could be performed.

Example 11
Preparation of writing implement 4.5 parts of 2- (2-chloroanilino) -6-di-n-butylaminofluorane as component (a) and 4,4 '-(2-methylpropylidene) bisphenol 4 as component (b) Reversible heat having a color memory consisting of 0.5 part, 7.5 parts of 2,2-bis (4'-hydroxyphenyl) hexafluoropropane, and 50.0 parts of 4-benzyloxyphenylethyl caprate as a component (c). Microcapsule pigment containing a discoloring composition (T ₁ : −20 ° C., T ₂ : −9 ° C., T ₃ : 40 ° C., T ₄ : 57 ° C., ΔH: 63 ° C., average particle diameter: 2.5 μm, (Reversible thermochromic composition / wall film = 2.6 / 1.0, changes color from black to colorless)
25.7 parts, 0.2 part of succinoglycan (shear-thinning agent), 5.5 parts of urea, 7.5 parts of glycerin, 0.03 part of nonionic penetrant, 0.0% of modified silicone defoamer .15 parts, a fungicide 0.1 part, a lubricant 0.5 part, triethanolamine 0.5 part and water 59.82 parts were prepared.
The ink (cooled in advance to −18 ° C. or less to cause the microcapsule pigment to develop a blue color and then allowed to stand at room temperature) is suction-filled into a polypropylene pipe (ink storage tube) having an inner diameter of 4.4 mm, and is made of resin. It was connected to a ballpoint pen tip via a holder.
Next, a viscoelastic ink backflow preventer (liquid stopper) containing polybutene as a main component was filled from the rear part of the polypropylene pipe, and a tail plug was fitted to the rear part of the pipe to form a refill. Further, the refill was assembled in a barrel (consisting of a front barrel and a rear barrel), fitted with a cap, and then deaerated by centrifugation to obtain a writing instrument (reversible thermochromic ballpoint pen).
The ball-point pen tip is formed by holding a stainless steel ball having a diameter of 0.7 mm at the tip of a tip formed by pressing and deforming the vicinity of the tip of a metal pipe inward from the outer surface, and the ball is a spring. The body was urged forward.
Also, an SEBS resin member having a convex curved top is mounted as a friction member at the end of the rear barrel.

Preparation of Thermochromic Print Set A thermochromic print set was obtained by combining the thermochromic print of Example 9 with a writing instrument.
The thermochromic printed matter set is initially a notebook-shaped printed matter in which black dates and days are formed, but is generated by rubbing a thermochromic image of an arbitrary portion of the surface using a friction member of a writing implement. It could be turned red by frictional heat and the discolored state could be maintained at room temperature, which was useful for schedule management.
In addition, the date and the day of the week provided on the back surface of the discolored portion did not dissipate heat when the thermochromic image on the front surface was discolored, so that accurate schedule management could be performed.
Furthermore, when the schedule is written using the writing instrument and the schedule is changed, the handwriting can be erased by friction using a friction member, and this state can be maintained at room temperature. I was able to write a new appointment.

Example 12
Preparation of thermochromic printed matter 4.5 parts of 2- (2-chloroanilino) -6-di-n-butylaminofluoran as component (a) and 4,4 '-(2-methylpropylidene as component (b) ) A color memory consisting of 4.5 parts of bisphenol, 7.5 parts of 2,2-bis (4'-hydroxyphenyl) hexafluoropropane and 50.0 parts of 4-benzyloxyphenylethyl caprate as a component (c). (T ₁ : −20 ° C., T ₂ : −9 ° C., T ₃ : 40 ° C., T ₄ : 57 ° C., ΔH: 63 ° C., average particle diameter: 2) 0.5 μm, reversible thermochromic composition / wall film = 2.6 / 1.0, changes color from black to colorless) 30 parts, red dye 5 parts,
A reversible thermochromic offset ink was prepared by uniformly dispersing and mixing in 65.0 parts of a linseed oil-based offset ink vehicle.
Offset printing was continuously performed at the same location three times using the offset ink on both the front and back surfaces of a high-quality paper as a print medium, and dried and cured to form a date (thermochromic image) to obtain a thermochromic print.
Note that the thermochromic images on the front and back surfaces are formed so as not to overlap.

The thermochromic printed matter is initially a notebook-shaped printed matter in which black dates are formed, but becomes red due to frictional heat generated by rubbing a thermochromic image of an arbitrary part of the surface using a friction body. It can be discolored, and the discolored state can be maintained at room temperature, which is useful for holiday schedule management.
In addition, on the date provided on the back surface of the discolored portion, when the thermochromic image on the front surface is discolored, heat is not transmitted and discolored, so that accurate schedule management could be performed.

Example 13
Preparation of Thermochromic Print Set A thermochromic print set was obtained by combining the thermochromic print of Example 12 with a friction body.
The thermochromic printed matter set is initially a notebook-shaped printed matter in which a black date is formed, but is red due to frictional heat generated by rubbing a thermochromic image of an arbitrary part of the surface using a friction body. It was useful for holiday schedule management because the discolored state could be maintained at room temperature.
In addition, on the date provided on the back surface of the discolored portion, when the thermochromic image on the front surface is discolored, heat is not transmitted and discolored, so that accurate schedule management could be performed.

Example 14
Preparation of Thermochromic Print Set A thermochromic print set was obtained by combining the thermochromic print of Example 12 and the writing implement of Example 3.
The thermochromic printed matter set is initially a notebook-shaped printed matter in which black dates are formed, but frictional heat generated by rubbing a thermochromic image of an arbitrary portion of the surface using a friction member of a writing instrument. Thus, the discolored state can be maintained at room temperature, which is useful for holiday schedule management.
In addition, on the date provided on the back surface of the discolored portion, when the thermochromic image on the front surface is discolored, heat is not transmitted and discolored, so that accurate schedule management could be performed.
Furthermore, when the schedule is written using the writing instrument and the schedule is changed, the handwriting can be erased by friction using a friction member, and this state can be maintained at room temperature. I was able to write a new appointment.

Example 15
Preparation of thermochromic printed matter 4.5 parts of 2- (2-chloroanilino) -6-di-n-butylaminofluoran as component (a) and 4,4 '-(2-methylpropylidene as component (b) ) A color memory consisting of 4.5 parts of bisphenol, 7.5 parts of 2,2-bis (4'-hydroxyphenyl) hexafluoropropane and 50.0 parts of 4-benzyloxyphenylethyl caprate as a component (c). (T ₁ : −20 ° C., T ₂ : −9 ° C., T ₃ : 40 ° C., T ₄ : 57 ° C., ΔH: 63 ° C., average particle diameter: 2) 0.5 μm, 27 parts of reversible thermochromic composition / wall film = 2.6 / 1.0, changing color from black to colorless), 3 parts of red dye, 60 parts of acrylic resin emulsion (solid content: 45%), 1 part of viscosity modifier, 0 of defoamer. A thermosensitive color-changeable color memory liquid composition (printing ink) was prepared by uniformly dispersing in a water-based ink vehicle consisting of 2 parts and 8.8 parts of water.
Screen printing was performed on both the front and back surfaces of high-quality paper as a print medium using the printing ink, and dried and cured to form a date (thermochromic image) to obtain a thermochromic print.
Note that the thermochromic images on the front and back surfaces are formed so as not to overlap.

The thermochromic printed matter is initially a notebook-shaped printed matter in which black dates are formed, but becomes red due to frictional heat generated by rubbing a thermochromic image of an arbitrary part of the surface using a friction body. It can be discolored, and the discolored state can be maintained at room temperature, which is useful for holiday schedule management.
In addition, on the date provided on the back surface of the discolored portion, when the thermochromic image on the front surface is discolored, heat is not transmitted and discolored, so that accurate schedule management could be performed.

Example 16
Preparation of Thermochromic Print Set A thermochromic print set was obtained by combining the thermochromic print of Example 15 with a friction body.
The thermochromic printed matter set is initially a notebook-shaped printed matter in which a black date is formed, but is red due to frictional heat generated by rubbing a thermochromic image of an arbitrary part of the surface using a friction body. It was useful for holiday schedule management because the discolored state could be maintained at room temperature.
In addition, on the date provided on the back surface of the discolored portion, when the thermochromic image on the front surface is discolored, heat is not transmitted and discolored, so that accurate schedule management could be performed.

Example 17
Preparation of Thermochromic Print Set A thermochromic print set was obtained by combining the thermochromic print of Example 15 with the writing implement of Example 3.
The thermochromic printed matter set is initially a notebook-shaped printed matter in which black dates are formed, but frictional heat generated by rubbing a thermochromic image of an arbitrary portion of the surface using a friction member of a writing instrument. Thus, the discolored state can be maintained at room temperature, which is useful for holiday schedule management.
In addition, on the date provided on the back surface of the discolored portion, when the thermochromic image on the front surface is discolored, heat is not transmitted and discolored, so that accurate schedule management could be performed.
Furthermore, when the schedule is written using the writing instrument and the schedule is changed, the handwriting can be erased by friction using a friction member, and this state can be maintained at room temperature. I was able to write a new appointment.

Example 18
Preparation of thermochromic printed matter 4.5 parts of 2- (2-chloroanilino) -6-di-n-butylaminofluoran as component (a) and 4,4 '-(2-methylpropylidene as component (b) ) A color memory consisting of 4.5 parts of bisphenol, 7.5 parts of 2,2-bis (4'-hydroxyphenyl) hexafluoropropane and 50.0 parts of 4-benzyloxyphenylethyl caprate as a component (c). (T ₁ : −20 ° C., T ₂ : −9 ° C., T ₃ : 40 ° C., T ₄ : 57 ° C., ΔH: 63 ° C., average particle diameter: 2) 0.5 μm, reversible thermochromic composition / wall film = 2.6 / 1.0, color change from black to colorless) 49 parts, red dye 5 parts, acrylic resin emulsion (solid content 40%) 44 parts , An aqueous defoamer comprising 2 parts of an antifoam A thermochromic color-memory liquid composition (printing ink) was prepared by uniformly dispersing the composition in a vehicle.
Gravure printing was performed on the front and back surfaces of high-quality paper as a print medium using the printing ink described above, followed by drying and curing to form a date (thermochromic image) to obtain a thermochromic print.
Note that the thermochromic images on the front and back surfaces are formed so as not to overlap.

The thermochromic printed matter is initially a notebook-shaped printed matter in which black dates are formed, but becomes red due to frictional heat generated by rubbing a thermochromic image of an arbitrary part of the surface using a friction body. It can be discolored, and the discolored state can be maintained at room temperature, which is useful for holiday schedule management.
In addition, on the date provided on the back surface of the discolored portion, when the thermochromic image on the front surface is discolored, heat is not transmitted and discolored, so that accurate schedule management could be performed.

Example 19
Preparation of Thermochromic Print Set A thermochromic print set was obtained by combining the thermochromic print of Example 18 with a friction body.
The thermochromic printed matter set is initially a notebook-shaped printed matter in which a black date is formed, but is red due to frictional heat generated by rubbing a thermochromic image of an arbitrary part of the surface using a friction body. It was useful for holiday schedule management because the discolored state could be maintained at room temperature.
In addition, on the date provided on the back surface of the discolored portion, when the thermochromic image on the front surface is discolored, heat is not transmitted and discolored, so that accurate schedule management could be performed.

Example 20
Preparation of Thermochromic Print Set The thermochromic print of Example 18 and the writing implement of Example 3 were combined to obtain a thermochromic print set.
The thermochromic printed matter set is initially a notebook-shaped printed matter in which black dates are formed, but frictional heat generated by rubbing a thermochromic image of an arbitrary portion of the surface using a friction member of a writing instrument. Thus, the discolored state can be maintained at room temperature, which is useful for holiday schedule management.
In addition, on the date provided on the back surface of the discolored portion, when the thermochromic image on the front surface is discolored, heat is not transmitted and discolored, so that accurate schedule management could be performed.
Furthermore, when the schedule is written using the writing instrument and the schedule is changed, the handwriting can be erased by friction using a friction member, and this state can be maintained at room temperature. I was able to write a new appointment.

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 1 Thermochromic print 2 Print medium 3 Thermal color change image 4 Non-color change image 5 Friction body 6 Writing implement 7 Friction member 8 Thermochromic print set

Claims (7)

  A printed matter provided with a thermochromic image selected from the date and / or day of the week on both sides of a print medium, wherein the thermochromic image irreversibly changes color from a color containing a thermochromic material to a different color. A thermochromic image provided on the front surface of the print medium and a thermochromic image provided on the back surface of the print medium do not overlap with each other. The thermochromic material comprises (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reaction medium for controlling the color reaction of (a) and (b). Is a reversible thermochromic microcapsule pigment encapsulating at least a reversible thermochromic composition, wherein the microcapsule pigment exhibits a large hysteresis characteristic with respect to a color density-temperature curve and exhibits a tautomerism between a colored state and a colorless state. , the holding temperature range both states can coexist are pigments in the normal temperature range, the pigment in the process of temperature increase from the colored state, begins decolorized to reach the temperature T _3, the temperature T ₃ higher than the temperature T ₄ become completely colorless state by the above temperature range, the process temperature is lowered from colorless state, begins to color to reach temperature T ₂ lower than the temperature T _3, completely at low temperature T ₁ of the following temperature range than temperature T ₂ Wear on Becomes a color state, the temperature T ₂ and shows the hysteresis characteristic colored state and a colorless state can coexist in a temperature range between the temperature T _3, temperatures T ₁ is in the range of -30～10 ° C., a temperature T ₄ The thermochromic print according to claim 1, wherein the temperature is in the range of 30 to 80C.   The thermochromic print according to claim 1, wherein the print medium is a paper print medium.   The thermochromic print according to any one of claims 1 to 3, wherein the schedule print is selected from a notebook, a notebook sheet, a notebook, and a calendar.   A thermochromic print set comprising the thermochromic print according to any one of claims 1 to 4 and a friction body.   A thermochromic print set comprising the thermochromic print according to any one of claims 1 to 4 and a writing implement provided with a friction member.   7. The thermochromic print set according to claim 6, wherein the writing implement contains an ink that can be erased by heating.

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