JP2022163219A - Thermochromic printed matter and thermochromic printed matter set using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermochromic printed matter that makes it easy to manage dates and days during schedule management and is rich in convenience and a thermochromic printed matter set using the same.

SOLUTION: There is provided a thermochromic printed matter 1, such as a pocketbook, sheets for a pocketbook, a notebook, and a calendar, which is a printed matter having a thermochromic image 3 chosen from dates and/or days printed on a print medium 2, and in which the thermochromic image irreversibly changes its color from a chromatic color containing a thermochromic material to a different chromatic color. There is also provided a thermochromic printed matter set which is comprised of the thermochromic printed matter and a writing instrument including a friction body or a friction member.

SELECTED DRAWING: Figure 1

COPYRIGHT: (C)2023,JPO&INPIT

Description

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

Conventionally, there are various types of printed materials such as notebooks and calendars on which schedules are printed, which are widely used for schedule management and used for schedule management (see Patent Documents 1 and 2, for example).

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

It is an object of the present invention to provide a thermochromic printed material that facilitates management of the date and day of the week in this type of printed material.

The present invention is a printed material having 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 irreversibly changed from a color containing a thermochromic material to a color having a different color. The requirement is a thermochromic print in which the thermochromic image provided on the front surface of the print medium and the thermochromic image provided on the back surface of the print medium do not overlap each other.
Furthermore, the thermochromic material comprises (a) an electron-donating color-developing organic compound, (b) an electron-accepting compound, and (c) controlling the color reaction of (a) and (b). a reversible thermochromic microcapsule pigment encapsulating a reversible thermochromic composition comprising at least a reaction medium, wherein the microcapsule pigment exhibits a large hysteresis characteristic with respect to the color density-temperature curve, and alternates between a colored state and a colorless state. The pigment exhibits modification and has a holding temperature range in which both states can coexist in the room temperature range, and in the process of increasing the temperature from the colored state _, the pigment begins to lose color when it reaches temperature T3 _, and is higher than temperature T3. It becomes completely colorless in the temperature range of temperature _T4 or higher, and in the process of decreasing the temperature from the colorless state, it begins to color when it reaches temperature T2 _, which is lower _than temperature T3, and begins to color when it reaches temperature T1, which is _{lower than} temperature T2. It becomes completely colored in the temperature range, and exhibits hysteresis characteristics in which the colored state and the colorless state can coexist in the temperature range between the temperature T2 and the temperature T3 _, and the temperature T1 is in the range of -30 to ₁₀ ° _C . , the temperature T ₄ is in the range of 30 to 80 ° C., the temperature T ₄ is in the range of 50 to 80 ° C., the print medium is a paper print medium, and the thermochromic print is a notebook , notebook sheets, notebooks, calendars, etc.
Furthermore, a thermochromic printed matter set comprising the thermochromic printed matter and a friction member, and a thermochromic printed matter set comprising the thermochromic printed matter and a writing instrument having a friction member are required.

INDUSTRIAL APPLICABILITY The present invention can provide a highly convenient thermochromic printed matter and a thermochromic printed matter set using the thermochromic printed matter that facilitates management of dates and days of the week when performing schedule management.

1 is a front view showing an example of a thermochromic printed material of the present invention; FIG. 1 is a front view showing an embodiment of a thermochromic printed material set of the present invention; FIG. FIG. 4 is a front view showing another embodiment of the thermochromic printed material set of the present invention; 4 is a graph illustrating hysteresis characteristics 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 dates and/or days of the week is formed on a print medium such as paper, synthetic paper, or fabric.
A paper print medium is preferably used as the print medium.
The thermochromic printed material includes a notebook having pages printed with the date and day of the week on both sides, a notebook sheet used in a loose-leaf type system notebook with the date and day of the week printed on both sides, and a date and day of the week printed on both sides. Examples include notebooks and booklets printed on both sides, and calendars with dates and days of the week printed on both sides.
In addition, the printed matter may have a configuration in which the month is printed in addition to the configuration in which the date and the day of the week are printed.
Furthermore, if desired, ruled lines such as front ruled lines, back ruled lines, wave ruled lines, perforated ruled lines, horizontal ruled lines, vertical ruled lines, and frame lines may be printed and provided, and the ruled lines and frame lines are heat-discolored images and non-discolored images. may be either.

The thermochromic image is an image that irreversibly changes color from a color containing a thermochromic material to a color with a different color. Schedule management can be facilitated by changing the color of holidays such as Saturdays and Sundays.

The thermochromic materials contained in the thermochromic image include (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) the temperature at which the color reaction of both of them occurs. A microcapsule pigment is effective in which a reversible thermochromic composition containing at least three essential components of the reaction medium and decolorized by heating is encapsulated in microcapsules.
Examples of the reversible thermochromic composition include JP-B-4-17154, JP-A-7-179777, JP-A-7-33997, JP-A-8-39936, JP-A-2005-1369, etc. shows a large hysteresis characteristic (ΔH = 8 to 70 ° C) described in , and the shape of the curve plotting the change in color density due to temperature change is the opposite of the case where the temperature is increased from the lower temperature side than the discoloration temperature range. The color change follows a significantly different path when the temperature is lowered from the high temperature side of the color change temperature range, and the color development state in the low temperature range or the color disappearance state in the high temperature range can be maintained in a specific temperature range. A reversible thermochromic composition (irreversible reversible thermochromic composition) having is preferably used.

The hysteresis characteristic in the color density-temperature curve of the reversible thermochromic composition will be described.
In FIG. 4, the vertical axis represents color density, and the horizontal axis represents temperature. Changes in color density due to temperature changes progress along the arrows. Here, A is a point indicating the density at a temperature T ₄ (hereinafter referred to as a complete decoloring temperature) at which a completely decolored state is reached, and B is a temperature T ₃ at which decoloring starts (hereinafter referred to as a decoloring start temperature). C is the point indicating the concentration at the temperature T ₂ at which color development starts (hereinafter referred to as the color development start temperature), and D is the temperature T ₁ at which the color develops completely (hereinafter referred to as the complete It is a point that indicates the density at a color development temperature).
_The discoloration temperature range is the temperature range between T1 and _T4 , in which _both the colored state and the decolored state can coexist, and the temperature range between T2 and T3 _, which is a range with a large difference in color density, is It is a substantial discoloration temperature range.
Further, the length of the line segment EF is a measure of the color change contrast, and the length of the line segment HG passing through the midpoint of the line segment EF is the temperature width (hereinafter referred to as hysteresis width ΔH) indicating the degree of hysteresis. If the ΔH value is small, only one of the states before and after discoloration can exist in the room temperature range. Also, when the ΔH value is large, it becomes easy to maintain each state before and after discoloration.

Specifically, the reversible thermochromic composition having color memory has a complete coloring temperature T ₁ that can be obtained only in a freezer room, a cold region, or the like, that is, -30 to 10 ° C., preferably -30 to 0. ° C., more preferably -30 to -10 ° C., and the complete decoloring temperature T ₄ is a temperature obtained from a familiar heating body such as friction heat by a friction body, that is, 30 to 90 ° C., preferably 36 to 80 ° C., More preferably 50 to 80 ° C., still more preferably 60 to 80 ° C. By specifying the ΔH value to 40 to 60 ° C., it is effective for maintaining the color exhibited in the normal state (daily life temperature range). can be made to function.
The thermochromic material to be applied in the present invention preferably has a configuration in which the thermochromic image does not easily discolor when touched with a finger, etc., and the discolored image does not recolor to its original color at normal temperature (room temperature). is preferred.
Therefore, the temperature setting of _T1 and _T4 mentioned above is an important requirement.

Specific examples of compounds for each of the components (a), (b), and (c) are shown below.
Component (a) of the present invention, that is, an electron-donating color-developing organic compound, is a component that determines color, and is a compound that donates electrons to component (b), which is a color developer, to develop color.
Examples of the electron-donating color-developing organic compounds include phthalide compounds, fluoran compounds, stilinoquinoline compounds, diazarhodamine lactone compounds, pyridine compounds, quinazoline compounds, bisquinazoline compounds and the like. preferable.
Examples of the phthalide compounds include diphenylmethanephthalide compounds, phenylindolylphthalide compounds, indolylphthalide compounds, diphenylmethaneazaphthalide compounds, phenylindolylazaphthalide compounds, and derivatives thereof. Among them, phenylindolylazaphthalide compounds and derivatives thereof are preferred.
Fluorane compounds include, for example, aminofluorane compounds, alkoxyfluorane compounds, and derivatives thereof.
These compounds are exemplified 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-Np-tolylamino)fluorane,
3-chloro-6-cyclohexylaminofluorane,
2-methyl-6-cyclohexylaminofluorane,
2-(2-chloroamino)-6-dibutylaminofluorane,
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,
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]
etc. can be mentioned.
As the fluoranes, in addition to the above compounds having a substituent on the phenyl group forming the xanthene ring, the phenyl group having a substituent on the phenyl group forming the xanthene ring and the phenyl group forming the lactone ring also has a substituent (for example, , an alkyl group such as a methyl group, and a halogen atom such as a chloro group) and exhibiting a blue or black color.

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 for the component (a).
Examples of the electron-accepting compounds include a group of compounds having an active proton and derivatives thereof, a group of pseudo-acidic compounds (a group of compounds that are not acids but act as acids in the composition to develop the color of component (a)), electron vacancies. There are compounds selected from the group of compounds having pores, etc. Among these, compounds selected from the group of compounds having active protons are preferred.
Examples of compounds having an active proton and derivatives thereof include compounds having a phenolic hydroxyl group and metal salts thereof, carboxylic acids and metal salts thereof, preferably aromatic carboxylic acids, aliphatic carboxylic acids having 2 to 5 carbon atoms and their metal salts, acidic phosphate esters and metal salts thereof, azole compounds and derivatives thereof, 1,2,3-triazole and derivatives thereof, and among these, effective heat discoloration properties can be expressed. A compound having a phenolic hydroxyl group is preferred because it is possible to
The compounds having a phenolic hydroxyl group are broadly included from monophenol compounds to polyphenol compounds, and further include bis-type, tris-type phenols, etc., and phenol-aldehyde condensed resins. Among compounds having a phenolic hydroxyl group, those having at least two benzene rings are preferred. In addition, 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 its ester or amide group, 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. be done.

Specific examples are given below.
Phenol, o-cresol, tert-butyl catechol, 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-hydroxyphenyl)n-heptane, 1,1-bis(4-hydroxyphenyl)n-octane, 1,1-bis(4-hydroxyphenyl)n-nonane, 1 , 1-bis(4-hydroxyphenyl)n-decane, 1,1-bis(4-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 ) and butane.
A compound having a phenolic hydroxyl group can exhibit the most effective thermochromic properties, but aromatic carboxylic acids, aliphatic carboxylic acids having 2 to 5 carbon atoms, carboxylic acid metal salts, acidic phosphate esters and their It may be a compound selected from metal salts, 1,2,3-triazoles and derivatives thereof, and the like.

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

Furthermore, in order to discolor with a large hysteresis characteristic with respect to the color density-temperature curve and to provide color memory depending on temperature change, a temperature of 5 ° C. or more and less than 50 ° C. described in JP-B-4-17154 is used. Carboxylic acid ester compounds exhibiting a ΔT value (melting point - clouding point), such as carboxylic acid esters containing substituted aromatic rings in the molecule, esters of carboxylic acids containing unsubstituted aromatic rings and aliphatic alcohols 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 fatty alcohols, dibenzyl cinnamate, heptyl stearate, didecyl adipate, dilauryl adipate, dimyristyl adipate, dicetyl adipate, distearyl adipate, trilaurin, trimyristin, tristearin, dimyristin, distearin, etc. are mentioned.

Fatty acid ester compound obtained from an odd aliphatic monohydric alcohol having 9 or more carbon atoms and an even aliphatic carboxylic acid having an even number of carbon atoms, n-pentyl alcohol or n-heptyl alcohol and an even aliphatic carboxylic acid 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 myristate, n-pentyl palmitate, n-heptyl palmitate, n-nonyl palmitate, n-undecyl palmitate, n-tridecyl palmitate, n-pentadecyl palmitate, n-nonyl stearate, n-undecyl stearate, n-tridecyl stearate, n-pentadecyl stearate, n-nonyl eicosanoate, n-undelsi eicosanoate, n-tridecyl eicosanoate, n-pentadecyl eicosanoate, behenic acid n-nonyl, n-undecyl behenate, n-tridecyl behenate, n-pentadecyl behenate and the like.

As ketones, aliphatic ketones having a total carbon number of 10 or more are effective. -dodecanone, 3-dodecanone, 4-dodecanone, 5-dodecanone, 2-tridecanone, 3-tridecanone, 2-tetradecanone, 2-pentadecanone, 8-pentadecanone, 2-hexadecanone, 3-hexadecanone, 9-heptadecanone, 2-pentadecanone , 2-octadecanone, 2-nonadecanone, 10-nonadecanone, 2-eicosanone, 11-eicosanone, 2-heneicosanone, 2-docosanone, laurone, stearone and the like.
Furthermore, arylalkyl ketones having a total carbon number of 12 to 24, such as n-octadecanophenone, n-heptadecanophenone, n-hexadecanophenone, n-pentadecanophenone, and n-tetradecanophenone. nophenone, 4-n-dodecaacetophenone, n-tridecanophenone, 4-n-undecanoacetophenone, n-laurophenone, 4-n-decanoacetophenone, n-undecanophenone, 4-n-nonylacetophenone, n-decanophenone, 4-n-octylacetophenone, n-nonanophenone, 4-n-heptylacetophenone, n-octanophenone, 4-n-hexylacetophenone, 4-n-cyclohexylacetophenone, 4-tert-butylpropiophenone , n-heptaphenone, 4-n-pentylacetophenone, cyclohexylphenyl ketone, benzyl-n-butyl ketone, 4-n-butylacetophenone, n-hexanophenone, 4-isobutylacetophenone, 1-acetonaphtone, 2-acenaphthone, cyclopentylphenyl ketones and the like.

As 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, ditri 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. mentioned.

Acid amides include acetamide, propionamide, butyric acid amide, caproic acid amide, caprylic acid amide, capric acid amide, lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, and oleic acid amide. , erucamide, benzamide, caproic acid anilide, caprylic acid anilide, capric acid anilide, lauric acid anilide, myristate anilide, palmitic acid anilide, stearic acid anilide, behenic acid anilide, oleic acid anilide, erucic acid anilide, caproic acid N -methylamide, caprylic acid N-methylamide, capric acid N-methylamide, lauric acid N-methylamide, myristate N-methylamide, palmitic acid N-methylamide, stearic acid N-methylamide, behenic acid N-methylamide, oleic acid N-methylamide , erucic acid N-methylamide, lauric acid N-ethylamide, myristate N-ethylamide, palmitic acid N-ethylamide, stearic acid N-ethylamide, oleic acid N-ethylamide, lauric acid N-butylamide, myristate N-butylamide, palmitic acid acid N-butylamide, stearic acid N-butylamide, oleic acid N-butylamide, lauric acid N-octylamide, myristate N-octylamide, palmitic acid N-octylamide, stearic acid N-octylamide, oleic acid N-octylamide amide, lauric acid N-dodecylamide, myristate N-dodecylamide, palmitic acid N-dodecylamide, stearic acid N-dodecylamide, oleic acid N-dodecylamide, dilauric acid amide, dimyristic acid amide, dipalmitic acid amide , distearic amide, dioleic amide, trilauric amide, trimyristic amide, tripalmitic amide, tristearic amide, trioleic amide, succinic amide, adipic amide, glutaric amide, malonic amide, azelaine 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 acid N-ethylamide, malonic acid N-ethylamide, azelaic acid N-ethylamide, succinic acid N-butylamide, adipic acid N- Butyramide, glutaric acid N-butylamide, malonic acid N-butylamide, adipic acid N-octylamide, adipic acid N-dodecylamide and the like.

〔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。 A compound represented by the following general formula (1) can also be used as the component (c).

[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 and the other represent a hydrogen atom, n represents an integer of 0 to 2, R ₂ represents an alkyl group or alkenyl group having 4 or more carbon atoms, Y ₁ and Y ₂ represent a hydrogen atom, and have 1 to 4 carbon atoms. is an alkyl group, a methoxy group, or a halogen, and r and p are integers of 1-3. ]
Among the compounds represented by the formula (1), when R ₁ is a hydrogen atom, it is preferable because a reversible thermochromic composition having a wider hysteresis width can be obtained, and R ₁ is a hydrogen atom, and , m are more preferably 0.
Among the compounds represented by the formula (1), the compounds represented by the following general formula (2) are more preferably used.

In the formula, R represents an alkyl group or alkenyl group having 8 or more carbon atoms, preferably an alkyl group having 10 to 24 carbon atoms, more preferably an alkyl group having 12 to 22 carbon atoms.
Specific examples of the compounds include 4-benzyloxyphenylethyl octanoate, 4-benzyloxyphenylethyl nonanoate, 4-benzyloxyphenylethyl decanoate, 4-benzyloxyphenylethyl undecanoate, and dodecanoic acid. -4-benzyloxyphenylethyl, -4-benzyloxyphenylethyl tridecanoate, -4-benzyloxyphenylethyl tetradecanoate, -4-benzyloxyphenylethyl pentadecanoate, -4-benzyloxyphenylethyl hexadecanoate, heptadecanoic acid -4-benzyloxyphenylethyl and 4-benzyloxyphenylethyl octadecanoate can be exemplified.

（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。 Furthermore, a compound represented by the following general formula (3) can also be used as the component (c).

(Wherein, R represents an alkyl group or alkenyl group having 8 or more carbon atoms, m and n each represent an integer of 1 to 3, X and Y are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carbon Alkoxy groups of numbers 1 to 4, halogen.)
Specific examples of the compounds 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。 Furthermore, a compound represented by the following general formula (4) can also be used as the component (c).

(Wherein, X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, or a halogen atom, m represents an integer of 1 to 3, and n represents an integer of 1 to 20.)
Examples of the compounds include a diester of malonic acid and 2-[4-(4-chlorobenzyloxy)phenyl)]ethanol, a diester of succinic acid and 2-(4-benzyloxyphenyl)ethanol, a diester of succinic acid and 2- [4-(3-methylbenzyloxy)phenyl)]ethanol diester, glutaric acid and 2-(4-benzyloxyphenyl)ethanol diester, glutaric acid and 2-[4-(4-chlorobenzyloxy) phenyl)]ethanol, adipic acid with 2-(4-benzyloxyphenyl)ethanol, pimelic acid with 2-(4-benzyloxyphenyl)ethanol, suberic acid with 2-(4- benzyloxyphenyl)ethanol, diester of suberic acid with 2-[4-(3-methylbenzyloxy)phenyl)]ethanol, suberic acid with 2-[4-(4-chlorobenzyloxy)phenyl)] Diesters of ethanol, diesters of suberic acid and 2-[4-(2,4-dichlorobenzyloxy)phenyl)]ethanol, diesters of azelaic acid and 2-(4-benzyloxyphenyl)ethanol, sebacic acid and 2-(4-benzyloxyphenyl)ethanol diester, 1,10-decanedicarboxylic acid and 2-(4-benzyloxyphenyl)ethanol diester, 1,18-octadecanedicarboxylic acid and 2-(4-benzyl) Examples include diesters with oxyphenyl)ethanol and diesters with 1,18-octadecanedicarboxylic acid and 2-[4-(2-methylbenzyloxy)phenyl)]ethanol.

（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。 Furthermore, a compound represented by the following general formula (5) can also be used as the component (c).

(Wherein, R represents an alkyl or alkenyl group having 1 to 21 carbon atoms, and n represents an integer of 1 to 3.)
Examples of the compounds include diesters of 1,3-bis(2-hydroxyethoxy)benzene and capric acid, diesters of 1,3-bis(2-hydroxyethoxy)benzene and undecanoic acid, 1,3-bis(2 -hydroxyethoxy)benzene with lauric acid, 1,3-bis(2-hydroxyethoxy)benzene with myristic acid, 1,4-bis(hydroxymethoxy)benzene with butyric acid, 1,4 - the diester of bis(hydroxymethoxy)benzene with isovaleric acid, the diester of 1,4-bis(2-hydroxyethoxy)benzene with acetic acid, the diester of 1,4-bis(2-hydroxyethoxy)benzene with propionic acid Diesters, diesters of 1,4-bis(2-hydroxyethoxy)benzene and valeric acid, diesters of 1,4-bis(2-hydroxyethoxy)benzene and caproic acid, 1,4-bis(2-hydroxyethoxy) ) diesters of benzene and caprylic acid, diesters of 1,4-bis(2-hydroxyethoxy)benzene and capric acid, diesters of 1,4-bis(2-hydroxyethoxy)benzene and lauric acid, 1,4 -Diesters of bis(2-hydroxyethoxy)benzene and myristic acid can be exemplified.

（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。 Furthermore, a compound represented by the following general formula (6) can also be used as the component (c).

(Wherein, X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, m represents an integer of 1 to 3, and n represents 1 to 20 indicates an integer of
Examples of the compounds include 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。 Furthermore, a compound represented by the following general formula (7) can also be used as the component (c).

(Wherein, R is an alkyl group having 4 to 22 carbon atoms, a cycloalkylalkyl group, a cycloalkyl group, or an alkenyl group having 4 to 22 carbon atoms, X is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and n is 0 or 1.)
Examples of the compounds 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-biphenylacetate lauryl, 4-biphenylacetate myristyl, 4-biphenylacetate tridecyl, 4-biphenylacetate pentadecyl, 4-biphenylacetate cetyl, 4-biphenylacetate cyclopentyl, 4-biphenylacetate cyclohexylmethyl, 4-biphenylacetate hexyl , 4-biphenylacetate cyclohexylmethyl.

（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。 Furthermore, a compound represented by the following general formula (8) can also be used as the component (c).

(Wherein, R represents either an alkyl group having 3 to 18 carbon atoms or an aliphatic acyl group having 3 to 18 carbon atoms, X is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, 1 or 2 carbon atoms is either an alkoxy group or a halogen atom, Y is a hydrogen atom or a methyl group, Z is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 or 2 carbon atoms, a halogen atom indicates either.)
Examples of the compounds include phenoxyethyl 4-butoxybenzoate, phenoxyethyl 4-pentyloxybenzoate, phenoxyethyl 4-tetradecyloxybenzoate, esters of phenoxyethyl 4-hydroxybenzoate and dodecanoic acid, and phenoxyethyl vanillate. can be exemplified by the dodecyl ether of

（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。 Furthermore, a compound represented by the following general formula (9) can also be used as the component (c).

(Wherein, R represents an alkyl group having 4 to 22 carbon atoms, an alkenyl group having 4 to 22 carbon atoms, a cycloalkylalkyl group, or a cycloalkyl group; X represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, Y is a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom, and n is 0 or 1.)
Examples of the above compounds 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- benzoic acid ester of dodecyl p-hydroxybenzoate. Examples include methoxybenzoic acid esters and benzoic acid esters 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。 Furthermore, a compound represented by the following general formula (10) can also be used as the component (c).

(wherein R is an alkyl group having 3 to 18 carbon atoms, a cycloalkylalkyl group having 6 to 11 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, or an alkenyl group having 3 to 18 carbon atoms X is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a halogen atom; Y is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, methoxy group, ethoxy group, or 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。 Furthermore, 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.)
Examples of the compounds include diesters of 1,3-bis(2-hydroxyethoxy)benzene and cyclohexanecarboxylic acid, diesters of 1,4-bis(2-hydroxyethoxy)benzene and cyclohexanepropionic acid, 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。 Furthermore, a compound represented by the following general formula (12) can also 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, a cycloalkylalkyl group having 5 to 8 carbon atoms, X is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, group, methoxy group, ethoxy group, halogen atom, and n is an integer of 1 to 3.)
Examples of the compounds include a diester of 4-phenylphenol ethylene glycol ether and cyclohexanecarboxylic acid, a diester of 4-phenylphenoldiethylene glycol ether and lauric acid, a diester of 4-phenylphenoltriethylene glycol ether and cyclohexanecarboxylic acid, - diesters of phenylphenol ethylene glycol ethers with octanoic acid, diesters of 4-phenylphenol ethylene glycol ethers with nonanoic acid, diesters of 4-phenylphenol ethylene glycol ethers with decanoic acid, 4-phenylphenol ethylene glycol ethers with myristine A diester with an acid can be exemplified.

Furthermore, (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 -105732), gallic acid ester (JP-A-2003-253149), and the like.

The reversible thermochromic composition is a compatible body containing the components (a), (b), and (c) as essential components, and the ratio of each component is the concentration, color change temperature, color change form, and type of each component. Generally, the component ratio at which the desired properties are obtained is (a) component 1, (b) component 0.1 to 100, preferably 0.1 to 50, more preferably 0 .5 to 20, component (c) 5 to 200, preferably 5 to 100, more preferably 10 to 100 (all the above proportions are parts by mass).

The reversible thermochromic composition can be used as a reversible thermochromic pigment by dispersing it in a thermoplastic resin or thermosetting resin, or encapsulating it in microcapsules.
In addition, microencapsulation can be performed by known interfacial polymerization method, in situ polymerization method, in-liquid curing coating method, phase separation method from aqueous solution, phase separation method from organic solvent, melting dispersion cooling method, air suspension coating method. , spray-drying method, etc., which are appropriately selected according to the application. Furthermore, depending on the purpose, the surface of the microcapsules may be provided with a secondary resin film to impart durability, or the surface properties may be modified for practical use.
The microcapsule pigment preferably has a content/wall film ratio of 7/1 to 1/1 (mass ratio). Inclusions/wall film=6/1 to 1/1 (mass ratio) is more preferable because deterioration of clarity can be prevented.

By using the thermochromic material that changes color from colored to colorless and the non-thermochromic material in combination, a thermochromic material that changes color from colored to different colors can be obtained.
Common pigments or dyes are used as the non-thermochromic material.

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. Printing ink used for screen printing, offset printing, process printing, gravure printing, etc. A thermochromic image can be formed on a print medium by preparing and printing an inkjet ink.

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 each other.
Since the thermochromic images provided on the front and back sides do not overlap, when the thermochromic image on the front side is discolored, heat will not be transferred to the thermochromic image on the back side and discoloration will not occur, enabling accurate schedule management. can do. In addition, when the thermochromic image on the back surface is discolored, heat is not transmitted to the thermochromic image on the front surface and discoloration does not occur.

The thermochromic image can be changed from colored to colored by rubbing with a finger, applying a friction body or a heat discoloring tool.
Examples of the heating device include an electric heating discoloring device equipped with a resistance heating element, a heating discoloring device filled with warm water, etc., and the like. is preferred.
As the friction body, elastic bodies such as elastomers and plastic foams, which are highly elastic and can generate frictional heat by generating moderate friction during friction, are suitable. It may be metal or cloth.
An eraser may be used for rubbing, but since eraser scum is generated during rubbing, 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), SEBS resin (styrene-ethylene-butylene-styrene block copolymer), and the like.
By combining the thermochromic printed matter and the friction member, a thermochromic printed matter set excellent in portability can be obtained.
In addition, by using a writing instrument having a friction member, it is possible to write on printed matter, so convenience can be improved.
Examples of the location where the friction member is fixed include the tip of the cap (top), the tip of the barrel (the portion where the writing tip is not provided), and the like.
Further, a friction member may be formed by providing a small protrusion of arbitrary shape on a portion of the cap or a portion of the barrel.
The ink contained in the writing instrument may be a non-thermochromic ink, but by using an ink that can be decolored by heating, it is possible to improve convenience by enabling repeated writing.
The above-described thermochromic material can be used as the colorant contained in the ink that can be decolored by heating.
Further, the writing instrument may be a solid writing instrument such as a pencil or a crayon.
By combining the thermochromic printed matter and a writing instrument having 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.
In addition, the part in an Example is a mass part.
Example 1 (see FIG. 1)
Preparation of thermochromic printed matter (a) 4.5 parts of 2-(2-chloroanilino)-6-di-n-butylaminofluorane as component, 4,4'-(2-methylpropylidene) as component (b) ) 4.5 parts of bisphenol, 7.5 parts of 2,2-bis(4'-hydroxyphenyl)hexafluoropropane, and 50.0 parts of 4-benzyloxyphenylethyl caprate as component (c). Microcapsule pigment containing a reversible thermochromic composition (T ₁ : -20 ° C., T ₂ : -9 ° C., T ₃ : 40 ° C., T ₄ : 57 ° C., ΔH: 63 ° C., average particle size: 2 .5 μm, reversible thermochromic composition/wall film=2.6/1.0, color changes 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 using the above-described offset ink on both front and back surfaces of high-quality paper as the printing medium 2, and the ink was dried and cured to form a date (thermochromic image 3).
Note that the thermochromic images on the front surface and the back surface are formed so as not to overlap each other.
Subsequently, offset printing was carried out using a non-discoloring black ink, followed by drying and curing to form a frame line (non-discoloring image 4) to obtain a thermochromic print.

The thermochromic printed matter is initially a notebook-shaped printed matter on which a black date is formed, but the frictional heat generated by rubbing the thermochromic image on any part of the surface with a friction body turns it red. Since it can be discolored and the discolored state can be maintained at room temperature, it was useful for holiday schedule management.
In addition, since the date provided on the back surface of the discolored part does not discolor due to heat transfer when discoloring the thermochromic image on the surface, it was possible to perform accurate schedule management.

Example 2
Preparation of thermochromic printed matter set (see Fig. 2)
A thermochromic printed matter set 8 was obtained by combining the thermochromic printed matter of Example 1 and a cylindrical friction body 5 having a convex portion at one end.
The thermochromic printed material set is initially a notebook-shaped printed material on which a black date is formed, but a red color is generated by frictional heat generated by rubbing the thermochromic image at an arbitrary location on the surface with a friction body. , and the discolored state can be maintained at room temperature, which is useful for holiday schedule management.
In addition, since the date provided on the back surface of the discolored part does not discolor due to heat transfer when discoloring the thermochromic image on the surface, it was possible to perform accurate schedule management.

Example 3
Preparation of writing instruments (see Fig. 3)
(a) 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 component (b), 4,4′-(2-methylpropylidene) Microcapsule pigment encapsulating a reversible thermochromic composition having color memory consisting of 3.0 parts of bisphenol and 50.0 parts of 4-benzyloxyphenylethyl caprate as 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, blue to colorless Color change) 25.7 parts, succinoglycan (shear thinning agent) 0.2 parts, urea 5.5 parts, glycerin 7.5 parts, nonionic permeability imparting agent 0.03 parts, modified silicone A reversible thermochromic ink was prepared consisting of 0.15 part antifoaming agent, 0.1 part antifungal agent, 0.5 part lubricant, 0.5 part triethanolamine, and 59.82 parts water.
Ink (preliminarily cooled to -18 ° C or less to develop a blue color of the microcapsule pigment and then left at room temperature) is sucked and filled into a polypropylene pipe (ink storage tube) with an inner diameter of 4.4 mm. It was connected to a ball-point pen tip via a holder.
Next, a viscoelastic ink backflow preventer (liquid plug) containing polybutene as a main component was filled from the rear portion of the polypropylene pipe, and a tail plug was fitted to the rear portion of the pipe to obtain a refill. Further, the refill was incorporated into a barrel (consisting of a front barrel and a rear barrel), a cap was fitted, and then degassing was performed by centrifugation to obtain a writing instrument 6 (reversible thermochromic ballpoint pen). .
The tip of the ball-point pen is formed by pressing and deforming the vicinity of the tip of a metal pipe inward from the outer surface, and holding a stainless steel ball with a diameter of 0.38 mm at the tip of the tip, and the ball is a spring. It is urged forward by the body.
Further, an SEBS resin member having a convex curved top is attached as a friction member 7 to the end of the rear barrel.

Preparation of Thermochromic Printed Matter Set The thermochromic printed matter of Example 1 and the writing instrument 6 were combined to obtain a thermochromic printed matter set.
The thermochromic printed matter set is initially a notebook-shaped printed matter on which a black date is formed, but the frictional heat generated by rubbing the thermochromic image at any point on the surface with the friction member of the writing instrument. The discolored state can be maintained at room temperature, so it was useful for holiday schedule management.
In addition, since the date provided on the back surface of the discolored part does not discolor due to heat transfer when discoloring the thermochromic image on the surface, it was possible to perform accurate schedule management.
Furthermore, when a schedule is written using the writing instrument, and the schedule is changed, the handwriting can be erased by rubbing it with a friction member. I was able to write a schedule.

Example 4
Preparation of thermochromic printed matter (a) 4,5,6,7-tetrachloro-3-[4-(diethylamino)-2-ethoxyphenyl]-3-[1-ethyl-2-methyl-1Hindole as component -3-yl]-1(3H)-isobenzofuranone 1.5 parts, 2,2-bis(4′-hydroxyphenyl)hexafluoropropane 5.0 parts as component (b), 4,4′-( 2-methylpropylidene) bisphenol 3.0 parts, microcapsule pigment encapsulating a reversible thermochromic composition having color memory consisting of 50.0 parts of 4-benzyloxyphenylethyl caprate as 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, which changes color from blue to colorless), 5 parts of a red dye, and 65.0 parts of a linseed oil-based offset ink vehicle were uniformly dispersed and mixed to prepare a reversible thermochromic offset ink.
Offset printing was performed using the above-described offset ink on both the front and back surfaces of fine paper as a printing medium, followed by drying and curing to form days of the week (thermochromic images) to obtain thermochromic prints.
Next, offset printing was performed using a non-discoloring black ink, and drying and curing were performed to form ruled lines, dates, and months.
Note that the thermochromic images on the front surface and the back surface are formed so as not to overlap each other.

The thermochromic printed matter is initially a calendar-shaped printed matter on which purple days of the week are formed. It can be discolored, and the discolored state can be maintained at room temperature, so it was useful for schedule management of lessons.
In addition, the day of the week provided on the back of the discolored portion was not discolored by heat transfer when discoloring the thermochromic image on the surface, so accurate schedule management could be performed.

Example 5
Preparation of thermochromic printed material set The thermochromic printed material of Example 4 was combined with a friction body to obtain a thermochromic printed material set.
The thermochromic printed matter set is initially a calendar-shaped printed matter on which purple days of the week are formed. It was useful for schedule management of lessons because it can be discolored to 100 degrees and the discolored state can be maintained at room temperature.
In addition, the day of the week provided on the back of the discolored portion was not discolored by heat transfer when discoloring the thermochromic image on the surface, so accurate schedule management could be performed.

Example 6
4,5,6,7-tetrachloro-3-[4-(diethylamino)-2-ethoxyphenyl]-3-[1-ethyl-2-methyl-1Hindole-3- as component (a) yl]-1(3H)-isobenzofuranone 1.5 parts, 2,2-bis(4'-hydroxyphenyl)hexafluoropropane 5.0 parts as component (b), 4,4'-(2-methyl Propylidene) bisphenol 3.0 parts, microcapsule pigment encapsulating a reversible thermochromic composition having color memory consisting of 50.0 parts of 4-benzyloxyphenylethyl caprate as 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, blue from colorless to colorless) 25.7 parts, succinoglycan (shear thinning agent) 0.2 parts, urea 5.5 parts, glycerin 7.5 parts, nonionic permeability imparting agent 0.03 parts, A reversible thermochromic ink was prepared comprising 0.15 parts of a modified silicone antifoaming agent, 0.1 parts of an antifungal agent, 0.5 parts of a lubricant, 0.5 parts of triethanolamine and 59.82 parts of water.
Ink (preliminarily cooled to -18 ° C or less to develop a blue color of the microcapsule pigment and then left at room temperature) is sucked and filled into a polypropylene pipe (ink storage tube) with an inner diameter of 4.4 mm. It was connected to a ball-point pen tip via a holder.
Next, a viscoelastic ink backflow preventer (liquid plug) containing polybutene as a main component was filled from the rear portion of the polypropylene pipe, and a tail plug was fitted to the rear portion of the pipe to obtain a refill. Further, the refill was incorporated into a barrel (consisting of a front barrel and a rear barrel), fitted with a cap, and degassed by centrifugation to obtain a writing instrument (reversible thermochromic ballpoint pen).
The tip of the ball-point pen is formed by pressing and deforming the vicinity of the tip of a metal pipe inward from the outer surface, and holding a stainless steel ball with a diameter of 0.7 mm at the tip of the tip, and the ball is a spring. It is urged forward by the body.
Also, an SEBS resin member having a convex curved top is attached as a friction member to the end of the rear barrel.

Preparation of Thermochromic Printed Matter Set The thermochromic printed matter of Example 4 was combined with a writing instrument to obtain a thermochromic printed matter set.
The thermochromic printed matter set is initially a calendar-shaped printed matter on which purple days of the week are formed. It is possible to change the color to red by , and the discolored state can be maintained at room temperature, so it was useful for schedule management of lessons.
In addition, the day of the week provided on the back of the discolored portion was not discolored by heat transfer when discoloring the thermochromic image on the surface, so accurate schedule management could be performed.
Furthermore, when a schedule is written using the writing instrument, and the schedule is changed, the handwriting can be erased by rubbing it with a friction member. I was able to write a schedule.

Example 7
Preparation of thermochromic printed matter (a) 4.5 parts of 2-(2-chloroanilino)-6-di-n-butylaminofluorane as component, 4,4'-(2-methylpropylidene) as component (b) ) 4.5 parts of bisphenol, 7.5 parts of 2,2-bis(4'-hydroxyphenyl)hexafluoropropane, and 50.0 parts of 4-benzyloxyphenylethyl caprate as component (c). Microcapsule pigment containing a reversible thermochromic composition (T ₁ : -20 ° C., T ₂ : -9 ° C., T ₃ : 40 ° C., T ₄ : 57 ° C., ΔH: 63 ° C., average particle size: 2 .5 μm, reversible thermochromic composition/wall film=2.6/1.0, color changes 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 using the offset ink on both front and back sides of high-quality paper as a printing medium, followed by drying and curing to form dates (thermochromic images) and days of the week (thermochromic images) to obtain thermochromic prints.
Note that the thermochromic images on the front surface and the back surface are formed so as not to overlap each other.

The thermochromic printed matter is initially a printed matter used for a loose-leaf type notebook with a black date formed, but it is produced by rubbing a thermochromic image on an arbitrary part of the surface with a friction body. It can be discolored blue by frictional heat, and the discolored state can be maintained at room temperature, so it was useful for schedule management of holidays and hospital visits.
In addition, since the date provided on the back surface of the discolored part does not discolor due to heat transfer when discoloring the thermochromic image on the surface, it was possible to perform accurate schedule management.

Example 8
Preparation of Thermochromic Printed Matter Set The thermochromic printed matter of Example 7 was combined with an electric heater to obtain a thermochromic printed matter set.
The thermochromic printed matter set is initially a notebook-shaped printed matter on which a black date is formed, but the thermochromic image at any point on the surface is heated with an electric heating tool to change the color to blue. Since the discolored state can be maintained at room temperature, it was useful for schedule management of holidays and hospital visits.
In addition, since the date provided on the back surface of the discolored part does not discolor due to heat transfer when discoloring the thermochromic image on the surface, it was possible to perform accurate schedule management.

Example 9
Preparation of thermochromic printed matter (a) 4.5 parts of 2-(2-chloroanilino)-6-di-n-butylaminofluorane as component, 4,4'-(2-methylpropylidene) as component (b) ) 4.5 parts of bisphenol, 7.5 parts of 2,2-bis(4'-hydroxyphenyl)hexafluoropropane, and 50.0 parts of 4-benzyloxyphenylethyl caprate as component (c). Microcapsule pigment containing a reversible thermochromic composition (T ₁ : -20 ° C., T ₂ : -9 ° C., T ₃ : 40 ° C., T ₄ : 57 ° C., ΔH: 63 ° C., average particle size: 2 .5 μm, reversible thermochromic composition/wall film=2.6/1.0, color changes 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 using the offset ink on both sides of fine paper as a printing medium, and drying and curing was performed to form dates (thermochromic images) and days of the week (thermochromic images).
Subsequently, offset printing was carried out using a non-discoloring black ink, followed by drying and curing to form ruled lines to obtain a thermodiscoloring print.
Note that the thermochromic images on the front surface and the back surface are formed so as not to overlap each other.

The thermochromic printed material is initially printed in the form of a notebook on which dates and days of the week are formed in black. It was useful for schedule management because it was possible to change the color to red and maintain the changed color at room temperature.
In addition, the date and day of the week provided on the back of the discolored part were not discolored by heat transfer when discoloring the thermochromic image on the surface, so accurate schedule management could be performed.

Example 10
Preparation of thermochromic printed material set The thermochromic printed material of Example 9 was combined with a friction body to obtain a thermochromic printed material set.
The thermochromic printed matter set is initially a notebook-shaped printed matter on which dates and days of the week are formed in black. It was useful for schedule management because it was possible to change the color to red by , and the discolored state could be maintained at room temperature.
In addition, the date and day of the week provided on the back of the discolored part were not discolored by heat transfer when discoloring the thermochromic image on the surface, so accurate schedule management could be performed.

Example 11
4.5 parts of 2-(2-chloroanilino)-6-di-n-butylaminofluorane as component (a) and 4,4'-(2-methylpropylidene)bisphenol as component (b) .5 parts, 7.5 parts of 2,2-bis(4'-hydroxyphenyl)hexafluoropropane, and 50.0 parts of 4-benzyloxyphenylethyl caprate as component (c). Microcapsule pigment encapsulating a color-changing composition (T ₁ : -20 ° C., T ₂ : -9 ° C., T ₃ : 40 ° C., T ₄ : 57 ° C., ΔH: 63 ° C., average particle size: 2.5 μm, Reversible thermochromic composition/wall film = 2.6/1.0, color change from black to colorless)
25.7 parts, 0.2 parts of succinoglycan (shear thinning agent), 5.5 parts of urea, 7.5 parts of glycerin, 0.03 parts of nonionic permeability imparting agent, modified silicone antifoaming agent 0 A reversible thermochromic ink was prepared consisting of 0.15 parts of antifungal agent, 0.5 parts of lubricant, 0.5 parts of triethanolamine, and 59.82 parts of water.
Ink (preliminarily cooled to -18 ° C or less to develop a blue color of the microcapsule pigment and then left at room temperature) is sucked and filled into a polypropylene pipe (ink storage tube) with an inner diameter of 4.4 mm. It was connected to a ball-point pen tip via a holder.
Next, a viscoelastic ink backflow preventer (liquid plug) containing polybutene as a main component was filled from the rear portion of the polypropylene pipe, and a tail plug was fitted to the rear portion of the pipe to obtain a refill. Further, the refill was incorporated into a barrel (consisting of a front barrel and a rear barrel), fitted with a cap, and degassed by centrifugation to obtain a writing instrument (reversible thermochromic ballpoint pen).
The tip of the ball-point pen is formed by pressing and deforming the vicinity of the tip of a metal pipe inward from the outer surface, and holding a stainless steel ball with a diameter of 0.7 mm at the tip of the tip, and the ball is a spring. It is urged forward by the body.
Also, an SEBS resin member having a convex curved top is attached as a friction member to the end of the rear barrel.

Preparation of Thermochromic Printed Matter Set The thermochromic printed matter of Example 9 was combined with a writing instrument to obtain a thermochromic printed matter set.
The thermochromic printed matter set is initially a notebook-shaped printed matter on which black dates and days of the week are formed. It was useful for schedule management because it can be discolored to red by frictional heat and the discolored state can be maintained at room temperature.
In addition, the date and day of the week provided on the back of the discolored part were not discolored by heat transfer when discoloring the thermochromic image on the surface, so accurate schedule management could be performed.
Furthermore, when a schedule is written using the writing instrument, and the schedule is changed, the handwriting can be erased by rubbing it with a friction member. I was able to write a schedule.

Example 12
Preparation of thermochromic printed matter (a) 4.5 parts of 2-(2-chloroanilino)-6-di-n-butylaminofluorane as component, 4,4'-(2-methylpropylidene) as component (b) ) 4.5 parts of bisphenol, 7.5 parts of 2,2-bis(4'-hydroxyphenyl)hexafluoropropane, and 50.0 parts of 4-benzyloxyphenylethyl caprate as component (c). Microcapsule pigment containing a reversible thermochromic composition (T ₁ : -20 ° C., T ₂ : -9 ° C., T ₃ : 40 ° C., T ₄ : 57 ° C., ΔH: 63 ° C., average particle size: 2 .5 μm, reversible thermochromic composition/wall film=2.6/1.0, color changes 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.
Using the above offset ink on both the front and back sides of fine paper as a printing medium, offset printing was continuously performed three times on the same place, and dried and cured to form a date (thermochromic image) to obtain a thermochromic print.
Note that the thermochromic images on the front surface and the back surface are formed so as not to overlap each other.

The thermochromic printed matter is initially a notebook-shaped printed matter on which a black date is formed, but the frictional heat generated by rubbing the thermochromic image on any part of the surface with a friction body turns it red. Since it can be discolored and the discolored state can be maintained at room temperature, it was useful for holiday schedule management.
In addition, since the date provided on the back surface of the discolored part does not discolor due to heat transfer when discoloring the thermochromic image on the surface, it was possible to perform accurate schedule management.

Example 13
Preparation of thermochromic printed material set The thermochromic printed material of Example 12 was combined with a friction body to obtain a thermochromic printed material set.
The thermochromic printed material set is initially a notebook-shaped printed material on which a black date is formed, but a red color is generated by frictional heat generated by rubbing the thermochromic image at an arbitrary location on the surface with a friction body. , and the discolored state can be maintained at room temperature, which is useful for holiday schedule management.
In addition, since the date provided on the back surface of the discolored part does not discolor due to heat transfer when discoloring the thermochromic image on the surface, it was possible to perform accurate schedule management.

Example 14
Preparation of thermochromic printed matter set The thermochromic printed matter of Example 12 and the writing instrument of Example 3 were combined to obtain a thermochromic printed matter set.
The thermochromic printed matter set is initially a notebook-shaped printed matter on which a black date is formed, but the frictional heat generated by rubbing the thermochromic image at any point on the surface with the friction member of the writing instrument. The discolored state can be maintained at room temperature, so it was useful for holiday schedule management.
In addition, since the date provided on the back surface of the discolored part does not discolor due to heat transfer when discoloring the thermochromic image on the surface, it was possible to perform accurate schedule management.
Furthermore, when a schedule is written using the writing instrument, and the schedule is changed, the handwriting can be erased by rubbing it with a friction member. I was able to write a schedule.

Example 15
Preparation of thermochromic printed matter (a) 4.5 parts of 2-(2-chloroanilino)-6-di-n-butylaminofluorane as component, 4,4'-(2-methylpropylidene) as component (b) ) 4.5 parts of bisphenol, 7.5 parts of 2,2-bis(4'-hydroxyphenyl)hexafluoropropane, and 50.0 parts of 4-benzyloxyphenylethyl caprate as component (c). Microcapsule pigment containing a reversible thermochromic composition (T ₁ : -20 ° C., T ₂ : -9 ° C., T ₃ : 40 ° C., T ₄ : 57 ° C., ΔH: 63 ° C., average particle size: 2 .5 μm, reversible thermochromic composition/wall film=2.6/1.0, color changes from black to colorless) 27 parts, red dye 3 parts acrylic resin emulsion (solid content 45%) 60 parts, A temperature-sensitive color-memorizing liquid composition (printing ink) was prepared by uniformly dispersing in an aqueous ink vehicle comprising 1 part of a viscosity modifier, 0.2 parts of an antifoaming agent, and 8.8 parts of water.
The above printing ink was applied to both the front and back surfaces of high-quality paper as a printing medium by screen printing, followed by drying and curing to form a date (thermochromic image) to obtain a thermochromic print.
Note that the thermochromic images on the front surface and the back surface are formed so as not to overlap each other.

The thermochromic printed matter is initially a notebook-shaped printed matter on which a black date is formed, but the frictional heat generated by rubbing the thermochromic image on any part of the surface with a friction body turns it red. Since it can be discolored and the discolored state can be maintained at room temperature, it was useful for holiday schedule management.
In addition, since the date provided on the back surface of the discolored part does not discolor due to heat transfer when discoloring the thermochromic image on the surface, it was possible to perform accurate schedule management.

Example 16
Preparation of thermochromic printed material set The thermochromic printed material of Example 15 was combined with a friction body to obtain a thermochromic printed material set.
The thermochromic printed material set is initially a notebook-shaped printed material on which a black date is formed, but a red color is generated by frictional heat generated by rubbing the thermochromic image at an arbitrary location on the surface with a friction body. , and the discolored state can be maintained at room temperature, which is useful for holiday schedule management.
In addition, since the date provided on the back surface of the discolored part does not discolor due to heat transfer when discoloring the thermochromic image on the surface, it was possible to perform accurate schedule management.

Example 17
Preparation of Thermochromic Printed Matter Set The thermochromic printed matter of Example 15 and the writing instrument of Example 3 were combined to obtain a thermochromic printed matter set.
The thermochromic printed matter set is initially a notebook-shaped printed matter on which a black date is formed, but the frictional heat generated by rubbing the thermochromic image at any point on the surface with the friction member of the writing instrument. The discolored state can be maintained at room temperature, so it was useful for holiday schedule management.
In addition, since the date provided on the back surface of the discolored part does not discolor due to heat transfer when discoloring the thermochromic image on the surface, it was possible to perform accurate schedule management.
Furthermore, when a schedule is written using the writing instrument, and the schedule is changed, the handwriting can be erased by rubbing it with a friction member. I was able to write a schedule.

Example 18
Preparation of thermochromic printed matter (a) 4.5 parts of 2-(2-chloroanilino)-6-di-n-butylaminofluorane as component, 4,4'-(2-methylpropylidene) as component (b) ) 4.5 parts of bisphenol, 7.5 parts of 2,2-bis(4'-hydroxyphenyl)hexafluoropropane, and 50.0 parts of 4-benzyloxyphenylethyl caprate as component (c). Microcapsule pigment containing a reversible thermochromic composition (T ₁ : -20 ° C., T ₂ : -9 ° C., T ₃ : 40 ° C., T ₄ : 57 ° C., ΔH: 63 ° C., average particle size: 2 .5 μm, reversible thermochromic composition/wall film=2.6/1.0, color changes from black to colorless) 49 parts, red dye 5 parts, acrylic resin emulsion (solid content 40%) 44 parts and a water-based ink vehicle comprising 2 parts of an antifoaming agent to prepare a thermochromic color-memory liquid composition (printing ink).
Gravure printing was performed using the above printing ink on both the front and back surfaces of high-quality paper as a printing medium, followed by drying and curing to form a date (thermochromic image) to obtain a thermochromic print.
Note that the thermochromic images on the front surface and the back surface are formed so as not to overlap each other.

The thermochromic printed matter is initially a notebook-shaped printed matter on which a black date is formed, but the frictional heat generated by rubbing the thermochromic image on any part of the surface with a friction body turns it red. Since it can be discolored and the discolored state can be maintained at room temperature, it was useful for holiday schedule management.
In addition, since the date provided on the back surface of the discolored part does not discolor due to heat transfer when discoloring the thermochromic image on the surface, it was possible to perform accurate schedule management.

Example 19
Preparation of thermochromic printed material set The thermochromic printed material of Example 18 was combined with a friction body to obtain a thermochromic printed material set.
The thermochromic printed material set is initially a notebook-shaped printed material on which a black date is formed, but a red color is generated by frictional heat generated by rubbing the thermochromic image at an arbitrary location on the surface with a friction body. , and the discolored state can be maintained at room temperature, which is useful for holiday schedule management.
In addition, since the date provided on the back surface of the discolored part does not discolor due to heat transfer when discoloring the thermochromic image on the surface, it was possible to perform accurate schedule management.

Example 20
Preparation of Thermochromic Printed Matter Set The thermochromic printed matter of Example 18 and the writing instrument of Example 3 were combined to obtain a thermochromic printed matter set.
The thermochromic printed matter set is initially a notebook-shaped printed matter on which a black date is formed, but the frictional heat generated by rubbing the thermochromic image at any point on the surface with the friction member of the writing instrument. The discolored state can be maintained at room temperature, so it was useful for holiday schedule management.
In addition, since the date provided on the back surface of the discolored part does not discolor due to heat transfer when discoloring the thermochromic image on the surface, it was possible to perform accurate schedule management.
Furthermore, when a schedule is written using the writing instrument, and the schedule is changed, the handwriting can be erased by rubbing it with a friction member. I was able to write a schedule.

T1 complete coloring temperature T2 coloring start temperature T3 decoloring start temperature T4 complete decoloring temperature ΔH hysteresis width ₁ thermochromic printed matter ₂ print medium ₃ thermochromic image ₄ non-discoloring image 5 friction member 6 writing instrument 7 friction member 8 Thermochromic print set

Claims (8)

A printed material provided with a thermochromic image selected from a date and/or a day of the week on a print medium, wherein the thermochromic image is an image containing a thermochromic material that irreversibly undergoes a color change from a color to a different color. A thermochromic printed material characterized by: 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). A reversible thermochromic microcapsule pigment encapsulating a reversible thermochromic composition comprising at least the above, wherein the microcapsule pigment exhibits a large hysteresis characteristic with respect to the color density-temperature curve and exhibits a colored state and a colorless state. , is a pigment whose holding temperature range in which both states can coexist is in the room temperature range, and in the process of increasing the temperature from the colored state, the pigment begins to lose color when it reaches temperature T3 _, and temperature _T4 is higher than temperature _T3 . It becomes completely colorless in the above temperature range, and in the process of decreasing the temperature from the colorless state, it begins to color when it reaches temperature T2 _, which is _lower than temperature T3, and is completely colored in the temperature range below temperature T1, which is _{lower than} temperature T2. , and exhibits hysteresis characteristics in which the colored state and the colorless state can coexist in the temperature range between the temperature T ₂ and the temperature T ₃ , the temperature T ₁ is in the range of -30 to 10 ° C., and the temperature T _4. The thermochromic printed material according to claim 1, wherein 4 is in the range of 30 to 80°C. The thermochromic printed matter according to claim ₂ , wherein said temperature T4 is in the range of 50-80°C. 4. The thermochromic printed material according to any one of claims 1 to 3, wherein the print medium is a paper print medium. The thermochromic printed material according to any one of claims 1 to 4, wherein the thermochromic printed material is selected from notebooks, notebook sheets, notebooks, and calendars. A thermochromic printed matter set comprising the thermochromic printed matter according to any one of claims 1 to 5 and a friction member. A thermochromic printed matter set comprising the thermochromic printed matter according to any one of claims 1 to 5 and a writing instrument provided with a friction member. 8. A set of thermochromic printed matter according to claim 7, wherein said writing utensil contains an ink which can be decolored by heating.

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