JP7280756B2 - Thermochromic ink composition for stamp and stamp using the same - Google Patents

Description

The present invention relates to a thermochromic ink composition for stamps and a stamp using the same. More specifically, the present invention relates to a thermochromic ink composition for stamps, which gives a stamp impression exhibiting various color changes with temperature change, and a stamp using the same.

Conventionally, there have been disclosed several thermochromic ink compositions for stamps in which a stamp impression (printed image) imprinted on a paper surface is erasable by frictional heat (see, for example, Patent Documents 1 and 2).
Frictional heat erasable stamps, which are commercially available by applying the above technology, contain ink whose decoloring temperature is set to about 60°C, and frictional heat is generated by rubbing the imprint with the attached erasing member. By heating to 60° C. or higher, the imprint becomes transparent and decolored.

JP 2015-209444 A JP 2018-141059 A

The ink composition can be visually decolored by heating the imprint when the imprint is erroneously stamped or when the imprint is no longer needed. It is very convenient because it makes it easy to make corrections that could not be made with conventional methods.
The present invention provides a two-stage discoloration ink that exhibits a color change from coloring (1) to coloring (2) and further to decoloring according to a change in temperature, and is unexpected and rich in decorativeness. A stamping heat with high commercial value, in which the residual color after decoloring is difficult to see, a clear imprint can be seen even when re-stamping on the decolored part, and the hue of coloring (2) is clearly visible. A discoloration ink composition and a stamp using the same are provided.

The present invention provides a thermochromic ink composition for stamps containing two or more colorants that become decolorized by heating, wherein the colorants have different hues and two types of decolorization temperatures T. It consists of either _A or TB (TA _< TB ₎ , and _the hue of the ink applied to JIS P3201 writing paper A is different from the hue immediately after being heated to TA or more, and is heated to TB _or more _. The residual color immediately after is 7 or less in color difference ΔE ^* _ab from writing paper A,
Furthermore, the coloring agent is composed of a low-temperature erasing coloring agent group A having a erasing temperature T _A and a high temperature erasing coloring agent group B having a erasing temperature T _B , and the low temperature erasing coloring agent group A A requirement is that the residual color ΔE ^* _ab (A) on the paper surface when decolored by itself is 10 or less .
Further, the high-temperature erasable coloring agent group B has a residual color ΔE ^* _ab (B) on the paper surface when the high-temperature erasable coloring agent group B alone is 10 or less; The color erasing temperature difference between the side coloring agent group A and the high temperature erasing coloring agent group B is 5° C. or more, and the content of the low temperature erasing coloring agent group A is 70% by mass or less in the total amount of the coloring agents. is required.
Further, the coloring agent is added in a range of 10 to 40% by mass based on the total amount of the ink composition, and the coloring agent comprises (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, ( C) The reversible thermochromic pigment is a reversible thermochromic pigment in which a reversible thermochromic composition comprising a reaction medium for controlling the color reaction of the above (a) and (b) is encapsulated in microcapsules.
Further, a stamp containing the thermochromic ink composition for stamp according to any one of the above is provided, and a friction member that discolors the imprint of the stamp by frictional heat is provided, and the friction member is from two kinds. Therefore, it is required that one side generates frictional heat in the range of T _A to T _B and the other side generates frictional heat equal to or higher than T _B due to friction with the paper surface.

The present invention provides a two-stage color-changing ink that changes color from coloring (1) to coloring (2) and then to decoloring, which is unexpected and rich in decorativeness. By paying attention, it is difficult to visually recognize the residual color when the stamp is erased, a clear impression can be visually recognized when re-stamping the erased part, and the hue when it changes to coloring (2) can be clearly obtained. A highly valuable thermochromic ink composition for stamps and a stamp using the same can be provided.

4 is a graph illustrating hysteresis characteristics in the color density-temperature curve of a reversible thermochromic composition. 1 is a graph illustrating hysteresis characteristics in a color density-temperature curve of a reversible thermochromic composition having color memory properties. Color concentration-temperature curves of low temperature erasable colorant group A and high temperature erasable colorant group B contained in the thermochromic ink composition for stamps of one example of the present invention (A: thin line, B: thick line ). Color concentration-temperature curves of low-temperature erasable colorant group A and high-temperature erasable colorant group B contained in the thermochromic ink composition for stamps of other examples of the present invention (A: thin line, B : thick line). Color concentration-temperature curves (A: thin line, B: thick line). Color concentration-temperature curves (A: thin line, B: thick line). BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a vertical cross-sectional explanatory view of an example of a stamp incorporating the thermochromic ink composition for stamps of the present invention.

Coloring agents that become decolorized by heating are those that change from a colored state to a decolored state (transparency or discoloration) by rubbing with a friction body or applying heat from an electric heat source. , can be applied selectively regardless of irreversibility.
Examples of the coloring agent include reversible thermochromic compositions disclosed in JP-A-2012-219160 and JP-A-2014-5422, and JP-A-2010-229332 and the like. Thermochromic compositions of the irreversible type are applicable.
In particular, it is preferable that the imprint of the stamp ink can be changed stably for a long period of time by encapsulating the thermochromic composition in microcapsules without causing a change in composition. As the thermochromic composition encapsulated in the microcapsules, from the viewpoint of repeated usability, accuracy of temperature change, etc., (a) an electron-donating color-developing organic compound, (b) an electron-accepting compound, (c) A reversible thermochromic composition comprising a reaction medium that determines the temperature at which the two color reactions occur is preferred.

The reversible thermochromic composition changes color before and after a predetermined temperature (color change point) as a boundary, and changes color in a temperature range above the high temperature color change point and in a color development state in a temperature range below the low temperature color change point. only one of the two states exists in a specific temperature range, and the other state is maintained as long as the heat or cold required to develop that state is applied However, it has a characteristic of a relatively small hysteresis width (ΔH) that returns to the original state when the application of heat or cold heat is stopped (see FIG. 1).
In addition, it shows a large hysteresis characteristic, that is, the shape of the curve plotting the change in color density due to temperature change decreases from the high temperature side of the discoloration temperature range, contrary to the case where the temperature is increased from the low temperature side from the discoloration temperature range. The color changes along a path that is significantly different from that when the color is changed, and the color develops in a low temperature range below the complete color development temperature (t ₁ ), or the color disappears in a high temperature range above the complete color disappearance temperature (t ₄ ). , Reversible heat of a heat-discoloring type (discoloring by heating and developing color by cooling) having color memory property in a specific temperature range [temperature range between t ₂ and t ₃ (substantially two-phase retention temperature range)] Color changing compositions can also be applied (see Figure 2).
In the present invention, "at the time of thermal erasure of handwriting" when the reversible thermochromic composition is used refers to a state of reaching the complete erasure temperature (t ₄ ) or higher.

The components (a), (b), and (c) are specifically described below.
Component (a), ie, an electron-donating color-forming organic compound, is a component that determines color, and is a compound that provides electrons to component (b), which is a color developer, to develop color.
Examples of the electron-donating color-forming organic compounds include phthalide compounds, fluorane compounds, stilinoquinoline compounds, pyridine compounds, quinazoline compounds, bisquinazoline compounds, and diazarhodamine lactone compounds. are pyridine compounds, quinazoline compounds, bisquinazoline compounds and diazarhodamine lactone compounds, with pyridine compounds being preferred.
As the pyridine-based compound,
4-(4′-methylbenzylaminophenyl)-pyridine,
2,6-diphenyl-4-(4′-dimethylaminophenyl)-pyridine,
2,6-diphenyl-4-(4′-N-phenyl-N-methylaminophenyl)-pyridine,
2,6-bis(2′-methyloxyphenyl)-4-(4′-dimethylaminophenyl)-pyridine,
2,6-bis(2′-ethyloxyphenyl)-4-(4′-dimethylaminophenyl)-pyridine,
2,6-bis(2′-propyloxyphenyl)-4-(4′-dimethylaminophenyl)-pyridine,
2,6-bis(2′-butyloxyphenyl)-4-(4′-dimethylaminophenyl)-pyridine,
2,6-bis(2′-pentyloxyphenyl)-4-(4′-dimethylaminophenyl)-pyridine,
2,6-bis(2'-hexyloxyphenyl)-4-(4'-dimethylaminophenyl)-pyridine,
2,6-bis(2'-heptyloxyphenyl)-4-(4'-dimethylaminophenyl)-pyridine,
2,6-bis(2'-octyloxyphenyl)-4-(4'-dimethylaminophenyl)-pyridine,
2,6-bis(2′-methyloxyphenyl)-4-(4′-diethylaminophenyl)-pyridine,
2,6-bis(2'-ethyloxyphenyl)-4-(4'-diethylaminophenyl)-pyridine,
2,6-bis(2′-propyloxyphenyl)-4-(4′-diethylaminophenyl)-pyridine,
2,6-bis(2'-butyloxyphenyl)-4-(4'-diethylaminophenyl)-pyridine,
2,6-bis(2'-pentyloxyphenyl)-4-(4'-diethylaminophenyl)-pyridine,
2,6-bis(2'-hexyloxyphenyl)-4-(4'-diethylaminophenyl)-pyridine,
2,6-bis(2'-heptyloxyphenyl)-4-(4'-diethylaminophenyl)-pyridine,
2,6-bis(2'-octyloxyphenyl)-4-(4'-diethylaminophenyl)-pyridine,
2,6-bis(2′-methyloxyphenyl)-4-(4′-N-phenyl-N-methylaminophenyl)-pyridine,
2,6-bis(2′-ethyloxyphenyl)-4-(4′-N-phenyl-N-methylaminophenyl)-pyridine,
2,6-bis(2′-butyloxyphenyl)-4-(4′-N-phenyl-N-methylaminophenyl)-pyridine,
2,6-bis(2'-hexyloxyphenyl)-4-(4'-N-phenyl-N-methylaminophenyl)-pyridine,
2,6-bis(2'-octyloxyphenyl)-4-(4'-N-phenyl-N-methylaminophenyl)-pyridine,
2,6-bis(2′-methyloxyphenyl)-4-(4′-N-chloroethyl-N-methylaminophenyl)-pyridine,
2,6-bis(2′-ethyloxyphenyl)-4-(4′-N-chloroethyl-N-methylaminophenyl)-pyridine,
2,6-bis(2′-butyloxyphenyl)-4-(4′-N-chloroethyl-N-methylaminophenyl)-pyridine,
2,6-bis(2'-hexyloxyphenyl)-4-(4'-N-chloroethyl-N-methylaminophenyl)-pyridine,
2,6-bis(2'-octyloxyphenyl)-4-(4'-N-chloroethyl-N-methylaminophenyl)-pyridine,
2,6-bis(2′-methyloxyphenyl)-4-(4′-N-ethyloxyethyl-N-methylaminophenyl)-pyridine,
2,6-bis(2′-ethyloxyphenyl)-4-(4′-N-ethyloxyethyl-N-methylaminophenyl)-pyridine,
2,6-bis(2′-butyloxyphenyl)-4-(4′-N-ethyloxyethyl-N-methylaminophenyl)-pyridine,
2,6-bis(2'-hexyloxyphenyl)-4-(4'-N-ethyloxyethyl-N-methylaminophenyl)-pyridine,
2,6-bis(2'-octyloxyphenyl)-4-(4'-N-ethyloxyethyl-N-methylaminophenyl)-pyridine,
2,6-bis(2'-methyloxyphenyl)-4-(4'-dibutylaminophenyl)-pyridine,
2,6-bis(2'-ethyloxyphenyl)-4-(4'-dibutylaminophenyl)-pyridine,
2,6-bis(2'-butyloxyphenyl)-4-(4'-dibutylaminophenyl)-pyridine,
2,6-bis(2'-hexyloxyphenyl)-4-(4'-dibutylaminophenyl)-pyridine,
2,6-bis(2'-octyloxyphenyl)-4-(4'-dibutylaminophenyl)-pyridine,
2,6-bis(2′-methyloxyphenyl)-4-(4′-N-isobutyl-N-ethylaminophenyl)-pyridine,
2,6-bis(2′-ethyloxyphenyl)-4-(4′-N-isobutyl-N-ethylaminophenyl)-pyridine,
2,6-bis(2′-propyloxyphenyl)-4-(4′-N-isobutyl-N-ethylaminophenyl)-pyridine,
2,6-bis(2′-butyloxyphenyl)-4-(4′-N-isobutyl-N-ethylaminophenyl)-pyridine,
2,6-bis(2′-pentyloxyphenyl)-4-(4′-N-isobutyl-N-ethylaminophenyl)-pyridine,
2,6-bis(2′-hexyloxyphenyl)-4-(4′-N-isobutyl-N-ethylaminophenyl)-pyridine,
2,6-bis(2'-heptyloxyphenyl)-4-(4'-N-isobutyl-N-ethylaminophenyl)-pyridine,
2,6-bis(2'-octyloxyphenyl)-4-(4'-N-isobutyl-N-ethylaminophenyl)-pyridine,
2,6-bis(2′-nonyloxyphenyl)-4-(4′-N-isobutyl-N-ethylaminophenyl)-pyridine,
2,6-bis(4′-methyloxyphenyl)-4-(4′-dimethylaminophenyl)-pyridine,
2,6-dimethyl-3,5-biscarboethoxy-4-(4'-dimethylaminophenyl)-pyridine,
2-(2'-octyloxyphenyl)-4-(4'-dimethylaminophenyl)-6-phenyl-pyridine,
2,6-diethyloxy-4-(4'-diethylaminophenyl)-pyridine 4-(4-methyloxyphenyl)-2,6-bis(4-dimethylaminophenyl)-pyridine,
4-phenyl-2,6-bis(4-dimethylaminophenyl)-pyridine,
4-(4-methylphenyl)-2,6-bis(4-dimethylaminophenyl)-pyridine,
2,4,6-tris(4-dimethylaminophenyl)-pyridine,
4-(2-chloro-4-dimethylaminophenyl)-2,6-bis(4-dimethylaminophenyl)-pyridine,
4-(3-nitrophenyl)-2,6-bis(4-dimethylaminophenyl)-pyridine,
4-(4-methyloxycarbonylphenyl)-2,6-bis(4-dimethylaminophenyl)-pyridine,
4-(4-dimethylaminophenyl)-2,6-bis(2-thienyl)-pyridine,
4-(4-dimethylaminophenyl)-2,6-bis(2-furyl)-pyridine,
4-(2-chloro-4-dimethylaminophenyl)-2,6-bis(2-thienyl)-pyridine,
4-[4-(1-piperidinyl)phenyl]-2,6-bis(4-dimethylaminophenyl)-pyridine,
4-(4-morpholinophenyl)-2,6-bis(4-dimethylaminophenyl)-pyridine,
4-(9-julolidinyl)-2,6-bis(4-dimethylaminophenyl)-pyridine,
4-(4-methylphenyl)-2,6-bis(4-dimethylaminophenyl)-pyridine,
4-(4-methyloxyphenyl)-2,6-bis(4-dimethylaminophenyl)-pyridine,
4-(4-methyloxyphenyl)-2,6-bis(4-morpholinophenyl)-pyridine,
4-(4-fluorophenyl)-2,6-bis(4-dimethylaminophenyl)-pyridine,
4-(4-N-octyloxyphenyl-N-methylamino)-2,6-diphenylpyridine,
4-(4-chlorophenyl)-2,6-bis(4-dimethylaminophenyl)-pyridine,
4-(4-nitrophenyl)-2,6-bis(4-dimethylaminophenyl)-pyridine,
4-(4-N-2-cyanoethyl-N-methylaminophenyl)-2,6-bis(4-dimethylaminophenyl)-pyridine,
4-(2,5-dimethyloxyphenyl)-2,6-bis(4-dimethylaminophenyl)-pyridine,
4-(4-diethylaminophenyl)-2,6-bis(4-dimethylaminophenyl)-pyridine,
4-(4-biphenylyl)-2,6-bis(4-dimethylaminophenyl)-pyridine,
4-(4-pyrrolidinylphenyl)-2,6-bis(4-dimethylaminophenyl)-pyridine,
4-(4-isoindolinylphenyl)-2,6-bis(4-dimethylaminophenyl)-pyridine,
4-(4-N-2-cyanoethyl-N-methylaminophenyl)-2,6-diphenylpyridine,
4-(4-N-methyl-N-phenylaminophenyl)-2,6-diphenylpyridine,
4-(4-N-chloroethyl-N-methylaminophenyl)-2,6-diphenylpyridine,
4-(4-N-ethyloxyethyl-N-methylaminophenyl)-2,6-diphenylpyridine,
2,6-bis(2′,4′-dimethyloxyphenyl)-4-(4′-dimethylaminophenyl)-pyridine,
2,6-bis(2′,4′-diethyloxyphenyl)-4-(4′-dimethylaminophenyl)-pyridine,
2,6-bis(2′,4′-dipropyloxyphenyl)-4-(4′-dimethylaminophenyl)-pyridine,
2,6-bis(2′,4′-dibutyloxyphenyl)-4-(4′-dimethylaminophenyl)-pyridine,
2,6-bis(2′,4′-dipentyloxyphenyl)-4-(4′-dimethylaminophenyl)-pyridine,
2,6-bis(2′,4′-dihexyloxyphenyl)-4-(4′-dimethylaminophenyl)-pyridine,
2,6-bis(2′,4′-dimethyloxyphenyl)-4-(4′-diethylaminophenyl)-pyridine,
2,6-bis(2′,4′-diethyloxyphenyl)-4-(4′-diethylaminophenyl)-pyridine,
2,6-bis(2′,4′-dipropyloxyphenyl)-4-(4′-diethylaminophenyl)-pyridine,
2,6-bis(2′,4′-dibutyloxyphenyl)-4-(4′-diethylaminophenyl)-pyridine,
2,6-bis(2′,4′-dipentyloxyphenyl)-4-(4′-diethylaminophenyl)-pyridine,
2,6-bis(2′,4′-dihexyloxyphenyl)-4-(4′-diethylaminophenyl)-pyridine,
2,6-bis(2′,4′-dimethyloxyphenyl)-4-(4′-dipropylaminophenyl)-pyridine,
2,6-bis(2′,4′-diethyloxyphenyl)-4-(4′-dipropylaminophenyl)-pyridine,
2,6-bis(2′,4′-dipropyloxyphenyl)-4-(4′-dipropylaminophenyl)-pyridine,
2,6-bis(2′,4′-dibutyloxyphenyl)-4-(4′-dipropylaminophenyl)-pyridine,
2,6-bis(2′,4′-dipentyloxyphenyl)-4-(4′-dipropylaminophenyl)-pyridine,
2,6-bis(2′,4′-dihexyloxyphenyl)-4-(4′-dipropylaminophenyl)-pyridine,
2,6-bis(2′,4′-dimethyloxyphenyl)-4-(4′-dibutylaminophenyl)-pyridine,
2,6-bis(2′,4′-diethyloxyphenyl)-4-(4′-dibutylaminophenyl)-pyridine,
2,6-bis(2′,4′-dipropyloxyphenyl)-4-(4′-dibutylaminophenyl)-pyridine,
2,6-bis(2′,4′-dibutyloxyphenyl)-4-(4′-dibutylaminophenyl)-pyridine,
2,6-bis(2',4'-dipentyloxyphenyl)-4-(4'-dibutylaminophenyl)-pyridine,
2,6-bis(2′,4′-dihexyloxyphenyl)-4-(4′-dibutylaminophenyl)-pyridine,
etc.

As the quinazoline compound,
2-(4′-dimethylaminophenyl)-4-methyloxy-quinazoline,
2-(4′-dimethylaminophenyl)-4-phenyloxy-quinazoline,
2-(4′-dimethylaminophenyl)-4-(4″-nitrophenyloxy)-quinazoline,
2-(4′-dimethylaminophenyl)-4-phenylthio-quinazoline,
2-(4′-N-phenyl-N-methylaminophenyl)-4-phenyloxy-quinazoline,
2-(4′-piperidinophenyl)-4-phenoxy-quinazoline,
2-(4′-dimethylaminophenyl)-4-(4″-chlorophenyloxy)-quinazoline,
2-(4′-dimethylaminophenyl)-4-(4″-methyloxyphenyloxy)-quinazoline,
2-(4′-dimethylaminophenyl)-4-(N-phenyl-N-methylamino)-quinazoline,
2-(4′-dimethylaminophenyl)-4-morpholino-quinazoline,
2-(4′-diethylaminophenyl)-4-phenyl-quinazoline,
2-(4′-diethylaminophenyl)-4-methyl-quinazoline,
2-(1′-ethyl-2′,2′,4′-trimethyl-tetrahydroquinolin-6′-yl)-4-phenyloxy-quinazoline,
2-(1′-ethyl-2′,2′,4′-trimethyl-tetrahydroquinolin-6′-yl)-4-methyloxy-quinazoline,
2-(1′,2′,2′,4′-tetramethyl-tetrahydroquinolin-6′-yl)-4-phenyloxy-quinazoline,
2-(1′-ethyl-2′-methyl-tetrahydroquinolin-6′-yl)-4-phenyloxy-quinazoline,
2-(1′,3′-dimethylindolin-5′-yl)-4-phenyloxy-quinazoline,
2-(3′,4′-dimethylbenzomorpholin-7′-yl)-4-phenyloxy-quinazoline,
2-(4′-diethylaminophenyl)-4-(2″-phenyloxyethyloxy)-quinazoline,
2-(4′-diethylaminophenyl)-4-(2″-N-phenyl-N-ethylaminoethyloxy)-quinazoline,
2-(4′-dimethylaminophenyl)-4-(2″-morpholinoethyloxy)-quinazoline,
2-(4′-dibenzylaminophenyl)-4-(2″-phenyloxyethyloxy)-quinazoline,
2-(4′-diethylaminophenyl)-4-(2″-phenyloxyethylthio)-quinazoline,
2-(4′-diethylaminophenyl)-4-[2″-(1-naphthyloxy)ethyloxy]-quinazoline,
2-(3′,4′-dimethylbenzomorpholin-7′-yl)-(2″-phenyloxyethyloxy)-quinazoline,
etc.

As the bisquinazoline compound,
4,4′-(ethylenedioxy)-bis[2-(4-diethylaminophenyl)-quinazoline],
4,4′-[propylenedioxy(1,3)]-bis[2-(4-diethylaminophenyl)-quinazoline],
4,4′-[butylenedioxy(1,3)]-bis[2-(4-diethylaminophenyl)-quinazoline],
4,4′-[butylenedioxy(1,4)]-bis[2-(4-diethylaminophenyl)-quinazoline],
4,4′-(oxydiethylene)-bis[2-(4-diethylaminophenyl)-quinazoline],
4,4′-ethylene-bis[2-(4-piperidinophenyl)-quinazoline],
4,4′-ethylene-bis[2-(4-di-n-propylaminophenyl)-quinazoline],
4,4′-(ethylenedioxy)-bis[2-(4-di-n-butylaminophenyl)-quinazoline],
4,4′-cyclohexylene-bis[2-(4-diethylaminophenyl)-quinazoline],
etc.

As the diazarhodamine lactone compound,
2-(dimethylamino)-8-(dimethylamino)-4-methyl-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′H)-isobenzofuran]-3 '-on,
2-(Diethylamino)-8-(diethylamino)-4-methyl-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′H)-isobenzofuran]-3′- on,
2-(di-n-propylamino)-8-(di-n-propylamino)-4-methyl-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′ H)-isobenzofuran]-3′-one,
2-(Di-n-butylamino)-8-(di-n-butylamino)-4-methyl-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′ H)-isobenzofuran]-3′-one,
2-(Di-n-butylamino)-8-(dimethylamino)-4-methyl-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′H)-iso benzofuran]-3′-one,
2-(Di-n-butylamino)-8-(diethylamino)-4-methyl-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′H)-isobenzofuran ]-3′-on,
2-(di-n-butylamino)-8-(N-ethyl-Ni-butylamino)-4-methyl-spiro[5H-[1]benzopyrano(2,3-g)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-g)pyrimidine-5,1′ (3′H)-isobenzofuran]-3′-one,
2-(di-n-butylamino)-8-(N-ethyl-Nn-hexylamino)-4-methyl-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1 '(3'H)-isobenzofuran]-3'-one,
2-(di-n-butylamino)-8-(di-n-amylamino)-4-methyl-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′H )-isobenzofuran]-3′-one,
2-(di-n-butylamino)-8-(n-octylamino)-4-methyl-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′H) -isobenzofuran]-3'-one,
2-(dimethylamino)-8-(diethylamino)-4-methyl-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′H)-isobenzofuran]-3′ -on,
2-(Diethylamino)-8-(dimethylamino)-4-methyl-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′H)-isobenzofuran]-3′ -on,
2-(morpholino)-8-(diethylamino)-4-methyl-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′H)-isobenzofuran]-3′- on,
2-(piperidino)-8-(diethylamino)-4-methyl-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′H)-isobenzofuran]-3′- on,
2-(N-methylpiperazino)-8-(diethylamino)-4-methyl-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′H)-isobenzofuran]-3 '-on,
2-(pyrrolidino)-8-(diethylamino)-4-methyl-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′H)-isobenzofuran]-3′- on,
2-(diethylamino)-8-(diethylamino)-4-methyl-4',5',6',7'-tetrachloro-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5, 1′(3′H)-isobenzofuran]-3′-one,
2-(diethylamino)-8-(diethylamino)-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′H)-isobenzofuran]-3′-one,
2-(Di-n-butylamino)-8-(di-n-butylamino)-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′H)-iso benzofuran]-3′-one,
2-(N-ethyl-Ni-amylamino)-8-(N-ethyl-Ni-amylamino)-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′ ( 3′H)-isobenzofuran]-3′-one,
2-(Di-n-butylamino)-8-(diethylamino)-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′H)-isobenzofuran]-3′ -on,
2-(Di-n-butylamino)-8-(N-ethyl-Ni-amylamino)-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′H )-isobenzofuran]-3′-one,
2-(piperidino)-8-(ethylamino)-4-methyl-7-methyl-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′H)-isobenzofuran ]-3′-on,
2-(Di-n-butylamino)-8-(diethylamino)-4-methyl-7-methyl-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′H )-isobenzofuran]-3′-one,
2-(Di-n-butylamino)-8-(diethylamino)-4-methyl-7-ethyl-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′H )-isobenzofuran]-3′-one,
2-(Di-n-butylamino)-8-(diethylamino)-4-phenyl-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′H)-isobenzofuran ]-3′-on,
2-(di-n-butylamino)-8-(di-n-butylamino)-4-phenyl-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′ H)-isobenzofuran]-3′-one,
2-(Di-n-butylamino)-8-(N-ethyl-Ni-amylamino)-4-phenyl-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′ (3′H)-isobenzofuran]-3′-one,
2-(piperidino)-8-(diethylamino)-4-phenyl-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′H)-isobenzofuran]-3′- on,
2-(N-methyl-N-cyclohexylamino)-8-(diethylamino)-4-phenyl-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′H)- isobenzofuran]-3′-one,
2-(dimethylamino)-8-(diethylamino)-4-phenyl-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′H)-isobenzofuran]-3′ -on,
2-(i-amylamino)-8-(diethylamino)-4-phenyl-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′H)-isobenzofuran]-3 '-on,
2-(pyrrolidino)-8-(diethylamino)-4-phenyl-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′H)-isobenzofuran]-3′- on,
2-(N-methylpiperazino)-8-(diethylamino)-4-phenyl-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′H)-isobenzofuran]-3 '-on,
2-(morpholino)-8-(diethylamino)-4-phenyl-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′H)-isobenzofuran]-3′- on,
2-(N-methyl-N-benzylamino)-8-(diethylamino)-4-phenyl-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′H)- isobenzofuran]-3′-one,
2-[di(2-methoxyethyl)amino]-8-(diethylamino)-4-phenyl-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′H)- isobenzofuran]-3′-one,
2-(di-n-butylamino)-8-(diethylamino)-4-(4-methoxyphenyl)-spiro[5H-[1]benzopyrano(2,3-d)pyrimidine-5,1′(3′ H)-isobenzofuran]-3′-one,
2-(di-n-butylamino)-8-(diethylamino)-4-(4-chlorophenyl)-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′H )-isobenzofuran]-3′-one,
2-(di-n-butylamino)-8-(diethylamino)-4-(4-methylphenyl)-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′ H)-isobenzofuran]-3′-one,
2-[di(2-ethoxyethyl)amino]-8-(dimethylamino)-4-phenyl-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′H) -isobenzofuran]-3'-one,
2-(Diethylamino)-8-[(2-methylphenyl)amino]-4-phenyl-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′H)-iso benzofuran]-3′-one,
2-(2,6-dimethylmorpholino)-8-(diethyamino)-4-phenyl-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′H)-isobenzofuran ]-3′-on,
2-(Dicyclohexylamino)-8-(dimethylamino)-4-phenyl-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′H)-isobenzofuran]-3 '-on,
2-(dibutylamino)-8-[(4-chlorophenyl)amino]-4-phenyl-spiro[5H-[1]benzopyrano(2,3-g)pyrimidine-5,1′(3′H)-iso benzofuran]-3′-one,
etc.

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 compound include a group of compounds having an active proton, a group of pseudo-acidic compounds [a group of compounds that are not acids but act as acids in the composition to develop the color of component (a)], and have electron vacancies. There are compounds selected from the group of compounds and the like, and among these, compounds selected from the group of compounds having an active proton are preferred.
Examples of compounds having an active proton include compounds having a phenolic hydroxyl group and derivatives thereof, carboxylic acids and derivatives thereof, preferably aromatic carboxylic acids and derivatives thereof, aliphatic carboxylic acids having 2 to 5 carbon atoms and their derivatives. Derivatives, acidic phosphates and their derivatives, azole compounds and their derivatives, 1,2,3-triazoles and their derivatives, cyclic carbosulfimides, halohydrins having 2 to 5 carbon atoms, sulfonic acids and their derivatives , inorganic acids and the like.
Examples of the pseudo-acidic compound group include metal salts of compounds having a phenolic hydroxyl group, metal salts of carboxylic acids, metal salts of acidic phosphoric acid esters, metal salts of sulfonic acids, aromatic and aliphatic carboxylic acids. Anhydrides, aromatic carboxylic acid-sulfonic anhydrides, cycloolefin dicarboxylic acid anhydrides, urea and its derivatives, thiourea and its derivatives, guanidine and its derivatives, halogenated alcohols and the like.
Examples of compounds having electron vacancies include borates, borate esters, and inorganic salts.
Among these, a compound having a phenolic hydroxyl group is preferable because it can exhibit effective thermochromic properties.
The compounds having phenolic hydroxyl groups include a wide range of compounds 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 carboxyl group, an ester or amide group thereof, a halogen group, and the like.
Examples of the metal contained in the metal salt of the compound having a phenolic hydroxyl group include sodium, potassium, calcium, zinc, zirconium, aluminum, magnesium, nickel, cobalt, tin, copper, iron, vanadium, titanium, lead, and molybdenum and the like.

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

Examples of compounds having two phenolic hydroxyl groups include resorcinol, 2-methylresorcinol, 4-n-hexylresorcinol, 4-n-octylresorcinol, 4-tert-octylresorcinol, 4-benzoylresorcinol, 4-nitroresorcinol, β -methyl resorcinate, benzyl β-resorcinate, 2-chloro-4-pentanoylresorcinol, 6-chloro-4-pentanoylresorcinol, 2-chloro-4-hexanoylresorcinol, 6-chloro-4-hexanoylresorcinol , 2-chloro-4-propanoylresorcinol, 6-chloro-4-propanoylresorcinol, 2,6-dichloro-4-propanoylresorcinol, 6-fluoro-4-propanoylresorcinol, 2-chloro-4-phenyl Acetylresorcin, 6-chloro-4-phenylacetylresorcin, 2-chloro-4-β-phenylpropanoylresorcin, 6-chloro-4-β-phenylpropanoylresorcin, 2-chloro-4-phenoxyacetylresorcin, 6 -chloro-4-phenoxyacetylresorcinol, 4-benzoyl-2-chlororesorcinol, 6-chloro-4-m-methylbenzoylresorcinol, 4-[1′,3′,4′,9′a-tetrahydro-6′ -hydroxyspiro(cyclohexane-1,9'-[9H]-xanthene)-4'a-[2H]-yl]-1,3-benzenediol, hydroquinone, methylhydroquinone, trimethylhydroquinone, catechol, 4-tert- butylcatechol, 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene,
2,4-dihydroxybenzophenone, 4,4'-dihydroxybenzophenone, 2,4-dihydroxy-2'-methylbenzophenone, 2,4-dihydroxy-3'-methylbenzophenone, 2,4-dihydroxy-4'-methylbenzophenone , 2,4-dihydroxy-4′-ethylbenzophenone, 2,4-dihydroxy-4′-n-propylbenzophenone, 2,4-dihydroxy-4′-isopropylbenzophenone, 2,4-dihydroxy-4′-n- Butylbenzophenone, 2,4-dihydroxy-4'-isobutylbenzophenone, 2,4-dihydroxy-4'-tert-butylbenzophenone, 2,4-dihydroxy-4'-n-pentylbenzophenone, 2,4-dihydroxy-4 '-n-hexylbenzophenone, 2,4-dihydroxy-4'-n-heptylbenzophenone, 2,4-dihydroxy-4'-n-octylbenzophenone, 2,4-dihydroxy-4'-n-decylbenzophenone, 2 ,4-dihydroxy-2',3'-dimethylbenzophenone, 2,4-dihydroxy-2',4'-dimethylbenzophenone, 2,4-dihydroxy-2',5'-dimethylbenzophenone, 2,4-dihydroxy- 2',6'-dimethylbenzophenone, 2,4-dihydroxy-3',4'-dimethylbenzophenone, 2,4-dihydroxy-3',5'-dimethylbenzophenone, 2,4-dihydroxy-2',4',6'-trimethylbenzophenone,2,4-dihydroxy-2'-methoxybenzophenone,2,4-dihydroxy-3'-methoxybenzophenone,2,4-dihydroxy-4'-methoxybenzophenone, 2,4-dihydroxy-2 '-ethoxybenzophenone, 2,4-dihydroxy-4'-ethoxybenzophenone, 2,4-dihydroxy-4'-n-propoxybenzophenone, 2,4-dihydroxy-4'-isopropoxybenzophenone, 2,4-dihydroxy- 4'-n-butoxybenzophenone, 2,4-dihydroxy-4'-isobutoxybenzophenone, 2,4-dihydroxy-4'-n-pentyloxybenzophenone, 2,4-dihydroxy-4'-n-hexyloxybenzophenone , 2,4-dihydroxy-4′-n-heptyloxybenzophenone, 2,4-dihydroxy-4′-n-octyloxybenzophenone, 2,4-dihydroxy-4′-n-nonyloxybenzophenone, 2,4- dihydroxy-2',3'-dimethoxybenzophenone, 2,4-dihydroxy-2',4'-dimethoxybenzophenone, 2,4-dihydroxy-2',5'-dimethoxybenzophenone, 2,4-dihydroxy-2', 6'-dimethoxybenzophenone, 2,4-dihydroxy-3',4'-dimethoxybenzophenone, 2,4-dihydroxy-3',5'-dimethoxybenzophenone, 2,4-dihydroxy-3',4'-diethoxy Benzophenone, 2,4-dihydroxy-2',3',4'-trimethoxybenzophenone, 2,4-dihydroxy-2',3',6'-trimethoxybenzophenone, 2,4-dihydroxy-3',4 ',5'-trimethoxybenzophenone, 2,4-dihydroxy-3',4',5'-triethoxybenzophenone and the like.

Furthermore, bis-type phenol compounds include 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)n-butane, 1,1-bis(4-hydroxyphenyl)n-pentane, 1,1-bis(4-hydroxyphenyl)n-hexane, 1,1-bis(4-hydroxyphenyl)n-heptane, 1,1-bis (4-hydroxyphenyl) n-octane, 1,1-bis(4-hydroxyphenyl) n-nonane, 1,1-bis(4-hydroxyphenyl) n-decane, 1,1-bis(4-hydroxy- 3-methylphenyl)decane, 1,1-bis(4-hydroxyphenyl)n-dodecane, 1,1-bis(4-hydroxyphenyl)-2-methylpropane, 1,1-bis(4-hydroxyphenyl) -3-methylbutane, 1,1-bis(4-hydroxyphenyl)-3-methylpentane, 1,1-bis(4-hydroxyphenyl)-2,3-dimethylpentane, 1,1-bis(4-hydroxy Phenyl)-2-ethylbutane, 1,1-bis(4-hydroxyphenyl)-2-ethylhexane, 1,1-bis(4-hydroxyphenyl)-3,7-dimethyloctane, 1,1-bis(4 -hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxy-3-methyl)cyclohexane, diphenolic acid, 1-phenyl -1,1-bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)n-butane, 2,2-bis(4- hydroxyphenyl)n-pentane, 2,2-bis(4-hydroxyphenyl)n-hexane, 2,2-bis(4-hydroxyphenyl)n-heptane, 2,2-bis(4-hydroxyphenyl)n -octane, 2,2-bis(4-hydroxyphenyl)n-nonane, 2,2-bis(4-hydroxyphenyl)n-decane, 2,2-bis(4-hydroxyphenyl)n-dodecane, 2, 2-bis(4-hydroxyphenyl)-6,10,14-trimethylpentadecane, 1-phenyl-1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)methylpropio 2,2-bis(4-hydroxyphenyl)butylpropionate, 2,2-bis(4-hydroxy-3-methylphenyl)methylpropionate, 2,2-bis(4-hydroxyphenyl)ethyl Propionate, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 2,2-bis(4-hydroxyphenyl)-4-methylhexane, 2,2-bis(4-hydroxyphenyl)hexa Fluoropropane, 2,2-bis(3,5-dihydroxymethyl-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4- Hydroxy-3-methylphenyl)butane, 2,2-bis(4-hydroxy-3-isopropylphenyl)propane, 2,2-bis(3-sec-butylphenyl-4-hydroxy)propane, 2,2-bis (4-hydroxy-3-phenylphenyl)propane, 2,2-bis(3-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(3-fluoro-4-hydroxyphenyl)propane, 2, 2-bis(3,5-dihydroxymethyl-4-hydroxyphenyl)propane, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,3-bis[2-(4-hydroxyphenyl)- 2-propyl]benzene, 1,4-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, 3,3-bis(4-hydroxyphenyl)oxindole, 3,3-bis(4-hydroxy -3-methylphenyl)oxindole, bis(2-hydroxyphenyl)methane, bis(2-hydroxy-5-methylphenyl)methane, bis(2-hydroxy-3-hydroxymethyl-5-methyl)methane, 4, 4'-[1,4-phenylenebis(1-methylethylidene)]bis(2-methylphenol), 1,1-bis(4-hydroxy-3-phenylphenyl)cyclohexane, 3,3-ethyleneoxydiphenol , 1,4-bis(4-hydroxybenzoate)-3-methylbenzene, 4,4″-dihydroxy-3″-methyl-p-terphenyl, 4,4″-dihydroxy-3″-isopropyl-p- terphenyl, 2,2-dimethyl-1,3-bis(4-hydroxybenzoyloxy)propane, 2,2′-biphenol, 4,4′″-dihydroxy-p-quaterphenyl,
4,4-dihydroxydiphenyl ether, bis(4-hydroxyphenylthioethyl) ether,
Bis(4-hydroxyphenyl)sulfone, 4-benzyloxy-4'-hydroxydiphenylsulfone, 4-(4-methylbenzyloxy)-4'-hydroxydiphenylsulfone, 4-(4-ethylbenzyloxy)-4' -hydroxydiphenylsulfone, 4-(4-n-propylbenzyloxy)-4'-hydroxydiphenylsulfone, 4-(4-isopropylbenzyloxy)-4'-hydroxydiphenylsulfone, 4-(4-n-butylbenzyl) oxy)-4'-hydroxydiphenylsulfone, 4-(4-isobutylbenzyloxy)-4'-hydroxydiphenylsulfone, 4-(4-sec-butylbenzyloxy)-4'-hydroxydiphenylsulfone, 4-(4 -tert-butylbenzyloxy)-4'-hydroxydiphenylsulfone, 4-(3-methylbenzyloxy)-4'-hydroxydiphenylsulfone, 4-(3-ethylbenzyloxy)-4'-hydroxydiphenylsulfone, 4 -(3-n-propylbenzyloxy)-4'-hydroxydiphenylsulfone, 4-(3-isopropylbenzyloxy)-4'-dihydroxyphenylsulfone, 4-(3-n-butylbenzyloxy)-4'- Hydroxydiphenylsulfone, 4-(3-isobutylbenzyloxy)-4'-hydroxydiphenylsulfone, 4-(3-sec-butylbenzyloxy)-4'-hydroxydiphenylsulfone, 4-(3-tert-butylbenzyloxy) )-4′-hydroxydiphenylsulfone, 4-(2-methylbenzyloxy)-4′-hydroxydiphenylsulfone, 4-(2-ethylbenzyloxy)-4′-hydroxydiphenylsulfone, 4-(2-n- propylbenzyloxy)-4'-hydroxydiphenylsulfone, 4-(2-isopropylbenzyloxy)-4'-hydroxydiphenylsulfone, 4-(2-n-butylbenzyloxy)-4'-hydroxydiphenylsulfone, 4- (2-isobutylbenzyloxy)-4'-hydroxydiphenylsulfone, 4-(2-sec-butylbenzyloxy)-4'-hydroxydiphenylsulfone, 4-(2-tert-butylbenzyloxy)-4'-hydroxy diphenyl sulfone, 2,4'-dihydroxydiphenyl sulfone, 3,4'-dihydroxydiphenyl sulfone, 4-hydroxydiphenyl sulfone, 4-methyl-4'-hydroxydiphenyl sulfone, 4-ethyl-4'-hydroxydiphenyl sulfone, 4-n-propyl-4'-hydroxydiphenylsulfone, 4-isopropyl-4'-hydroxydiphenylsulfone, 4-chloro-4'-hydroxydiphenylsulfone, 4-fluoro-4'-hydroxydiphenylsulfone, 4-chloro- 2-methyl-4'-hydroxydiphenylsulfone, 4-methoxy-4'-hydroxydiphenylsulfone, 4-ethoxy-4'-hydroxydiphenylsulfone, 4-n-propoxy-4'-hydroxydiphenylsulfone, 4-isopropoxy -4'-hydroxydiphenylsulfone, 4-n-butoxy-4'-hydroxydiphenylsulfone, 4-isobutoxy-4'-hydroxydiphenylsulfone, 4-sec-butoxy-4'-hydroxydiphenylsulfone, 4-tert-butoxy -4'-hydroxydiphenylsulfone, 4-n-pentyloxy-4'-hydroxydiphenylsulfone, 4-isopentyloxy-4'-hydroxydiphenylsulfone, 4-(1-propenyloxy)-4'-hydroxydiphenylsulfone , 4-(2-propenyloxy)-4'-hydroxydiphenylsulfone, 4-benzyloxy-4'-hydroxydiphenylsulfone, 4-(β-phenoxyethoxy)-4'-hydroxydiphenylsulfone, 4-(β- phenoxypropoxyl)-4'-hydroxydiphenylsulfone, bis(2-allyl-4-hydroxydiphenyl)sulfone, bis[4-hydroxy-3-(2-propenyl)phenyl]sulfone, bis(3,5-dibromo- 4-hydroxyphenyl)sulfone, bis(3,5-dichloro-4-hydroxyphenyl)sulfone, bis(3-phenyl-4-hydroxyphenyl)sulfone, bis(4-hydroxy-3-n-propylphenyl)sulfone, bis(4-hydroxy-3-methylphenyl)sulfone, 3,4-dihydroxydiphenylsulfone, 3′,4′-dihydroxy-4-methyldiphenylsulfone, 3,4,4′-trihydroxydiphenylsulfone, bis(3 ,4-dihydroxyphenyl)sulfone, 2,3,4-trihydroxydiphenylsulfone, 4-isopropoxy-4'-hydroxydiphenylsulfone, 4-n-propoxy-4'-hydroxydiphenylsulfone, 4-allyloxy-4' -hydroxydiphenylsulfone, 4-benzyloxy-4'-hydroxydiphenylsulfone, 4-(2-propenyloxy)-4'-hydroxydiphenylsulfone, 3-benzyl-4-benzyloxy-4'-hydroxydiphenylsulfone, 3-phenethyl-4-phenethyloxy-4'-hydroxydiphenylsulfone, 3-methylbenzyl-4-methylbenzyloxy-4'-hydroxydiphenylsulfone, 4-benzyloxy-3'-benzyl-4'-hydroxydiphenylsulfone , 4-phenethyloxy-3′-phenethyl-4′-hydroxydiphenylsulfone, 4-methylbenzyloxy-3′-methylbenzyl-4′-hydroxydiphenylsulfone, α,α′-bis{4-(p-hydroxy phenylsulfone)phenoxy}-p-xylene, 4,4′-{oxybis(ethylene oxide-p-phenylenesulfonyl)}diphenol,
bis(4-hydroxyphenyl)sulfide, bis(4-hydroxy-3-methylphenyl)sulfide, bis(3,5-dimethyl-4-hydroxyphenyl)sulfide, bis(3-ethyl-4-hydroxyphenyl)sulfide, bis(3,5-diethyl-4-hydroxyphenyl) sulfide, bis(4-hydroxy-3-n-propylphenyl) sulfide, bis(3,5-di-n-propyl-4-hydroxyphenyl) sulfide, bis (3-tert-butyl-4-hydroxyphenyl) sulfide, bis (3,5-di-tert-butyl-4-hydroxyphenyl) sulfide, bis (4-hydroxy-3-n-pentylphenyl) sulfide, bis ( 3-n-hexyl-4-hydroxyphenyl)sulfide, bis(3-n-heptyl-4-hydroxyphenyl)sulfide, bis(5-tert-octyl-2-hydroxyphenyl)sulfide, bis(2-hydroxy-3 -tert-octylphenyl)sulfide, bis(2-hydroxy-5-n-octyl-phenyl)sulfide, bis(5-chloro-2-hydroxyphenyl)sulfide, bis(3-cyclohexyl-4-hydroxyphenyl)sulfide, bis(4-hydroxyphenylthioethoxy)methane, 1,5-(4-hydroxyphenylthio)-3-oxypentane, 1,8-bis(4-hydroxyphenylthio)-3,6-dioxaoctane and the like mentioned.

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

Furthermore, as a tris-type phenol compound,
4,4′,4″-methylidyne trisphenol,
4,4′,4″-methylidynetris(2-methylphenol),
4,4′-[(2-hydroxyphenyl)methylene]bis(2,3,5-trimethylphenol),
4,4′-[(4-hydroxyphenyl)methylene]bis(2-methylphenol),
4,4′-[(4-hydroxyphenyl)methylene]bis(2,6-dimethylphenol),
4,4′-[(4-hydroxy-3-methoxyphenyl)methylene]bisphenol,
4,4′-[(4-hydroxyphenyl)methylene]bis(2-cyclohexyl-5-methylphenol),
4,4′,4″-ethylidine trisphenol,
4,4′,4″-ethylidine tris(2-methylphenol),
4,4′-[(2-hydroxyphenyl)methylene]bis(2-cyclohexyl-5-methylphenol),
2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol,
2,4-bis[(2-hydroxy-5-methylphenyl)methyl]-6-cyclohexylphenol,
4,4′-[1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}methylidene]bisphenol,
4,4′-[1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bisphenol,
4,4′-[1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}propylidene]bisphenol,
4,4′-[1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}butylidene]bisphenol,
4,4′-[1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}pentylidene]bisphenol,
4,4′-[1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}hexylidene]bisphenol,
4,4′-[1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}heptylidene]bisphenol,
4,4′-[1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}isobutylidene]bisphenol,
4,4′-[1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}neopentylidene]bisphenol,
2,2′-[1-{4-[1-(2-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bisphenol,
3,3′-[1-{4-[1-(3-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bisphenol,
4,4′-[1-{4-[1-(3-fluoro-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis(2-fluorophenol),
4,4′-[1-{4-[1-(3-chloro-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis(2-chlorophenol),
4,4′-[1-{4-[1-(3-bromo-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis(2-bromophenol),
4,4′-[1-{4-[1-(4-hydroxy-3-methylphenyl)-1-methylethyl]phenyl}ethylidene]bis(2-methylphenol),
4,4′-[1-{4-[1-(3-ethyl-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis(2-ethylphenol),
4,4′-[1-{4-[1-(3-tert-butyl-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis(2-tert-butylphenol),
4,4′-[1-{4-[1-(4-hydroxy-3-trifluoromethylphenyl)-1-methylethyl]phenyl}ethylidene]bis(2-trifluoromethylphenol),
1,1-bis(4-hydroxyphenyl)-4-(4-hydroxy-α-ethyl)benzylcyclohexane,
4,4′-[(3-ethoxy-4-hydroxysiphenyl)methylene]bisphenol,
4,4′-[(3-hydroxyphenyl)methylene]bis(2,6-dimethylphenol),
2,2′-[(4-hydroxyphenyl)methylene]bis(3,5-dimethylphenol),
4,4′-[(4-hydroxy-3-methoxyphenyl)methylene]bis(2,6-dimethylphenol),
2,2′-[(2-hydroxyphenyl)methylene]bis(3,5,6-trimethylphenol),
4,4′-[(3-hydroxyphenyl)methylene]bis(2,3,6-trimethylphenol),
4,4′-[(4-hydroxyphenyl)methylene]bis(2,3,6-trimethylphenol),
4,4′-[(3-hydroxyphenyl)methylene]bis(2-cyclohexyl-5-methylphenol),
4,4′-[(4-hydroxyphenyl-3-methoxy)methylene]bis(2-cyclohexyl-5-methylphenol),
1,1-bis(4-hydroxylphenyl)-4-hydroxyphenylcyclohexane,
4,4′-[3-(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3-phenyl)propylidene]bis(2-cyclohexyl-5-methylphenol),
4,4′-[(2-hydroxyphenyl)methylene]bis(2-methylphenol),
2,4′,4″-methylidyne trisphenol,
4,4′-[(2-hydroxyphenyl)methylene]bis(3-methylphenol),
4,4′-[4-(4-hydroxyphenyl)-sec-butylidene]bis(4-hydroxyphenol),
2,2′-[(3-hydroxyphenyl)methylene]bis(3,5-dimethylphenol),
4,4′-[(2-hydroxy-3-methoxyphenyl)methylene]bis(2,5-dimethylphenol),
4,4′-[(2-hydroxy-3-methoxyphenyl)methylene]bis(2,6-dimethylphenol),
2,2′-[(2-hydroxy-3-methoxyphenyl)methylene]bis(3,5-dimethylphenol),
2,2′-[(3-hydroxy-4-methoxyphenyl)methylene]bis(3,5-dimethylphenol),
2,2′-[(4-hydroxy-3-methoxyphenyl)methylene]bis(3,5-dimethylphenol),
4,4′-[(2-hydroxyphenyl)methylene]bis(2-isopropylphenol),
4,4′-[(3-hydroxyphenyl)methylene]bis(2-isopropylphenol),
4,4′-[(4-hydroxyphenyl)methylene]bis(2-isopropylphenol),
2,2′-[(3-hydroxyphenyl)methylene]bis(3,5,6-trimethylphenol),
2,2′-[(4-hydroxyphenyl)methylene]bis(3,5,6-trimethylphenol),
2,2′-[(4-3-ethoxy-4-hydroxyphenyl)methylene]bis(3,5-dimethylphenol),
1,1-bis(4-hydroxy-3-methylphenyl)-4-(4-hydroxyphenyl)cyclohexane,
4,4′-[(2-hydroxy-3-methoxyphenyl)methylene]bis(2-isopropylphenol),
4,4′-[(3-hydroxy-4-methoxyphenyl)methylene]bis(2-isopropylphenol),
4,4′-[(4-hydroxy-3-methoxyphenyl)methylene]bis(2-isopropylphenol),
2,2′-[(2-hydroxy-3-methoxyphenyl)methylene]bis(3,5,6-trimethylphenol,
2,2′-[(3-hydroxy-4-methoxyphenyl)methylene]bis(3,5,6-trimethylphenol),
2,2′-[(4-hydroxy-3-methoxyphenyl)methylene]bis(3,5,6-trimethylphenol),
4,4′-[(3-ethoxy-4-hydroxyphenyl)methylene]bis(2-isopropylphenol),
2,2′-[(3-ethoxy-4-hydroxyphenyl)methylene]bis(3,5,6-trimethylphenol),
4,4′-[(3-ethoxy-4-hydroxyphenyl)methylene]bis(2,3,6-trimethylphenol),
1,1-bis(3,5-dimethyl-4-hydroxyphenyl)-4-(4-hydroxyphenyl)cyclohexane,
4,4′-[(4-hydroxy-3-methoxyphenyl)methylene]bis(2-tert-butyl-5-methylphenol),
4,4′-[(2-hydroxyphenyl)methylene]bis(2-cyclohexylphenol),
4,4′-[(3-hydroxyphenyl)methylene]bis(2-cyclohexylphenol),
4,4′-[(3-ethoxy-4-hydroxyphenyl)methylene]bis(2-tert-butyl-6-methylphenol),
4,4′-[(3-methoxy-2-hydroxyphenyl)methylene]bis(2-cyclohexylphenol),
4,4′-[(3-hydroxy-4-methoxyphenyl)methylene]bis(2-cyclohexylphenol),
4,4′-[1-{4-[1-(3-fluoro-4-hydroxylophenyl)-1-methylethyl]phenyl}ethylidene]bis(2-tert-butylphenol),
4,4′-[1-{4-[1-(3,5-dimethyl-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis(2,6-dimethylphenol),
4,4′-[(3-ethoxy-4-hydroxyphenyl)methylene]bis(2-cyclohexyl-5-methylphenol),
4,4′-[(3-cyclohexyl-4-hydroxyphenyl)ethylidene]bis(2-cyclohexylphenol),
4,4′-[(5-cyclohexyl-4-hydroxy-2-methoxyphenyl)ethylidene]bis(2-cyclohexyl-5-methylphenol),
4,4′-[1-{4-[1-(3-cyclohexyl-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis(2-cyclohexylphenol),
4,4′-[1-{4-[1-(3-fluoro-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bisphenol,
4,4′-[1-{4-[1-(3-fluoro-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis(2-methylphenol),
4,4′-[1-{4-[1-(3-fluoro-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis(2,6-dimethylphenol),
2,6-bis[(5-fluoro-2-hydroxyphenyl)methyl]-4-methylphenol,
2,6-bis[(3,5-dimethyl-4-hydroxyphenyl)methyl]-4-methylphenol,
2,6-bis[(4-hydroxyphenyl)methyl]-4-methylphenol, 2,6-bis[(4-hydroxyphenyl)methyl]-4-ethylphenol,
2,4-bis[(4-hydroxy-3-methylphenyl)methyl]-6-methylphenol,
2,6-bis[(4-hydroxy-3-methylphenyl)methyl]-4-methylphenol,
2,6-bis[(4-hydroxy-3-methylphenyl)methyl]-4-ethylphenol,
2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-ethylphenol,
2,6-bis[(3,5-dimethyl-2-hydroxyphenyl)methyl]-4-methylphenol,
2,6-bis[(2,4-dimethyl-6-hydroxyphenyl)methyl]-4-methylphenol,
2,4-bis[(4-hydroxyphenyl)methyl]-6-cyclohexylphenol,
2,6-bis[(2,5-dimethyl-4-hydroxyphenyl)methyl]-3,4-dimethylphenol,
2,6-bis[(2,5-dimethyl-4-hydroxyphenyl)methyl]-4-ethylphenol,
2,6-bis[(4-hydroxy-2,3,6-trimethylphenyl)methyl]-4-methylphenol,
2,4-bis[(4-hydroxy-3-methylphenyl)methyl]-6-cyclohexylphenol,
2,6-bis[(4-hydroxy-3-methylphenyl)methyl]-4-cyclohexylphenol,
2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-cyclohexylphenol,
2,6-bis[(4-hydroxy-2,3,5-trimethylphenyl)methyl]-4-ethylphenol,
2,4-bis[(2,5-dimethyl-4-hydroxyphenyl)methyl]-6-cyclohexylphenol,
4,4′,4″-methylidinetris(2,6-dimethylphenol),
α-(4-hydroxy-3-methylphenyl)-α,α'-bis(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene,
α′-(4-hydroxy-3-methylphenyl)-α,α-bis(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene,
α,α-bis(4-hydroxy-3-methylphenyl)-α'-(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene,
α,α'-bis(4-hydroxy-3-methylphenyl)-α-(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene,
1,1-bis(4-hydroxyphenyl)-4-[1-(4-hydroxyphenyl)-1-methylpropyl]cyclohexane,
2,6-bis[(3,5-dimethyl-4-hydroxyphenyl)methyl]-4-ethylphenol,
1,1′-bis(4-hydroxyphenyl)-4-[1-(4-hydroxyphenyl)propyl]cyclohexane,
1,1′-bis(4-hydroxy-3-methylphenyl)-4-[1-(4-hydroxyphenyl)propyl]cyclohexane,
1,1′-bis(3,5-dimethyl-4-hydroxyphenyl)-4-[1-(4-hydroxyphenyl)propyl]cyclohexane,
1-(4-hydroxyphenyl)-1-[4,4-bis(4-hydroxyphenyl)cyclohexyl]-4-isopropylcyclohexane,
4,4′-[3-(2,5-dimethyl-4-hydroxyphenyl)butylene]bis(2,5-dimethylphenol),
1,3,5-tri(4-hydroxy-3-phenylphenyl)adamantane,
1,3,5-tri(3-cyclohexyl-4-hydroxyphenyl)adamantane,
2,4-bis[(3,5-dimethyl-4-hydroxyphenyl)methyl]-6-cyclohexylphenol,
2,6-bis[(2,5-dimethyl-4-hydroxyphenyl)methyl]-4-cyclohexylphenol,
2,4-bis[(3-cyclohexyl-4-hydroxyphenyl)methyl]-6-methylphenol,
2,4-bis[(4-hydroxy-2,3,5-trimethylphenyl)methyl]-6-cyclohexylphenol,
2,6-bis[(5-fluoro-2-hydroxyphenyl)methyl]-4-fluorophenol,
2,6-bis[(3-fluoro-4-hydroxyphenyl)methyl]-4-fluorophenol,
2,4-bis[(3-fluoro-4-hydroxyphenyl)methyl]-6-methylphenol,
4,4′-[3-(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3-biphenylpropylidene]bis(5-cyclohexyl-2-methylphenol),
4,4′-[3-(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropylidene]bis(2,5-dimethylphenol),
2,4-bis[(2,5-dimethyl-4-hydroxyphenyl)methyl]-6-methylphenol, 1,1,2-tris(4-hydroxyphenyl)ethane,
1,1,3-tris(4-hydroxyphenyl)propane, 1,1,4-tris(4-hydroxyphenyl)butane,
1,2,2-tris(4-hydroxyphenyl)propane, 1,2,2-tris(4-hydroxyphenyl)butane,
1,2,2-tris(4-hydroxyphenyl)pentane, 1,2,2-tris(4-hydroxyphenyl)hexane,
1,2,2-tris(4-hydroxyphenyl)heptane, 1,2,2-tris(4-hydroxyphenyl)octane,
1,2,2-tris(4-hydroxyphenyl)-3-methylbutane 1,2,2-tris(4-hydroxyphenyl)-3,3-dimethylbutane,
1,2,2-tris(4-hydroxyphenyl)-4,4-dimethylpentane, 1,3,3-tris(4-hydroxyphenyl)butane,
1,3,3-tris(4-hydroxyphenyl)pentane, 1,3,3-tris(4-hydroxyphenyl)hexane,
1,3,3-tris(4-hydroxyphenyl)heptane, 1,3,3-tris(4-hydroxyphenyl)octane,
1,3,3-tris(4-hydroxyphenyl)nonane, 1,4,4-tris(4-hydroxyphenyl)pentane,
1,4,4-tris(4-hydroxyphenyl)hexane, 1,4,4-tris(4-hydroxyphenyl)heptane,
1,4,4-tris(4-hydroxyphenyl)octane, 1,4,4-tris(4-hydroxyphenyl)nonane,
1,4,4-tris(4-hydroxyphenyl)decane, 1,2,2-tris(2-hydroxyphenyl)propane,
1,1,2-tris(3-hydroxyphenyl)propane,
1-(4-hydroxyphenyl)-2,2-bis(2-hydroxyphenyl)propane,
1,2,2-tris(3-fluoro-4-hydroxyphenyl)propane,
1,2,2-tris(3-chloro-4-hydroxyphenyl)propane,
1,2,2-tris(3-bromo-4-hydroxyphenyl)propane,
2,2-bis(3-ethyl-4-hydroxyphenyl)-1-(4-hydroxyphenyl)propane,
2,2-bis(3-tert-butyl-4-hydroxyphenyl)-1-(4-hydroxyphenyl)propane,
2,2-bis(2-hydroxy-3-biphenylyl)-1-(4-hydroxyphenyl)propane,
2,2-bis(3-trifluoromethyl-4-hydroxyphenyl)-1-(4-hydroxyphenyl)propane,
2-(3-methyl-4-hydroxyphenyl)-1,2-bis(4-hydroxyphenyl)propane,
1-(3-methyl-4-hydroxyphenyl)-2,2-bis(4-hydroxyphenyl)propane,
3-(3-methyl-4-hydroxyphenyl)-1,3-bis(4-hydroxyphenyl)butane,
1-(3-methyl-4-hydroxyphenyl)-3,3-bis(4-hydroxyphenyl)butane,
4-(3-methyl-4-hydroxyphenyl)-1,4-bis(4-hydroxyphenyl)pentane,
1-(3-methyl-4-hydroxyphenyl)-4,4-bis(4-hydroxyphenyl)pentane,
1,2-bis(3-methyl-4-hydroxyphenyl)-2-(4-hydroxyphenyl)propane,
3,3-bis(3-methyl-4-hydroxyphenyl)-1-(4-hydroxyphenyl)butane,
1,3-bis(3-methyl-4-hydroxyphenyl)-3-(4-hydroxyphenyl)butane,
4,4-bis(3-methyl-4-hydroxyphenyl)-1-(4-hydroxyphenyl)pentane,
1,4-bis(3-methyl-4-hydroxyphenyl)-4-(4-hydroxyphenyl)pentane,
1,1,2-tris(3-methyl-4-hydroxyphenyl)ethane,
1,2,2-tris(3-methyl-4-hydroxyphenyl)propane,
1,1,3-tris(3-methyl-4-hydroxyphenyl)propane,
1,3,3-tris(3-methyl-4-hydroxyphenyl)butane,
1,1,4-tris(3-methyl-4-hydroxyphenyl)butane,
1,4,4-tris(3-methyl-4-hydroxyphenyl)pentane,
4,4′-[4-(4-hydroxyphenyl)-sec-butylidene]bis(2-methylphenol)
etc.

As a compound having four or more phenolic hydroxyl groups,
bis[2-hydroxy-3-(2-hydroxy-5-methylbenzyl)-5-methylphenyl]methane,
4,6-bis[(4-hydroxyphenyl)methyl)-1,3-benzenediol,
4,4′-[(3,4-dihydroxyphenyl)methylene]bis(2,6-dimethylphenol),
4,4′-[(3,4-dihydroxyphenyl)methylene]bis(2-cyclohexyl-5-methylphenol),
4,4′-[(3,4-dihydroxyphenyl)methylene]bis(2-methylphenol),
4,4′-[(3,4-dihydroxyphenyl)methylene]bis(2,3,6-trimethylphenol),
1,1,2,2-tetrakis(4-hydroxyphenyl)ethane,
1,1,2,2-tetrakis(4-hydroxy-3-methylphenyl)ethane,
1,1,2,2-tetrakis(3,5-dimethyl-4-hydroxyphenyl)ethane,
1,1,4,4-tetrakis(3,5-dimethyl-4-hydroxyphenyl)benzene,
2,2′-bis[4,4-(4-hydroxy-3-methylphenyl)cyclohexyl]propane,
2,2′-[(3,4-dihydroxyphenyl)methylene]bis(3,5-dimethylphenol),
3,6-bis[(3,5-dimethyl-4-hydroxyphenyl)methyl)catechol,
4,6-bis[(3,5-dimethyl-4-hydroxyphenyl)methyl)-1,3-benzenediol,
2,2′-[(3,4-dihydroxyphenyl)methylene]bis(3,5,6-trimethylphenol),
4,4′-[(3,4-dihydroxyphenyl)methylene]bis(2-cyclohexylphenol),
bis[3-(2-hydroxybenzyl)-4-hydroxy-5-methylphenyl]methane,
bis[3-(3-hydroxybenzyl)-4-hydroxy-5-methylphenyl]methane,
bis[3-(4-hydroxybenzyl)-4-hydroxy-5-methylphenyl]methane,
bis[3-(2-hydroxybenzyl)-2-hydroxy-5-methylphenyl]methane,
bis[3-(2-hydroxybenzyl)-3-hydroxy-5-methylphenyl]methane,
bis[3-(2-hydroxybenzyl)-4-hydroxy-5-methylphenyl]methane,
bis[3-(3-hydroxy-2-methylbenzyl)-2-hydroxy-5-methylphenyl]methane,
bis[3-(4-hydroxy-3-methylbenzyl)-2-hydroxy-5-methylphenyl]methane,
bis[3-(3-hydroxy-4-methylbenzyl)-2-hydroxy-5-methylphenyl]methane,
bis[3-(2-hydroxy-3-methylbenzyl)-2-hydroxy-5-methylphenyl]methane,
α,α′,α″,α′″-tetrakis(4-hydroxyphenyl)benzene,
bis[3-(3,6-dimethyl-2-hydroxybenzyl)-2-hydroxy-5-methylphenyl]methane,
[3-(3,6-dimethyl-2-hydroxybenzyl)-2-hydroxy-5-methylphenyl],
[3-(2,5-dimethyl-4-hydroxybenzyl)-2-hydroxy-5-methylphenyl]methane,
bis[3-(2,5-dimethyl-4-hydroxybenzyl)-2-hydroxy-5-methylphenyl]methane,
bis[3-(3,5-dimethyl-4-hydroxybenzyl)-2-hydroxy-5-methylphenyl]methane,
bis[3-(2-hydroxy-3,4,6-trimethylbenzyl)-2-hydroxy-5-methylphenyl]methane,
bis[2-hydroxy-3-(4-hydroxy-2,3,5-trimethylbenzyl)-5-methylphenyl]methane,
4,4′,4″,4′″-tetrakis(4-hydroxyphenyl)-1,1′-bicyclohexyl,
2,2′-bis[4,4-bis(4-hydroxyphenyl)cyclohexyl]propane,
4,4′,4″,4′″-tetrakis(4-hydroxy-3-methylphenyl)-1,1′-bicyclohexyl,
bis[3-(5-cyclohexyl-4-hydroxy-2-methylbenzyl)-4-hydroxy-5-methylphenyl]methane,
4,4′,4″,4′″-tetrakis(3,5-dimethyl-4-hydroxyphenyl)-1,1′-bicyclohexyl,
1,1-bis[3-(2-hydroxy-5-methylbenzyl)-5-cyclohexyl-4-hydroxyphenyl]cyclohexane,
1,1-bis[3-(3,5-dimethyl-4-hydroxybenzyl)-5-cyclohexyl-4-hydroxyphenyl]cyclohexane,
1,1-bis[3-(5-cyclohexyl-4-hydroxy-2-methylbenzyl)-5-cyclohexyl-4-hydroxyphenyl]cyclohexane,
4,6-bis[α-methyl-(4-hydroxyphenyl)benzyl-1,3-benzenediol,
2,2-bis[3-(4-hydroxy-3-methylbenzyl)-4-hydroxy-5-methylphenyl]propane,
2,6-bis[(3,5-dimethyl-4-hydroxyphenyl)benzyl]-4-[α-methyl-(3,5-dimethyl-4-hydroxyphenyl)benzyl]phenol,
4,4′,4″,4′″-tetrakis(4-hydroxy-3-isopropylphenyl)-1,1′-bicyclohexyl,
4,4′-bis[(3,4-dihydroxyphenyl)methylene]bis(2-isopropylphenol)
2,4,6-tris(4-hydroxybenzyl)-1,3-benzenediol,
4,6-bis(3,5-dimethyl-4-hydroxybenzyl)pyrogallol,
3,3′-[(2-hydroxyphenyl)methylene]bis(5-methylcatechol),
2,6-bis(2,4-dihydroxybenzyl)-4-ethylphenol,
2,4-bis(2,4-dihydroxybenzyl)-6-cyclohexylphenol,
2,6-bis(5-tert-butyl-2,3-dihydroxybenzyl)-4-methylphenol,
2,4,6-tris(3,5-dimethyl-4-hydroxybenzyl)resorcin,
2,4,6-tris(3,5-dimethyl-2-hydroxybenzyl)resorcin,
2,6-bis(2,4-dihydroxybenzyl)-3,4-dimethylphenol,
2,6-bis[3-(2-hydroxy-5-methylbenzyl)-2,5-dimethyl-4-hydroxybenzyl]-3,4-dimethylphenol,
4,6-bis(α-methyl-4-hydroxybenzyl)pyrogallol,
4,4′-[1-{4-[1-(3,5-bis(4-hydroxybenzyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[2,6-bis( 4-hydroxybenzyl)phenol],
4,4′-[1-{4-[1-(3,5-bis(4-hydroxy-3-methylbenzyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[2, 6-bis(4-hydroxy-3-methylbenzyl)phenol],
4,4′-[1-{4-[1-(3,5-bis(3,5-dimethyl-4-hydroxybenzyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[ 2,6-bis(3,5-dimethyl-4-hydroxybenzyl)phenol],
4,4′-[1-{4-[1-(3,5-bis(4-hydroxy-2,3,6-trimethylbenzyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene] bis[2,6-bis(4-hydroxy-2,3,6-trimethylbenzyl)phenol],
bis[5-(2,4-dihydroxybenzyl)-4-hydroxy-3-methylphenyl]methane, bis[3-(2,4-dihydroxybenzyl)-2,5-dimethyl-4-hydroxyphenyl]methane,
bis[3-(2,4-dihydroxy-3-methylbenzyl)-2,5-dimethyl-4-hydroxyphenyl]methane,
bis[5-(4-hydroxybenzyl)-2,3,4-trihydroxyphenyl]methane,
1,1-bis[5-(4-hydroxybenzoyl)-2,3,4-trihydroxyphenyl]ethane,
3,3′,5,5′-tetrakis(4-hydroxybenzyl)-4,4′-dihydroxybiphenyl,
3,3′,5,5′-tetrakis(4-hydroxy-3-methylbenzyl)-4,4′-dihydroxybiphenyl,
3,3′,5,5′-tetrakis(2-hydroxy-5-methylbenzyl)-4,4′-dihydroxybiphenyl,
3,3′,5,5′-tetrakis(3,5-dimethyl-4-hydroxybenzyl)-4,4′-dihydroxybiphenyl,
bis[3-(α,α-bis(4-hydroxy-3-methylphenyl)methyl-4-hydroxyphenyl]methane,
bis[3,5-bis(2-hydroxy-5-methylbenzyl)-4-hydroxyphenyl]methane,
4,4′,4″-ethylidinetris{[2-(2-hydroxy-5-methyl)benzyl]-6-methylphenol},
2,2-bis[3,5-bis(2-hydroxy-5-methylphenylmethyl)phenyl]propane,
bis[3-(α,α-bis(2,5-dimethyl-4-hydroxyphenyl)methyl-4-hydroxyphenyl]methane,
bis[5-(3,5-dimethyl-4-hydroxybenzyl)-2,3,4-trihydroxyphenyl]methane,
bis[3-(2,3,4-trihydroxybenzyl)-2,5-dimethyl-4-hydroxyphenyl]methane,
1,1-bis[3-(2,3,4-trihydroxybenzyl)-5-cyclohexyl-4-hydroxyphenyl]cyclohexane,
1,8,15,22-tetranonyl-3,5,10,12,17,19,24,26-octahydroxy[1,1,1,1]-metacyclophane,
4,4′-[1-{4-[1-(3,5-bis(4-hydroxy-2-methylbenzyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[2, 6-bis(4-hydroxy-2-methylbenzyl)phenol],
4,4′-[1-{4-[1-(3,5-bis(2-hydroxy-5-methylbenzyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[2, 6-bis(2-hydroxy-5-methylbenzyl)phenol],
4,4′-[1-{4-[1-(3,5-bis(3-ethyl-4-hydroxybenzyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[2, 6-bis(3-ethyl-4-hydroxybenzyl)phenol],
4,4′-[1-{4-[1-(3,5-bis(3,5-dimethyl-2-hydroxyphenyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[ 2,6-bis(3,5-dimethyl-2-hydroxyphenyl)phenol],
4,4′-[1-{4-[1-(3,5-bis(4-hydroxy-3-isopropylphenyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[2, 6-bis(4-hydroxy-3-isopropylphenyl)phenol],
bis[3-(α,α-bis(3,5-dimethyl-4-hydroxyphenyl)methyl-4-hydroxyphenyl]methane,
bis[3-(α,α-bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)methyl-4-hydroxyphenyl]methane,
4,4′-[4-hydroxy-3,5-bis(2-hydroxybenzyl)methylene]bis[2,6-bis(2-hydroxybenzyl)]phenol,
4,4′-[4-hydroxy-3,5-bis(4-hydroxybenzyl)methylene]bis[2,6-bis(4-hydroxybenzyl)]phenol,
4,4′,4″-ethylidinetris[2,6-bis(2-hydroxybenzyl)phenol],
4,4′,4″-ethylidinetris[2,6-bis(4-hydroxybenzyl)phenol],
2,2-bis[3,5-bis(4-hydroxy-3-methylbenzyl)-4-hydroxyphenyl]propane,
1,8,15,22-tetraethyl-3,5,10,12,17,19,24,26-octahydroxy[1,1,1,1]-metacyclophane,
α,α′,α″,α′″-tetrakis(3,5-dimethyl-4-hydroxyphenyl)-1,4-dimethylbenzene,
4,4′-[1-{4-[1-(3,5-bis(2-hydroxy-5-isopropylphenyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[2, 6-bis(2-hydroxy-5-isopropylphenyl)phenol],
4,4′-[1-{4-[1-(3,5-bis(4-hydroxy-2,3,5-trimethylphenyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene] bis[2,6-bis(4-hydroxy-2,3,5-trimethylphenyl)phenol],
4,4′-[1-{4-[1-(3,5-bis(3-sec-butyl-4-hydroxyphenyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[ 2,6-bis(3-sec-butyl-4-hydroxyphenyl)phenol],
4,4′-[1-{4-[1-(3,5-bis(3-tert-butyl-4-hydroxyphenyl)-4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bis[ 2,6-bis(3-tert-butyl-4-hydroxyphenyl)phenol],
2,6-bis{[3-(2,4-dihydroxybenzyl)-2,5-dimethyl-4-hydroxy]benzyl}-4-methylphenol,
1,1-bis[5-(2,4-dihydroxybenzyl)-3-cyclohexyl-4-hydroxyphenyl]cyclohexane,
1,1-bis[5-(2,3,4-trihydroxybenzyl)-3-cyclohexyl-4-hydroxyphenyl]cyclohexane,
2,2-bis[4,4',4'',4'''-tetrakis(3,5-dihydroxymethyl-4-hydroxyphenyl)cyclohexyl]propane and the like.

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

Examples of the acidic phosphoric ester compounds include methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, isodecyl acid phosphate, isotridecyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, monobutyl phosphate, dibutyl phosphate, monoisodecyl phosphate, bis(2-ethylhexyl) phosphate and the like.

A compound having a phenolic hydroxyl group can exhibit the most effective thermochromic properties, but aromatic carboxylic acids and aliphatic carboxylic acids having 2 to 5 carbon atoms, carboxylic acid metal salts, acidic phosphate esters and metals thereof Compounds selected from salts, 1,2,3-triazoles and derivatives thereof, and the like may also be used.

The electron-accepting compound is not only the reversible thermochromic composition of the present invention in which a fluorane derivative having a specific structure is applied as an electron-donating color-developing organic compound, but also conventionally known phthalide compounds, fluoran compounds, and stilinoquinoline compounds. , diazarhodamine lactone compounds, pyridine compounds, quinazoline compounds, and bisquinazoline compounds.
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.
In addition, examples of fluoran compounds include aminofluoran compounds, alkoxyfluoran compounds, and derivatives thereof.

These compounds are exemplified below.
3,3-bis(4-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 also a substituent on the phenyl group forming the lactone ring (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 (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.
When applying the above compound to microencapsulation and secondary processing, since low molecular weight compounds evaporate out of the capsules when subjected to high heat treatment, in order to stably hold them in the capsules, a compound containing 10 or more carbon atoms Compounds are preferably used.
As alcohols, aliphatic monohydric saturated alcohols having 10 or more carbon atoms are effective, and specific examples include decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, and hexadecyl. alcohol, heptadecyl alcohol, octadecyl alcohol, eicosyl alcohol, docosyl alcohol and the like.

As esters, esters having 10 or more carbon atoms are effective, and any combination of monohydric carboxylic acid having aliphatic and alicyclic or aromatic ring and monohydric alcohol having aliphatic and alicyclic or aromatic ring Esters obtained from any combination of polycarboxylic acids having aliphatic and alicyclic or aromatic rings and monohydric alcohols having aliphatic and alicyclic or aromatic rings, aliphatic and alicyclic Alternatively, esters obtained from any combination of a monovalent carboxylic acid having an aromatic ring and a polyhydric alcohol having an aliphatic, alicyclic or aromatic ring can be mentioned, specifically ethyl caprylate, octyl caprylate, capryl Stearyl acid, myristyl caprate, docosyl caprate, 2-ethylhexyl laurate, n-decyl laurate, 3-methylbutyl myristate, cetyl myristate, isopropyl palmitate, neopentyl palmitate, nonyl palmitate, cyclohexyl palmitate, stearin n-butyl acid, 2-methylbutyl stearate, 3,5,5-trimethylhexyl stearate, n-undecyl stearate, pentadecyl stearate, stearyl stearate, cyclohexylmethyl stearate, isopropyl behenate, hexyl behenate, behene Lauryl acid, behenyl behenate, cetyl benzoate, p-tert-butyl stearyl benzoate, dimyristyl phthalate, distearyl phthalate, dimyristyl oxalate, dicetyl oxalate, dicetyl malonate, dilauryl succinate, dilauryl glutarate, adipine diundecyl acid, dilauryl azelate, di-(n-nonyl) sebacate, dineopentyl 1,18-octadecylmethylenedicarboxylate, ethylene glycol dimyristate, propylene glycol dilaurate, propylene glycol distearate, hexylene glycol dipalmitate, 1,5-pentanediol distearate, 1,2,6-hexanetriol trimyristate, 1,4-cyclohexanediol didecyl, 1,4-cyclohexanedimethanol dimyristate, xylene glycol dicaprinate, xylene glycol distearate and the like.

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

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. is 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, 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, adipate N-butylamide, glutaric acid N-butylamide, malonic acid N-butylamide, adipic acid N-octylamide, adipic acid and N-dodecylamide.

〔式中、Ｒ_１は水素原子又はメチル基を示し、ｍは０～２の整数を示し、Ｘ_１、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 represents an integer of 1 to 3, X and Y each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carbon An alkoxy group of numbers 1 to 4 and a 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).

[In the formula, 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; 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 represents 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; 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).

[In the formula, R represents either an alkyl group having 3 to 18 carbon atoms or an aliphatic acyl group having 3 to 18 carbon atoms, X represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or 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).

[In the formula, R represents an alkyl group having 4 to 22 carbon atoms, an alkenyl group having 4 to 22 carbon atoms, a cycloalkylalkyl group, or a cycloalkyl group, and X represents a hydrogen atom, an alkyl group, an alkoxy group, or a halogen Y represents any one of a hydrogen atom, an alkyl group, an alkoxy group and a halogen atom; n represents 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、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 represents any one of an alkyl group having 3 to 18 carbon atoms, a cycloalkylalkyl group having 6 to 11 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, and an alkenyl group having 3 to 18 carbon atoms, X is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a halogen atom; Y is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, or an ethoxy group; , represents 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。 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).

[In the formula, 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, X is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, group, methoxy group, ethoxy group, halogen atom, 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 Diesters with acids can be exemplified.

The reversible thermochromic composition is a compatible body containing the above-mentioned (a), (b), and (c) components as essential components, and the ratio of each component varies depending on the concentration, color change temperature, color change form, and each component. Although it depends on the type, the component ratio at which the desired properties are generally obtained is 0.1 to 100, preferably 0.1 to 50, more preferably 0.1 to 50, more 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).

Furthermore, various light stabilizers can be added as required.
The light stabilizer is contained in order to prevent photodegradation of the reversible thermochromic composition consisting of components (a), (b) and (c). It is contained in a proportion of up to 24% by mass, preferably 0.3 to 16% by mass. Among the light stabilizers, the ultraviolet absorber effectively cuts ultraviolet rays contained in sunlight or the like, thereby preventing photodegradation caused by the excited state due to the photoreaction of the component (a). In addition, antioxidants, singlet oxygen quenchers, superoxide anion quenchers, ozone quenchers and the like suppress the oxidation reaction caused by light.
The light stabilizers may be used alone, or two or more of them may be used in combination.

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 conventionally 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, suspension in air. There are a coating method, a spray-drying method, and the like, 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 encapsulating in the microcapsules, a chemically and physically stable pigment can be constructed, and the practical particle size range is 0.01 to 50 μm, preferably 0.1 to 30 μm, more preferably 0.5 to 20 μm. satisfy sex.
For the measurement of the average particle size, the particle area is determined using the image analysis type particle size distribution measurement software "MacView" manufactured by Mountec, and the projected area circle equivalent diameter (Heywood diameter) is calculated from the area of the particle area. It is a value measured as an average particle diameter of particles equivalent to a sphere of equal volume based on the calculated value.
In addition, when the particle diameter of all or most of the particles exceeds 0.2 μm, an isovolumetric sphere is measured by the Coulter method using a particle size distribution analyzer (manufactured by Beckman Coulter, Inc., product name: Multisizer 4e). It can also be measured as the mean particle size of the equivalent particles.

The discoloration of the reversible thermochromic pigment will be described.
The reversible thermochromic pigment is completely colored when it reaches the complete coloring temperature (t ₁ ) by lowering the temperature from the bleached state, and reaches the completely bleaching temperature (t ₄ ) by raising the temperature from the colored state. It is a completely decolorized pigment.
Specifically, in FIG. 2, the hysteresis characteristic in the color density-temperature curve of the reversible thermochromic pigment is represented by the color density on the vertical axis and the temperature on the horizontal axis. Changes in color density due to temperature changes progress along the arrows. Here, _t4 is the point indicating the density at the temperature at which the color reaches a completely decolored state (hereinafter referred to as the complete decoloring temperature), and _t3 is the temperature at which the color begins to be decolored (hereinafter referred to as the decoloring start temperature). ), _t2 is the point indicating the density at the temperature at which color starts to develop (hereinafter referred to as the color development start temperature), and _t1 is the temperature at which the color is completely developed (hereinafter referred to as the complete color development temperature (referred to as ).
In addition, the vertical distance between the upper straight line between t ₁ and t ₃ and the lower straight line between t ₂ and t ₄ is a scale showing the color change contrast, and the vertical line between t ₁ and t ₂ and the vertical line between t ₃ and t The distance between the vertical line and the median value between ₄ is the temperature width indicating the degree of hysteresis (hereinafter referred to as hysteresis width ΔH), and the larger the ΔH value, the easier it is to maintain each state before and after discoloration. .
Here, the difference between _t4 and _t3 , or the difference between _t2 and _t1 (Δt) is a measure of the color change sensitivity.

As an example, visual changes in colorant groups A and B having different hues will be specifically described with reference to the color density-temperature curve in FIG. For the sake of convenience, the low-temperature erasable colorant group A is called a reversible thermochromic pigment A, and the high-temperature erasable colorant group B is called a reversible thermochromic pigment B.
One reversible thermochromic pigment B (high-temperature erasable coloring agent group B) is placed on the higher temperature side than the complete erasing temperature (t ₄ ) of one reversible thermochromic pigment A (low-temperature erasing-side coloring agent group A). In order to satisfy the complete color erasing temperature (t′ ₄ ) [hereinafter, the reversible thermochromic pigment B is referred to as (t′) to distinguish it from the reversible thermochromic pigment A], the reversible thermochromic pigments A and B are When the temperature is raised from the state of coloring (1) in which both colors are developed and reaches the complete decoloring temperature (t ₄ ), the reversible thermochromic pigment A is decolorized to become colored (2), and the complete decoloring temperature When (t′ ₄ ) is reached, the reversible thermochromic pigment B is decolorized, so that a color change from coloring (2) to decoloring is visually recognized.
When the temperature is lowered to reach the complete coloring temperature (t ₁ =t' ₁ ), the reversible thermochromic pigment A and the reversible thermochromic pigment B develop colors and return to coloring (1).
Incidentally, by adding a non-discoloring coloring agent, the color change of coloring (1), coloring (2), and coloring (3) can be visually recognized, and three types of handwriting can be visually recognized.

Further, as another example _, specifically explaining with reference to FIG. In order to satisfy t′ ₄ ), the temperature is raised from the state of coloring (1) in which both the reversible thermochromic pigments A and B develop color, and when the complete color disappearance temperature (t ₄ ) is reached, the reversible thermochromic pigment When A is decolored and becomes colored (2) and reaches the complete decoloring temperature (t′ ₄ ), the reversible thermochromic pigment B is decolored, so that the color change from coloring (2) to decoloring occurs. visible.
When the temperature is lowered to reach the complete coloring temperature (t' ₁ ), the reversible thermochromic pigment B develops color and returns to coloring ( ₂ ). Color-changing pigment A develops color and returns to coloring (1).

Further, as another example, specifically explaining with reference to _FIG . In order to satisfy t′ ₄ ), the temperature is raised from the state of coloring (1) in which both the reversible thermochromic pigments A and B develop color, and when the complete color disappearance temperature (t ₄ ) is reached, the reversible thermochromic pigment When A is decolored and becomes colored (2) and reaches the complete decoloring temperature (t′ ₄ ), the reversible thermochromic pigment B is decolored, so that the color change from coloring (2) to decoloring occurs. visible.
When the temperature is lowered to reach the complete coloring temperature (t' ₁ ), the reversible thermochromic pigment B develops color and returns to coloring ( ₂ ). Color-changing pigment A develops color and returns to coloring (1).

Furthermore, as another example _, specifically explaining with reference to FIG. In order to satisfy t′ ₄ ), the temperature is raised from the state of coloring (1) in which both the reversible thermochromic pigments A and B develop color, and when the complete color disappearance temperature (t ₄ ) is reached, the reversible thermochromic pigment When A is decolored and becomes colored (2) and reaches the complete decoloring temperature (t′ ₄ ), the reversible thermochromic pigment B is decolored, so that the color change from coloring (2) to decoloring occurs. visible.
When the temperature is lowered to reach the complete coloring temperature (t ₁ ), the reversible thermochromic pigment A develops color and becomes colored ( ₃ ). Pigment B develops color and returns to coloring (1).

In any of the above cases, the reversible thermochromic pigment _B (colorant _group By having the complete discoloration temperature (t′ ₄ ) (T _B ) of B), the color change can be clearly visually recognized, and is preferably 10° C. or higher, more preferably 15° C. or higher.
Furthermore, by having the complete decoloring temperature (t′ ₄ ) of the reversible thermochromic pigment B 5 to 70° C. higher than the complete decoloring temperature (t ₄ ) of the reversible thermochromic pigment A, color change , preferably 10 to 60°C, more preferably 15 to 50°C.
In the case of discoloring due to frictional heat generated by a friction body, which will be described later, the reversible heat is 15 to 40 ° C., preferably 20 to 35 ° C. higher than the complete discoloration temperature (t ₄ ) of the reversible thermochromic pigment A. Due to having the complete discoloration temperature (t′ ₄ ) of the color-changing pigment B, it is easy to develop a color change due to frictional heat.
Further, the reversible thermochromic pigment A has a complete discoloration temperature (t ₄ ) of 50° C. or higher, preferably 55° C. or higher, more preferably 60° C. or higher, and a complete coloring temperature (t ₁ ) of 0° C. or lower, preferably 0° C. or lower. is -5 ° C. or lower, more preferably -10 ° C. or lower, and the complete color development temperature (t' ₁ ) of the reversible thermochromic pigment B is 0 ° C. or lower, preferably -5 ° C. or lower, more preferably -10 ° C. or lower. By being, it becomes easy to hold|maintain the discolored state at normal temperature.

Next, the ink composition containing the colorant that becomes decolorized by heating will be described.
The ink composition contains antioxidants, ultraviolet absorbers, infrared absorbers, solubilizers, antiseptic/antifungal agents, non-thermochromic dyes, and Various additives such as pigments can be added.

As a medium, water and, if necessary, a water-soluble organic solvent are used.
Examples of the water-soluble organic solvent include glycols such as glycerin, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,3-butylene glycol, ethylene glycol monomethyl ether, lower alkyl ethers thereof, 2-pyrrolidone, N- Examples include vinylpyrrolidone, and glycerin and propylene glycol are preferably used.

Examples of the thickener include xanthan gum, welan gum, succinoglycan (average molecular weight of about 100 to 8 million), which is an organic acid-modified heteropolysaccharide composed of glucose and galactose, guar gum, locust bean gum and its derivatives, hydroxy Ethyl cellulose, alginic acid alkyl esters, polymers with a molecular weight of 100,000 to 150,000 mainly composed of alkyl esters of methacrylic acid, glycomannan, thickening polysaccharides with gelling ability extracted from seaweed such as agar and carrageenan, benzylidene sorbitol and benzylidene xylitol or their derivatives, crosslinkable acrylic acid polymer, inorganic fine particles, polyglycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene lanolin/lanolin alcohol Examples include nonionic surfactants with an HLB value of 8 to 12, such as beeswax derivatives, polyoxyethylene alkyl ethers, polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, fatty acid amides, and salts of dialkyl or dialkenyl sulfosuccinic acid. can be used alone or in combination.
As the thickener, an alkali-soluble acrylic emulsion is preferably used.
When an alkali-soluble acrylic emulsion is used as the thickener, the pH of the ink composition is adjusted to 6-11, preferably 7-11, more preferably 7-10.

Furthermore, a binder resin may be added for the fixation of the impression and the adjustment of viscosity.
The binder resin is selected from resin emulsions, alkali-soluble resins, and water-soluble resins.
Examples of the resin emulsion include polyacrylic acid ester, styrene-acrylic acid copolymer, polyvinyl acetate, ethylene-vinyl acetate copolymer, ethylene-vinyl chloride copolymer, methacrylic acid-maleic acid copolymer, ethylene- Aqueous dispersions of methacrylic acid copolymers, α-olefin-maleic acid copolymers, polyesters, polyurethanes, etc., and examples of the alkali-soluble resins include styrene-maleic acid copolymers and ethylene-maleic acid copolymers. , styrene-acrylic acid copolymers, and the like, and the water-soluble resins include polyvinyl alcohol, polyvinyl butyral, and the like, and can be used singly or in combination of two or more.

In addition, additives such as pH adjusters, preservatives and antifungal agents can be added as necessary.
Examples of the pH adjuster include inorganic salts such as ammonia, sodium carbonate, sodium phosphate, sodium hydroxide and sodium acetate, and organic basic compounds such as water-soluble amine compounds such as triethanolamine and diethanolamine.
Examples of the antiseptic or antifungal agent include phenolic acid, sodium salt of 1,2-benzisothiazolin-3-one, sodium benzoate, sodium dehydroacetate, potassium sorbate, propyl parahydroxybenzoate, 2,3,5,6 -tetrachloro-4-(methylsulfonyl)pyridine and the like.
In addition, antifoaming agents such as fluorine-based surfactants, nonionic, anionic, cationic surfactants, and dimethylpolysiloxane, which improve solvent permeability, can also be added.
In addition, a non-thermochromic dye or pigment is blended in the ink composition to form a thermochromic image exhibiting color (1) and color (2) to color (3) alternation with a change in temperature. It can also be configured to

The ink composition has an ink viscosity of 3,000 to 10,000 mPa·s, preferably 3,500 to 7,000 mPa·s, more preferably 4,000 to 6,000 mPa·s, measured at 25° C. and 6 rpm using a BL viscometer, and has a thixotropic (ink viscosity measured at 6 rpm/ink viscosity measured at 60 rpm) is 1.1 to 2.5, preferably 1.2 to 2.0. can satisfy the application.
If the ink viscosity is less than 3000 mPa·s, the impression formed on paper using the ink composition tends to blur. If it exceeds 10,000 mPa·s, the fluidity of the microcapsule pigment in the continuous pores is insufficient, and smooth flow of the ink composition onto the printing surface cannot be ensured, resulting in the formation of unclear impressions in continuous stamping operations.
When the thixotropic index is less than 1.1, the impression formed on paper using the ink composition tends to bleed. smooth flow of the ink composition cannot be ensured, and a vague impression is formed by continuous stamping operations.

The thermochromic ink composition for stamps has a color difference ΔE ^* _ab of 7 or less, preferably 6 or less, more preferably 6 or less, when the coated portion is uniformly applied to JIS P3201 writing paper A and is heat-erased from the writing paper A. By setting the value to 5 or less, the residual color after erasing the imprint is difficult to see, and the contrast between the handwriting and the erased part becomes clear, so when re-stamping the erased part, a clear imprint can be seen. It becomes a valuable ink composition.
Incidentally, in the present invention, the size of the above-described color difference is also called residual color.

The color difference ΔE ^* _ab is a value obtained by heating and erasing a portion of the thermochromic ink composition evenly applied to JIS P3201 writing paper A, and measuring the decolored portion with a commercially available measuring device (writing paper (corrected by the white portion of A), and in the present invention, it was measured with a fluorescence spectrodensitometer FD-7 manufactured by Konica Minolta.
When the color difference ΔE ^* _ab between the writing paper A (blank paper) and the decolored portion of the ink is 7 or less, the decolored state of the ink is hardly visible as a residual color, and coloring using two types of coloring agents (1 ) to coloring (2), the hue of coloring (2) can be clearly displayed.

Further, when a plurality of types of coloring agents with different hues are used and are composed of one of two types of decoloring temperatures T _A and T _B (T _A <T _B ), the hue at the time of stamping, The hue immediately after being heated to _TA or higher is different, and the color difference ΔE ^* _ab between the stamp imprint and writing paper A immediately after being heated to _TB or higher is 7 or less, preferably 6 or less, more preferably 5 or less. By doing so, in the two-stage color change ink that changes color from coloring (1) to coloring (2) and further to the decolored state, the residual color when the imprint is decolored (when all the coloring agents are decolored) is difficult to see. Become. As a result, the ink composition has high stamp erasability and a high commercial value in which a clear impression can be visually recognized when re-stamping on a decolored portion.

Further, when the coloring agent is composed of a low-temperature erasing coloring agent group A having a decoloring temperature T _A and a high temperature erasing coloring agent group B having a decoloring temperature T _B , decoloring in each coloring agent group By paying attention to the residual color of time, it was found that when heat is applied to the seal impression, the contrast between the discolored state and the decolored state becomes excellent at each temperature.
Specifically, the color difference (residual color) ΔE ^* _ab (A) with respect to the surface of the paper when decolorized is set to 10 or less in the impression stamped on the writing paper A using the ink of the low-temperature erasable colorant group A alone. As a result, the hue of the coloring (2) developed only by the coloring agent group B is clearly expressed.

In particular, when the coloring agent group A having the above color difference is 70% by mass or less, preferably 60% by mass or less, of the total amount of the coloring agent, the residual color ΔE ^* _ab of the entire ink after decoloring can be easily obtained regardless of the hue. It becomes possible to adjust to 7 or less. Further, preferably, by making it 50% by mass or less, the proportion of the coloring agent group B is increased and the residual color of the coloring agent group A is reduced, so that the hue of coloring (2) is likely to be clearly expressed. . Therefore, in the two-stage color change ink that changes color from colored (1) to colored (2) and further to colorless, the contrast at the time of color change is high and clear, and the residual color is difficult to see when the stamp is erased. and is particularly useful.

Furthermore, the color difference ΔE ^* _ab from the decolorized portion of the ink is 7 or less, and the color difference (remaining By setting ΔE ^* _ab (B) to 10 or less, it is possible to form a seal impression in which the hue of the coloring (2) is clear and in which the residual color is difficult to be visually recognized in the erased state of the seal after heating. .

In the above configuration, if the residual color ΔE ^* _ab (A) of the colorant group A on the low-temperature erasing side is 10 or less, the residual color ΔE ^* _ab (A) when the colorant group A is decolorized is Even if it is mixed with the hue of the coloring agent group B in the colored state, it does not inhibit the hue of the coloring agent group B, and is mixed with the residual color ΔE ^* _ab (B) of the high temperature erasing side coloring agent group B in the decolored state. When they are exposed to each other, the remaining colors [ΔE ^* _ab (A), ΔE ^* _ab (B)] are visually fainter than when they are viewed alone. Therefore, the imprint after discoloration of the imprint in the first stage is clear, and the imprint can be clearly seen when re-imprinting in the second stage of discoloration. become things.

The thermochromic ink composition is used as an ink composition for a stamp pad and a stamp ink composition provided with a stamp material having continuous pores.
A stamp pad is obtained by impregnating a stamp pad with the ink composition for a stamp pad to supply the ink composition to the stamp surface of the stamp to be brought into contact with the stamp pad, or the ink composition for a stamp provided with a stamp material having continuous pores is provided with continuous pores. The stamp is obtained by impregnating the impression material of the stamp provided with the stamp material.
A stamp having a stamp material with continuous pores is made by impregnating a rubber-like elastic body having continuous pores, which is the stamp material, with an ink composition. Transfer to the surface and the surface shape of the stamp is transferred. Areas where transfer is not desired are recessed or their openings are closed to prevent the ink composition from adhering to the target surface.
Examples of the surface shape of the stamp include dates, symbols, characters such as "confidential", "CONFIDENTIAL", "completed", and "accepted".
The stamp material having continuous pores is preferably placed in the stamp substrate so that the stamp surface is exposed, and the exposed surface is preferably provided with a cap to prevent the ink composition from drying out when not in use or from being contaminated by accidental contact.
An ink reservoir for supplying an ink composition to the stamp material may be provided at the rear of the stamp material having continuous pores to increase the number of times of stamping.
The stamp material may be previously impregnated with the ink composition and attached to the stamp, or the stamp material attached to the stamp material may be impregnated with the ink composition.
When impregnating the ink composition into the stamp material attached to the stamp material, the ink composition can be impregnated from the front surface of the stamp material, or the ink can be impregnated from the rear surface of the stamp material.
Similarly, in the case of a stamp having an ink reservoir, the ink reservoir may be filled with ink in advance, or the ink reservoir of the stamp provided with the stamp material and the ink reservoir may be filled with the ink composition.

The imprint formed from the thermochromic ink composition can be discolored by a cooler or a heater.
Examples of the cooling device include a cold-heat discoloring device using a Peltier element, a cold-heat discoloring device filled with a refrigerant such as cold water or ice chips, and a refrigerator or freezer.
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, and a hair dryer. Used.

As the friction member, an elastic body such as an elastomer or a plastic foam, which is highly elastic and can generate frictional heat by generating moderate friction when rubbed, is suitable.
An eraser can be used to rub the seal impression, but since eraser shavings are generated during the rubbing, the above-mentioned friction member that hardly generates erasing shavings is preferably used.
As the material of the friction member, silicone resin, styrene resin (styrene ethylene butadiene styrene block copolymer, etc.), polyester resin, or the like is used.
As for the friction member, a stamp set can be obtained by combining a stamp and a separate member (friction body) having an arbitrary shape.

It should be noted that it is also possible to provide two or more types of the friction member. In this case, due to friction with the paper surface, one side generates frictional heat in the range of TA to _TB , which is the seal discoloration temperature, and the other side generates frictional heat equal to or higher than _TB , which _is the seal discoloration temperature. preferable. By doing so, it is possible to easily and reliably develop a desired discoloration stage according to each friction member without worrying about the amount of force applied when rubbing the imprint.

Examples are described below. The parts in the examples are parts by mass, and the average particle diameter was measured by the Coulter method using a particle size distribution analyzer (manufactured by Beckman Coulter, Inc., product name: Multisizer 4e). value.
Further, the color difference ΔE ^* _ab was measured by uniformly applying the ink composition to JIS P3201 writing paper A using a bar coater, then heating and decoloring the portion with a fluorescent spectrodensitometer FD-7 manufactured by Konica Minolta ( (calibrated with white portion of writing paper A).

Example 1
Preparation of reversible thermochromic pigment A (a) 9-ethyl(3-methylbutyl)amino-spiro[12H-benzo(a)xanthene-12,1'(3'H)isobenzofuran]-3'-one as component Reversible thermochromic composition a consisting of 1 part, 5 parts of 2,2-bis(4'-hydroxyphenyl)hexafluoropropane as component (b), and 50 parts of 4-benzyloxyphenylethyl caprate as component (c) was encapsulated in microcapsules to prepare a reversible thermochromic pigment A.
The reversible thermochromic pigment A has an average particle size of 2.0 μm, a complete color erasing temperature (t ₄ ) of 64° C., and a complete coloring temperature (t ₁ ) of −14° C., and changes color from pink to colorless with temperature change. .

Preparation of Reversible Thermochromic Pigment B (a) 1 part of 2,6-bis(2,4-diethyloxyphenyl)-4-(4-bis(4-methylphenyl)aminophenyl)pyridine as component (b) A reversible thermochromic composition comprising 5 parts of 2,2-bis(4'-hydroxyphenyl)hexafluoropropane as a component and 50 parts of a diester of pimelic acid and 2-(4-benzyloxyphenyl)ethanol as a component (c). A reversible thermochromic pigment B was prepared by encapsulating the substance b in microcapsules.
The reversible thermochromic pigment B has an average particle size of 2.0 μm, a complete discoloration temperature (t′ ₄ ) of 78° C., and a complete color development temperature (t′ ₁ ) of −11° C., and changes color from orange to colorless with temperature change. do.

Preparation of thermochromic ink composition for stamp (see FIG. 4)
10 parts of the reversible thermochromic pigment A, 10 parts of the reversible thermochromic pigment B, 50.0 parts of glycerin, 1.5 parts of alkali-soluble acrylic emulsion [Rohm and Haas Japan Co., Ltd., trade name: Primal DR73] , triethanolamine 0.9 parts, polyvinylpyrrolidone 50% aqueous solution 10.0 parts, silicone antifoaming agent 0.2 parts, penetration leveling agent 0.5 parts, antiseptic agent 0.2 parts, water 16.7 parts The parts were mixed to obtain a thermochromic ink composition for stamps.
The ink viscosity measured at 25° C. and 6 rpm using a BL-type viscometer was 4700 mPa·s, the ink viscosity measured at 60 rpm was 2400 mPa·s, and the thixotropy (at 6 rpm The measured ink viscosity/ink viscosity measured at 60 rpm) was 1.95.

Measurement of Residual Color of Ink Composition 1 g of the thermochromic ink composition for stamping was placed on a piece of writing paper A according to JIS P3201, and the ink was uniformly applied using a 10 mil wire bar coater. After being sufficiently dried, the coating was heated in a constant temperature bath at 120° C. for 1 minute to obtain a coated article in which the ink was completely decolored. The color difference ΔE ^* _ab with respect to the surface of the paper was measured using a fluorescence spectrodensitometer, and the result was 2.28. Visually confirming the decolored portion, residual color was found to be very small.
In addition, the hue when the coated material in the first colored state was heated to 70° C. to make it orange (second colored state) was not different from the printed matter of ink composition B below, and was clearly visible. .

Measurement of residual color of reversible thermochromic pigment In the thermochromic ink composition for stamps, 20 parts of reversible thermochromic pigment A (i.e., removing reversible thermochromic pigment B and replacing with reversible thermochromic pigment A) ), the ink composition A is prepared, and 20 parts of the reversible thermochromic pigment B is added (that is, the reversible thermochromic pigment A is removed and replaced with the reversible thermochromic pigment B). Composition B was prepared.
1 g of each of the ink compositions A and B was placed on JIS P3201 writing paper A, and the ink was uniformly applied using a 10 mil wire bar coater, dried sufficiently, and then heated in a constant temperature bath at 120 ° C. for 1 minute. By doing so, coated materials A and B were obtained in which the ink was completely decolored.
When the color difference ΔE ^* _ab with respect to the paper surface was measured for the obtained coatings A and B using a fluorescence spectrodensitometer, the coatings A and B were 3.16 and 1.78, respectively. In addition, when the decolored portion was visually confirmed, there was very little residual color in any case.

Create a stamp (see Figure 7)
A stamp material 2 having continuous pores and a reservoir 6 were impregnated with the ink composition, fixed to a stamp substrate 3 so that the stamp surface of the stamp material was exposed, and a cap 5 was fitted to obtain a stamp 1 . A friction member 4 made of SEBS resin is provided at the rear end of the stamp base material 3 .
When the stamp 1 is repeatedly pressed against a target surface (paper), the ink composition smoothly flows out from the stamp surface of the stamp material and transfers to the target surface, thereby forming a clear impression continuously without blurring. was made.

Color Change Behavior of Imprint The imprint obtained with the stamp 1 exhibits a bright vermillion color, which is a mixture of the pigments A and B, at room temperature (25° C.). At 64° C., pigment A fades (t ₄ ) with no residual color, and vivid orange handwriting by pigment B is visible. It fades (t′ ₄ ) and becomes colorless.
When cooled from this state to -11°C, the pigment B completely develops color (t' ₁ ) and vivid orange handwriting is visible, and when the temperature reaches -14°C, the pigment A completely develops color (t ₁ ). As a result, a bright vermilion handwriting in which the pigment A and the pigment B were mixed was visually recognized.
The reversible state change from vivid vermilion to vivid orange to colorlessness can be properly visually distinguished by heating and cooling, and the variation of the gradual color change was rich.
As an example of use, a check for watering potted plants was performed as follows.
The stamp 1 is used to form a vivid vermilion "flower" pattern on a notebook, and when the potted flower is watered, the imprint is rubbed with the attached friction member 4 to create a bright orange pattern. I changed the color to a "flower" pattern. When the potted plant is watered again, the imprint can be further rubbed to make the "flower" pattern colorless. It was most suitable for decoloring and reprinting.

Examples 2-5, Comparative Examples 1-3
A thermochromic ink composition for stamps in the same manner as in the thermochromic ink composition for stamps, except that the reversible thermochromic pigment A (pigment group A) and the reversible thermochromic pigment B (pigment group B) are changed. was prepared to obtain a thermochromic stamp.
The pigment composition of each example and comparative example and the results of each color difference and residual color test are shown in the following table.
In addition, in the measurement of the residual color of Pigment Group A in Example 4, an ink composition was prepared by replacing Pigment B while maintaining the ratio of each thermochromic pigment constituting Pigment Group A.

The residual color test is performed by heating a first colored seal impression written on JIS P3201 white writing paper A with an attached friction body to a second colored state, and then further heating to make it a decolored state. Each handwriting was visually confirmed.
Each symbol is as follows.
⊚: The second colored state was visually recognized as vividly as that of the pigment group B alone, and almost no residual color was observed in the decolored state.
◯: The second colored state was clearly visible, and almost no residual color was observed in the decolored state.
x: Color mixture occurs and the second colored state is not clearly visible, and residual color is observed in the decolored state.

t ₁ , t' ₁ complete color development temperature t ₂ , t' ₂ color development start temperature t ₃ , t' ₃ decoloration start temperature t ₄ , t' ₄ complete decolorization temperature 1 stamp 2 stamp material 3 stamp substrate 4 friction member 5 cap 6 reservoir

Claims (9)

It contains two or more kinds of colorants that become decolorized by heating, the colorants have different hues, and two types of decolorization temperatures T _A and T _B (T _A <T _B ) are selected. Therefore, the hue of the ink applied to JIS P3201 writing paper A is different from the hue immediately after being heated to TA or more, and the residual color immediately after being heated to TB _or more is the color difference ΔE * ab from _writing ^paper _A. is 7 or less at
Furthermore, the coloring agent is composed of a low-temperature erasing coloring agent group A having a erasing temperature T _A and a high temperature erasing coloring agent group B having a erasing temperature T _B , and the low temperature erasing coloring agent group A A thermochromic ink composition for stamps, which has a residual color ΔE ^* _ab (A) of 10 or less on a paper surface when decolored by itself . 2. The high temperature erasable coloring agent group B has a residual color ΔE ^* _ab (B) of 10 or less with respect to the paper surface when the high temperature erasable coloring agent group B alone is decolored . Thermochromic ink composition for stamps as described. 3. The thermochromic ink composition for stamps according to claim 2 , wherein the difference in color erasing temperature between the low temperature erasable colorant group A and the high temperature erasable colorant group B is 5[deg.] C. or more. 4. The thermochromic ink composition for stamps according to any one of claims 1 to 3 , wherein the low-temperature erasable colorant group A accounts for 70% by mass or less of the total amount of the colorant. The thermochromic ink composition for stamps according to any one of claims 1 to 4, wherein the coloring agent is added in an amount of 10 to 40% by mass based on the total amount of the ink composition. The coloring agent comprises (a) an electron-donating color-developing organic compound, (b) an electron-accepting compound, and (c) a reaction medium for controlling the color reaction of (a) and (b). The thermochromic ink composition for stamps according to any one of claims 1 to 5 , which is a reversible thermochromic pigment obtained by encapsulating the composition in microcapsules. A stamp incorporating the thermochromic ink composition for a stamp according to any one of claims 1 to 6 . 8. The stamp according to claim 7 , comprising a friction member for discoloring the imprint of said stamp by frictional heat. 9. The stamp according to claim 8 , wherein said friction member consists of two types, one of which generates frictional heat in the range of T _A to T B and the other of which generates frictional heat of T _{B or} more by friction with the paper surface.

Images