JP7036583B2 - Multicolor discolorable ink composition for writing tools and writing tools using it - Google Patents

Description

The present invention relates to a multicolor discolorable water-based ink composition for writing tools and a writing tool using the same. More specifically, the present invention relates to a multicolor discolorable water-based ink composition for a writing tool, which can obtain handwriting showing various color changes due to a temperature change, and a writing tool using the same.

Conventionally, there have been disclosed ink compositions for writing tools that can obtain handwritings exhibiting a plurality of colors due to temperature changes (see, for example, Patent Document 1).
The handwriting obtained by writing with a writing tool filled with the ink composition is colored (1) to colored (2) due to a temperature change, further colored (3), or colored (1) to colored (2). Furthermore, it exhibits a multicolored color change to colorless.

Japanese Unexamined Patent Publication No. 2004-149726

The present invention pursues the color change of the handwriting obtained by the above-mentioned ink composition for writing tools exhibiting multicolor color change, and obtains a writing tool rich in vividness of each color before and after the color change and having high commercial value. It is an object of the present invention to provide a multicolor discolorable ink composition for writing tools and a writing tool using the same.

The present invention reversibly causes an electron transfer reaction between (a) an electron-donating color-developing organic compound, (b) an electron-accepting compound, and (c) the above-mentioned (a) and (b) components in a specific temperature range. A reversible thermochromic pigment A containing a reversible thermochromic composition a composed of a reaction medium to be generated, (a) an electron-donating color-developing organic compound, (b) an electron-accepting compound, and (c). At least a reversible thermochromic pigment B containing a reversible thermochromic composition b comprising a reaction medium that reversibly causes an electron transfer reaction by the components (a) and (b) in a specific temperature range, and the medium. When the reversible thermochromic pigments A and B reach the complete color development temperature (t ₁ ) by lowering the temperature from the decolorized state, they are completely in the color development state, and the temperature rise from the color development state causes the complete decolorization temperature (t ₄ ). It is a pigment showing a hysteresis curve that completely _decolorizes when it reaches A multicolor discolorable ink composition for a writing instrument, which has a decoloring temperature (t ₄ ) and is characterized in that the reversible thermochromic pigment B is a pigment having fluorescence at the time of color development, is a requirement.
Further, the (a) electron-donating color-developing organic compound in the reversible thermochromic pigment B is a compound selected from a pyridine compound, a quinazoline compound, a bisquinazoline compound, and a diazarodamine lactone compound. The reversible thermal discoloration pigment A has a complete decolorization temperature (t ₄ ) at a temperature 10 to 70 ° C. higher than the complete decolorization temperature (t ₄ ) of the reversible thermochromic pigment A. The complete decolorization temperature (t ₄ ) of the sex pigment A is 50 ° C. or higher, the complete color development temperature (t ₁ ) is 0 ° C. or lower, and the complete color development temperature (t ₁ ) of the reversible thermochromic pigment B is 0 ° C. The requirements are as follows.
Further, a writing tool containing the multicolor discolorable ink composition for a writing tool and a writing tool containing the multicolor discoloring ink composition for a writing tool and having a friction body are required.

The present invention has a complete decoloring temperature (t ₄ ) of the other reversible thermochromic pigment on the higher temperature side than the complete decoloring temperature (t ₄ ) of one reversible thermochromic pigment, and has a reversible thermochromic property. Since the pigment B is a pigment having fluorescence at the time of color development, it is rich in the vividness of each color before and after the color change, and it is possible to obtain a writing tool having high commercial value. We can provide the writing tools that we had.

It is a graph explaining the hysteresis characteristic in the color density | temperature curve of a reversible thermochromic composition. It is a graph explaining the hysteresis characteristic in the color density-temperature curve of the reversible thermochromic composition having color memory. Color concentration-temperature curve of reversible thermochromic pigment A and reversible thermochromic pigment B contained in the multicolor discolorable ink composition for writing tools of one embodiment of the present invention (pigment A: thin line, pigment B: thick line) Is shown. Color concentration-temperature curve of reversible thermochromic pigment A and reversible thermochromic pigment B contained in the multicolor discolorable ink composition for writing tools of another embodiment of the present invention (pigment A: thin line, pigment B: thick line) ) Is shown. Color concentration-temperature curve of reversible thermochromic pigment A and reversible thermochromic pigment B contained in the multicolor discolorable ink composition for writing tools of another embodiment of the present invention (pigment A: thin line, pigment B: thick line) ) Is shown. Color concentration-temperature curve of reversible thermochromic pigment A and reversible thermochromic pigment B contained in the multicolor discolorable ink composition for writing tools of another embodiment of the present invention (pigment A: thin line, pigment B: thick line) ) Is shown.

The reversible thermochromic compositions a and b are (a) an electron-donating color-developing organic compound, (b) an electron-accepting compound, and (c) a reaction medium that determines the temperature at which the color reaction of both of them occurs. Examples thereof include a heat-decoloring type (decoloring by heating and developing color by cooling) reversible thermochromic composition containing at least three essential components.
The reversible thermochromic composition changes color before and after a predetermined temperature (discoloration point), and is in a decolorized state in a temperature range above the high temperature side discoloration point and in a color development state in a temperature range below the low temperature side discoloration point. Presented, only one of the above states exists in a specific temperature range, and the other state is maintained as long as the heat or cold required for the state to develop is applied. However, it has a characteristic that the hysteresis width (ΔH) is relatively small, which returns to the original state when the application of the heat or cold heat is removed (see FIG. 1).
In addition, the shape of the curve showing a large hysteresis characteristic, that is, plotting the change in coloring density due to temperature change, decreases from the high temperature side of the discoloration temperature range, contrary to the case where the temperature rises from the low temperature side of the discoloration temperature range. The color changes by following a path that is significantly different from that of the case where the color is changed, and the color development state in the low temperature range below the complete color development temperature (t ₁ ) or the decolorization state in the high temperature range above the complete decolorization temperature (t ₄ ) , Reversible heat of heat decolorization type (decolorizes by heating and develops color by cooling) having color memory in a specific temperature range [temperature range between t ₂ and t ₃ (substantially two-phase holding temperature range)] A discolorable composition can also be applied (see FIG. 2).

The components (a), (b), and (c) will be specifically described below.
The component (a) of the present invention, that is, the electron-donating color-developing organic compound is a component that determines a color and is a compound that donates electrons to the component (b) that is a color developer to develop a color.
Examples of the electron-donating color-developing organic compound include a phthalide compound, a fluorine compound, a stirinoquinoline compound, a pyridine compound, a quinazoline compound, a bisquinazoline compound, and a diazarodamine lactone compound, and among them, because they have fluorescence at the time of color development. A pyridine compound, a quinazoline compound, a bisquinazoline compound, and a diazarodamine lactone-based compound are used, and the pyridine compound is preferably used.
As the pyridine 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-Durolidinyl) -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-Isoindrinylphenyl) -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,
And so on.

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-tetrahydroquinoline-6'-yl) -4-phenyloxy-quinazoline,
2- (1'-ethyl-2', 2', 4'-trimethyl-tetrahydroquinoline-6'-yl) -4-methyloxy-quinazoline,
2- (1', 2', 2', 4'-tetramethyl-tetrahydroquinoline-6'-yl) -4-phenyloxy-quinazoline,
2- (1'-ethyl-2'-methyl-tetrahydroquinoline-6'-yl) -4-phenyloxy-quinazoline,
2- (1', 3'-dimethylindoline-5'-yl) -4-phenyloxy-quinazoline,
2- (3', 4'-dimethylbenzomorpholine-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'-dimethylbenzomorpholine-7'-yl)-(2''-phenyloxyethyloxy) -quinazoline,
And so on.

As the bisquinazoline compound,
4,4'-(Ethylenedioxy) -bis [2- (4-diethylaminophenyl) -quinazoline],
4,4'-[Propenedioxy (1,3)]-bis [2- (4-diethylaminophenyl) -quinazoline],
4,4'-[Butrangeoxy (1,3)]-bis [2- (4-diethylaminophenyl) -quinazoline],
4,4'-[Butrangeoxy (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],
And so on.

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'-on,
2- (Di-n-Butylamino) -8- (Di-n-Butylamino) -4-Methyl-Spiro [5H- [1] Benzopyrano (2,3-g) Pyrimidine-5,1'(3') H) -Isobenzofuran] -3'-on,
2- (Di-n-butylamino) -8- (dimethylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1'(3'H) -iso Benzofuran] -3'-on,
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-N-i-Butylamino) -4-Methyl-Spiro [5H- [1] Benzopyrano (2,3-g) Pyrimidine-5,1 ′ (3 ′ H) -isobenzofuran] -3 ′-on,
2- (Di-n-butylamino) -8- (N-ethyl-N-i-amylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1'(3'H) -isobenzofuran] -3'-on,
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 ′-on,
2- (Di-n-butylamino) -8- (di-n-amylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1'(3'H) ) -Isobenzofuran] -3'-on,
2- (Di-n-butylamino) -8- (n-octylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1'(3'H) -Isobenzofuran] -3'-on,
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- (Morpholine) -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-Methylpiperadino) -8- (diethylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1'(3'H) -isobenzofuran] -3 '-on,
2- (Pyrrolidineo) -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'-on,
2- (diethylamino) -8- (diethylamino) -spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1'(3'H) -isobenzofuran] -3'-on,
2- (Di-n-Butylamino) -8- (Di-n-Butylamino) -Spiro [5H- [1] Benzopyrano (2,3-g) Pyrimidine-5,1'(3'H) -iso Benzofuran] -3'-on,
2- (N-ethyl-N-i-amylamino) -8- (N-ethyl-N-i-amylamino) -spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1'( 3'H) -isobenzofuran] -3'-on,
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-N-i-amylamino) -spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1'(3'H) ) -Isobenzofuran] -3'-on,
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'-on,
2- (Di-n-butylamino) -8- (diethylamino) -4-methyl-7-ethyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1'(3'H) ) -Isobenzofuran] -3'-on,
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'-on,
2- (Di-n-butylamino) -8- (N-ethyl-N-i-amylamino) -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1'(3'H) -isobenzofuran] -3'-on,
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'-on,
2- (Dimethylamino) -8- (diethylamino) -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1'(3'H) -isobenzofuran] -3' -on,
2- (i-Amilamino) -8- (diethylamino) -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1'(3'H) -isobenzofuran] -3 '-on,
2- (Pyrrolidineo) -8- (diethylamino) -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1'(3'H) -isobenzofuran] -3'- on,
2- (N-Methylpiperadino) -8- (diethylamino) -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1'(3'H) -isobenzofuran] -3 '-on,
2- (Morpholine) -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'-on,
2- [Di (2-methoxyethyl) amino] -8- (diethylamino) -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1'(3'H)- Isobenzofuran] -3'-on,
2- (Di-n-butylamino) -8- (diethylamino) -4- (4-methoxyphenyl) -spiro [5H- [1] benzopyrano (2,3-d) pyrimidine-5,1'(3') H) -Isobenzofuran] -3'-on,
2- (Di-n-Butylamino) -8- (diethylamino) -4- (4-chlorophenyl) -spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1'(3'H) ) -Isobenzofuran] -3'-on,
2- (Di-n-butylamino) -8- (diethylamino) -4- (4-methylphenyl) -spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1'(3') H) -Isobenzofuran] -3'-on,
2- [Di (2-ethoxyethyl) amino] -8- (dimethylamino) -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1'(3'H) -Isobenzofuran] -3'-on,
2- (diethylamino) -8-[(2-Methylphenyl) amino] -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1'(3'H) -iso Benzofuran] -3'-on,
2- (2,6-dimethylmorpholine) -8- (diethiamino) -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'-on,
And so on.

Examples of the electron-accepting compound of the component (b) include a group of compounds having an active proton, a group of pseudoacid compounds (not an acid, but a group of compounds that act as an acid in the composition to develop the color of the component (a)). There are compounds having electron vacancies and the like.
Examples of compounds having an active proton include monophenols to polyphenols as compounds having a phenolic hydroxyl group, and as its substituents, an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, a carboxy group and an ester thereof. Alternatively, those having an amide group, a halogen group and the like, bis-type and Tris-type phenols and the like, phenol-aldehyde condensed resins and the like can be mentioned. Further, it may be a metal salt of the compound having a phenolic hydroxyl group.
Specific examples are given below.
Phenol, o-cresol, tertiary butyl catechol, nonylphenol, n-octylphenol, n-dodecylphenol, n-stearylphenol, p-chlorophenol, p-bromophenol, o-phenylphenol, p-hydroxybenzoate n-butyl , P-Hydroxybenzoate n-octyl, resorcin, dodecyl phosphite, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfide, bis (3-allyl-4-hydroxyphenyl) sulfone, 4-hydroxy Phenyl-4-isopropoxyphenyl sulfone, 4-benzyloxyphenyl-4-hydroxyphenyl sulfone, 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) Hydroxyphenyl) n-heptane, 1,1-bis (4-hydroxyphenyl) n-octane, 1,1-bis (4-hydroxyphenyl) n-nonane, 1,1-bis (4-hydroxyphenyl) n- Decane, 1,1-bis (4-hydroxyphenyl) n-dodecane, 1,1-bis (4-hydroxyphenyl) -2-methylpropane, 1,1-bis (4-hydroxyphenyl) -3-methylbutane, 1,1-bis (4-hydroxyphenyl) -3-methylpentane, 1,1-bis (4-hydroxyphenyl) -2,3-dimethylpentane, 1,1-bis (4-hydroxyphenyl) -2- Ethylbutane, 1,1-bis (4-hydroxyphenyl) -2-ethylhexane, 1,1-bis (4-hydroxyphenyl) -3,7-dimethyloctane, 1,1-bis (4-hydroxyphenyl) cyclohexane , 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) Propane, 2,2-bis (4-hydroxyphenyl) n-butane, 2,2-bis (4-hydroxyphenyl) n-pentane, 2,2-bis (4-hydroxyphenyl) n-hexane, 2,2 -Bis (4-hydroxyphenyl) n-heptane, 2,2-bis (4-hydroxyphenyl) n-octane , 2,2-Bis (4-hydroxyphenyl) n-nonane, 2,2-bis (4-hydroxyphenyl) n-decane, 2,2-bis (4-hydroxyphenyl) n-dodecane, 2,2- Bis (4-hydroxyphenyl) ethyl propionate, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 2,2-bis (4-hydroxyphenyl) -4-methylhexane, 2,2- Bis (4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,3-bis [2- (4-Hydroxyphenyl) -2-propyl] benzene, bis (2-hydroxyphenyl) methane, 1,1,1-tris (4-hydroxyphenyl) ethane, 2,2-bis (3-methyl- 4-Hydroxyphenyl) butane, 4-t-butyl-2', 4'-dihydroxybenzophenone and the like.
The compound having a phenolic hydroxyl group can exhibit the most effective thermal discoloration property, but is an aromatic carboxylic acid, an aliphatic carboxylic acid having 2 to 5 carbon atoms, a carboxylic acid metal salt, an acidic phosphoric acid ester, and the like thereof. It may be a compound selected from a metal salt, 1,2,3-triazole and a derivative thereof.

The component (c) of the reaction medium that reversibly causes the electron transfer reaction by the components (a) and (b) in a specific temperature range will be described.
Examples of the component (c) include alcohols, esters, ketones, ethers, and acid amides.
When the compound is applied to microencapsulation and secondary processing, low molecular weight compounds evaporate outside the capsule when subjected to high heat treatment, so the number of carbon atoms is 10 or more in order to stably retain the compound in the capsule. Compounds are preferably used.
As alcohols, aliphatic monohydric saturated alcohols having 10 or more carbon atoms are effective, and specifically, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, and hexadecyl. Examples thereof include alcohols, heptadecyl alcohols, octadecyl alcohols, eicosyl alcohols, docosyl alcohols and the like.

As the esters, esters having 10 or more carbon atoms are effective, and any combination of a monovalent carboxylic acid having an aliphatic and an alicyclic or aromatic ring and a monovalent alcohol having an aliphatic and an alicyclic or aromatic ring is effective. Esters, aliphatic and alicyclic esters obtained from any combination of a polyvalent carboxylic acid having an aliphatic and alicyclic or aromatic ring and a monovalent alcohol having an alicyclic or alicyclic or aromatic ring. Alternatively, esters obtained from any combination of monovalent carboxylic acid having an aromatic ring and an aliphatic and polyvalent alcohol having an alicyclic or aromatic ring can be mentioned, and specific examples thereof include ethyl caprylate, octyl caprylate, and capryl. Stearyl acid, myristyl caprate, docosyl caprate, 2-ethylhexyl laurate, n-decyl laurate, 3-methylbutyl myristate, cetyl myristine, isopropyl palmitate, neopentyl palmitate, nonyl palmitate, cyclohexyl palmitate, stearer N-butyl acid, 2-methylbutyl stearate, 3,5,5-trimethylhexyl stearate, n-undecyl stearate, pentadecyl stearate, stearyl stearate, cyclohexylmethyl stearate, isopropyl behenate, hexyl behenate, behen Lauryl acid, behenyl behenyl, cetyl benzoate, p-tert-butyl stearyl benzoate, dimyristyl phthalate, disstearyl phthalate, dimyristyl oxalate, disetyl oxalate, disetyl malonate, dilauryl succinate, dilauryl glutarate, adipine Diundecyl acid, dilauryl azelaite, di- (n-nonyl) sebacate, dineopentyl 1,18-octadecylmethylene dicarboxylate, ethylene glycol dimyristate, propylene glycol dilaurate, propylene glycol distearate, hexylene glycol dipalmitate, 1,5-Pentanediol distearate, 1,2,6-hexanetrioltrimylstate, 1,4-cyclohexanediol didecyl, 1,4-cyclohexanedimethanol dimyristate, xylene glycol dicaprineate, xylene glycol Examples include distearate.

Also, esters of saturated fatty acids and branched fatty alcohols, esters of unsaturated fatty acids or fatty alcohols that are branched or branched from saturated fatty acids having branches or substituents, or esters of 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 capric acid, 3,5,5-trimethylhexyl laurate, 3,5,5-trimethylhexyl palmitate, 3,5,5-trimethylhexyl stearate, 2-methylbutyl caproate, 2-methylbutyl caprylate, 2-methylbutyl caprice, 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 capric acid, 2-methylpentyl laurate, 2-methylpentyl 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 lauric acid, 1-methylpentyl capric acid, palmitic acid 2-Methylhexyl, 2-methylhexyl stearate, 2-methylhexyl behenate, 3,7-dimethyloctyl laurate, 3,7-dimethyloctyl myristate, 3,7-dimethyloctyl palmitate, 3, stearate 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-fluoromyristine, cetyl butyrate, stearyl butyrate, behenyl butyrate And so on.

Further, in order to change the color by showing a large hysteresis characteristic with respect to the color density-temperature curve and to give color memory depending on the temperature change, it is described in Japanese Patent Publication No. 4-17154 and is not more than 5 ° C and less than 50 ° C. A carboxylic acid ester compound showing a ΔT value (melting point-cloud point), for example, a carboxylic acid ester containing a substituted aromatic ring in the molecule, a carboxylic acid containing an unsubstituted aromatic ring, and an ester of an aliphatic alcohol having 10 or more carbon atoms. , Esters containing cyclohexyl groups in molecules, fatty acids with 6 or more carbon atoms and unsubstituted aromatic alcohols or phenol esters, fatty acids with 8 or more carbon atoms and branched aliphatic alcohols or esters, dicarboxylic acids and aromatic alcohols or Esters of branched aliphatic alcohols, dibenzyl silicate, heptyl stearate, didecyl adipate, dilauryl adipate, dimyristyl adipate, disetyl adipate, distearyl adipate, trilaurin, trimyristin, tristea, dimyristin, distea, etc. Can be mentioned.

An odd aliphatic monohydric alcohol having 9 or more carbon atoms and a fatty acid ester compound obtained from an 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. Aliphatic ester compounds having a total carbon number of 17 to 23 obtained from an acid are also effective.
Specifically, n-pentadecyl acetate, n-tridecyl butyrate, n-pentadecyl butyrate, n-undecyl caproate, n-tridecyl caproate, n-pentadecyl caproate, n-nonyl caprylate, n-undecyl caprylate, N-Tridecyl caprylate, n-pentadecyl caprylate, n-heptyl capricate, n-nonyl caprice, n-undecyl caprice, n-tridecyl caprice, n-pentadecyl caprice, 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 eikosanoate, n-undersi eikosanoate, n-tridecyl eikosanoate, n-pentadecyl eikosanoate, behenic acid Examples thereof include n-nonyl, n-undecyl behenate, n-tridecyl behenate, n-pentadecyl behenate and the like.

As the ketones, aliphatic ketones having a total carbon number of 10 or more are effective, and 2-decanone, 3-decanone, 4-decanone, 2-undecanone, 3-undecanone, 4-undecanone, 5-undecanone, 2 -Dodecanone, 3-Dodecanone, 4-Dodecanone, 5-Dodecanone, 2-Tridecanone, 3-Tridecanone, 2-Tetradecanone, 2-Pentadecanone, 8-Pentadecanone, 2-Hexadecanone, 3-Hexadecanone, 9-Heptadecanone, 2-Pentadecanone , 2-octadecanone, 2-nonadecanone, 10-nonadecanone, 2-eicosanone, 11-eicosanone, 2-heneicosanone, 2-docosanone, lauron, stearone and the like.
Furthermore, arylalkylketones having a total carbon number of 12 to 24, such as n-octadecanophenone, n-heptadecanophenone, n-hexadecanophenone, n-pentadecanophenone, n-tetradeca. Nophenone, 4-n-dodecaacetophenone, n-tridecanophenone, 4-n-undecanoacetophenone, n-laurofenone, 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, cyclohexylphenylketone, benzyl-n-butylketone, 4-n-butylacetophenone, n-hexanophenone, 4-isobutylacetophenone, 1-acetonaphthone, 2-acetonafton, cyclopentylphenyl Examples include ketones.

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, zidodecyl ether, and 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. Can be mentioned.

Examples of acid amides include acetamide, propionic acid amide, butyric acid amide, caproic acid amide, capric acid amide, capric acid amide, lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, and oleic acid amide. , Elcaic acid amide, benzamide, caproic acid anilide, capric acid anilide, capric acid anilide, laurate anilide, myristic acid anilide, palmitate anilide, stearate anilide, behenic acid anilide, oleic acid anilide, erucate anilide, caproic acid N -Methylamide, capric acid N-methylamide, capric acid N-methylamide, lauric acid N-methylamide, myristic acid N-methylamide, palmitic acid N-methylamide, stearate N-methylamide, behenic acid N-methylamide, oleic acid N-methylamide , Elcaic acid N-methylamide, lauric acid N-ethylamide, myristic acid N-ethylamide, palmitic acid N-ethylamide, stearic acid N-ethylamide, oleic acid N-ethylamide, lauric acid N-butylamide, myristic acid N-butylamide, palmitin Acid N-butylamide, stearate N-butylamide, oleic acid N-butylamide, lauric acid N-octylamide, myristic acid N-octylamide, palmitic acid N-octylamide, steaic acid N-octylamide, oleic acid N-octylamide. Amide, lauric acid N-dodecylamide, myristic acid N-dodecylamide, palmitic acid N-dodecylamide, stearic acid N-dodecylamide, oleic acid N-dodecylamide, dilauric acid amide, dimyristic acid amide, dipalmitic acid amide , Distearic acid amide, Dioleic acid amide, Trilauric acid amide, Trimyristic acid amide, Tripalmitic acid amide, Tristea acid amide, Trioleic acid amide, Succinic acid amide, Adipic acid amide, Glutamic acid amide, Malonic acid amide, Azelin 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, glutaru Acid N-ethylamide, malonic acid N-ethylamide, azelaic acid N-ethylamide, succinic acid N-butylamide, adipic acid N- Examples thereof include butylamide, glutaric acid N-butylamide, malonic acid N-butylamide, adipic acid N-octylamide, and adipic acid N-dodecylamide.

〔式中、Ｒ_１は水素原子又はメチル基を示し、ｍは０～２の整数を示し、Ｘ_１、Ｘ_２のいずれか一方は－（ＣＨ_２）_ｎＯＣＯＲ_２又は－（ＣＨ_２）_ｎＣＯＯＲ_２、他方は水素原子を示し、ｎは０～２の整数を示し、Ｒ_２は炭素数４以上のアルキル基又はアルケニル基を示し、Ｙ_１及びＹ_２は水素原子、炭素数１～４のアルキル基、メトキシ基、又は、ハロゲンを示し、ｒ及びｐは１～３の整数を示す。〕
前記式（１）で示される化合物のうち、Ｒ_１が水素原子の場合、より広いヒステリシス幅を有する可逆熱変色性組成物が得られるため好適であり、更にＲ_１が水素原子であり、且つ、ｍが０の場合がより好適である。
なお、式（１）で示される化合物のうち、より好ましくは下記一般式（２）で示される化合物が用いられる。

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

[In the formula, R ₁ indicates a hydrogen atom or a methyl group, m indicates an integer of 0 to 2, and either X ₁ or X ₂ is-(CH ₂ ) _n OCOR ₂ or-(CH ₂ ) _n . COOR ₂ indicates a hydrogen atom, n indicates an integer of 0 to 2, R ₂ indicates an alkyl group or an alkenyl group having 4 or more carbon atoms, Y ₁ and Y ₂ indicate a hydrogen atom and 1 to 4 carbon atoms. Represents an alkyl group, a methoxy group, or a halogen, and r and p represent integers of 1 to 3. ]
Among the compounds represented by the above formula (1), when R ₁ is a hydrogen atom, it is suitable because a reversible thermochromic composition having a wider hysteresis width can be obtained, and further, R ₁ is a hydrogen atom and , M is more preferably 0.
Of the compounds represented by the formula (1), the compound represented by the following general formula (2) is more preferably used.

R in the formula represents an alkyl group or an alkenyl group having 8 or more carbon atoms, preferably an alkyl group having 10 to 24 carbon atoms, and more preferably an alkyl group having 12 to 22 carbon atoms.
Specifically, the compounds include octanoic acid-4-benzyloxyphenylethyl, nonanoic acid-4-benzyloxyphenylethyl, decanoic acid-4-benzyloxyphenylethyl, undecanoic acid-4-benzyloxyphenylethyl, and dodecanoic acid. -4-benzyloxyphenylethyl, 4-benzyloxyphenylethyl tridecanoic acid, -4-benzyloxyphenylethyl tetradecanoic acid, -4-benzyloxyphenylethyl pentadecanoic acid, -4-benzyloxyphenylethyl hexadecanoic acid, heptadecanoic acid Examples thereof include -4-benzyloxyphenylethyl and -4-benzyloxyphenylethyl octadecanoic acid.

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

(In the formula, R represents an alkyl group or an alkoxy group having 8 or more carbon atoms, m and n represent integers of 1 to 3, respectively, and X and Y represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and carbon, respectively. Indicates an alkoxy group of numbers 1 to 4 and a halogen.)
Specifically, the compounds include octanoic acid 1,1-diphenylmethyl, nonanoic acid 1,1-diphenylmethyl, decanoic acid 1,1-diphenylmethyl, undecanoic acid 1,1-diphenylmethyl, and dodecanoic acid 1,1-. Diphenylmethyl, tridecanoic acid 1,1-diphenylmethyl, tetradecanoic acid 1,1-diphenylmethyl, pentadecaneic acid 1,1-diphenylmethyl, hexadecane acid 1,1-diphenylmethyl, heptadecanoic acid 1,1-diphenylmethyl, octadecanoic acid 1,1-Diphenylmethyl can be exemplified.

（式中、Ｘは水素原子、炭素数１乃至４のアルキル基、メトキシ基、ハロゲン原子のいずれかを示し、ｍは１乃至３の整数を示し、ｎは１乃至２０の整数を示す。）
前記化合物としては、マロン酸と２－〔４－(４－クロロベンジルオキシ）フェニル）〕エタノールとのジエステル、こはく酸と２－（４－ベンジルオキシフェニル）エタノールとのジエステル、こはく酸と２－〔４－(３－メチルベンジルオキシ）フェニル）〕エタノールとのジエステル、グルタル酸と２－（４－ベンジルオキシフェニル）エタノールとのジエステル、グルタル酸と２－〔４－(４－クロロベンジルオキシ）フェニル）〕エタノールとのジエステル、アジピン酸と２－（４－ベンジルオキシフェニル）エタノールとのジエステル、ピメリン酸と２－（４－ベンジルオキシフェニル）エタノールとのジエステル、スベリン酸と２－（４－ベンジルオキシフェニル）エタノールとのジエステル、スベリン酸と２－〔４－(３－メチルベンジルオキシ）フェニル）〕エタノールとのジエステル、スベリン酸と２－〔４－(４－クロロベンジルオキシ）フェニル）〕エタノールとのジエステル、スベリン酸と２－〔４－(２，４－ジクロロベンジルオキシ）フェニル）〕エタノールとのジエステル、アゼライン酸と２－（４－ベンジルオキシフェニル）エタノールとのジエステル、セバシン酸と２－（４－ベンジルオキシフェニル）エタノールとのジエステル、１，１０－デカンジカルボン酸と２－（４－ベンジルオキシフェニル）エタノールとのジエステル、１，１８-オクタデカンジカルボン酸と２－（４－ベンジルオキシフェニル）エタノールとのジエステル、１，１８-オクタデカンジカルボン酸と２－〔４－(２－メチルベンジルオキシ）フェニル）〕エタノールとのジエステルを例示できる。 Further, as the component (c), a compound represented by the following general formula (4) can also be used.

(In the formula, X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, or a halogen atom, m represents an integer of 1 to 3, and n represents an integer of 1 to 20.)
Examples of the compound include a diester of malonic acid and 2- [4- (4-chlorobenzyloxy) phenyl)] ethanol, a diester of succinic acid and 2- (4-benzyloxyphenyl) ethanol, and a diester of succinic acid and 2-. [4- (3-Methylbenzyloxy) phenyl)] Diester with ethanol, Diester with glutaric acid and 2- (4-benzyloxyphenyl) ethanol, Diester with glutaric acid 2- [4- (4-chlorobenzyloxy) Phenyl)] Diester with ethanol, diester with adipic acid and 2- (4-benzyloxyphenyl) ethanol, diester with pimelic acid and 2- (4-benzyloxyphenyl) ethanol, suberic acid and 2- (4-) Diester with benzyloxyphenyl) ethanol, diester with Sveric acid and 2- [4- (3-methylbenzyloxy) phenyl)] Diester with ethanol, Diester with Sveric acid and 2- [4- (4-chlorobenzyloxy) phenyl)] Diester with ethanol, diester with suberic acid and 2- [4- (2,4-dichlorobenzyloxy) phenyl)] ethanol, diester with azelaic acid and 2- (4-benzyloxyphenyl) ethanol, with sebacic acid Diester with 2- (4-benzyloxyphenyl) ethanol, diester with 1,10-decandicarboxylic acid and 2- (4-benzyloxyphenyl) ethanol, 1,18-octadecanedicarboxylic acid and 2- (4-benzyl) Examples thereof include a diester with oxyphenyl) ethanol, and a diester 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。 Further, as the component (c), a compound represented by the following general formula (5) can also be used.

(In the formula, R represents an alkyl group or an alkenyl group having 1 to 21 carbon atoms, and n represents an integer of 1 to 3).
Examples of the compound include a diester of 1,3-bis (2-hydroxyethoxy) benzene and capric acid, a diester of 1,3-bis (2-hydroxyethoxy) benzene and undecanoic acid, and 1,3-bis (2). -Diester of hydroxyethoxy) benzene and lauric acid, diester of 1,3-bis (2-hydroxyethoxy) benzene and myristic acid, diester of 1,4-bis (hydroxymethoxy) benzene and butyric acid, 1,4 -Diester of bis (hydroxymethoxy) benzene and isovaleric acid, diester of 1,4-bis (2-hydroxyethoxy) benzene and acetic acid, 1,4-bis (2-hydroxyethoxy) benzene and propionic acid Diester, diester of 1,4-bis (2-hydroxyethoxy) benzene and valerate, diester of 1,4-bis (2-hydroxyethoxy) benzene and caproic acid, 1,4-bis (2-hydroxyethoxy) ) Diester of benzene and capric acid, Diester of 1,4-bis (2-hydroxyethoxy) benzene and capric acid, Diester of 1,4-bis (2-hydroxyethoxy) benzene and lauric acid, 1,4 An example is an example of a diester of bis (2-hydroxyethoxy) benzene and myristic acid.

（式中、Ｘは水素原子、炭素数１乃至４のアルキル基、炭素数１乃至４のアルコキシ基、ハロゲン原子のいずれかを示し、ｍは１乃至３の整数を示し、ｎは１乃至２０の整数を示す。）
前記化合物としては、こはく酸と２－フェノキシエタノールとのジエステル、スベリン酸と２－フェノキシエタノールとのジエステル、セバシン酸と２－フェノキシエタノールとのジエステル、１，１０-デカンジカルボン酸と２－フェノキシエタノールとのジエステル、１，１８-オクタデカンジカルボン酸と２－フェノキシエタノールとのジエステルを例示できる。 Further, as the component (c), a compound represented by the following general formula (6) can also be used.

(In the formula, X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, m represents an integer of 1 to 3, and n represents 1 to 20. Indicates an integer of.)
Examples of the compound include a diester of succinic acid and 2-phenoxyethanol, a diester of suberic acid and 2-phenoxyethanol, a diester of sebacic acid and 2-phenoxyethanol, and a diester of 1,10-decandycarboxylic acid and 2-phenoxyethanol. Examples of the diester of 1,18-octadecanedicarboxylic acid and 2-phenoxyethanol can be exemplified.

（式中、Ｒは炭素数４乃至２２のアルキル基、シクロアルキルアルキル基、シクロアルキル基、炭素数４乃至２２のアルケニル基のいずれかを示し、Ｘは水素原子、炭素数１乃至４のアルキル基、炭素数１乃至４のアルコキシ基、ハロゲン原子のいずれかを示し、ｎは０又は１を示す。）
前記化合物としては、４－フェニル安息香酸デシル、４－フェニル安息香酸ラウリル、４－フェニル安息香酸ミリスチル、４－フェニル安息香酸シクロヘキシルエチル、４－ビフェニル酢酸オクチル、４－ビフェニル酢酸ノニル、４－ビフェニル酢酸デシル、４－ビフェニル酢酸ラウリル、４－ビフェニル酢酸ミリスチル、４－ビフェニル酢酸トリデシル、４－ビフェニル酢酸ペンタデシル、４－ビフェニル酢酸セチル、４－ビフェニル酢酸シクロペンチル、４－ビフェニル酢酸シクロヘキシルメチル、４－ビフェニル酢酸ヘキシル、４－ビフェニル酢酸シクロヘキシルメチルを例示できる。 Further, as the component (c), a compound represented by the following general formula (7) can also be used.

(In the formula, R represents any of an alkyl group having 4 to 22 carbon atoms, a cycloalkylalkyl group, a cycloalkyl group, and an alkoxy group having 4 to 22 carbon atoms, and X is a hydrogen atom and an alkyl having 1 to 4 carbon atoms. A group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, where n indicates 0 or 1).
Examples of the compound include decyl 4-phenylbenzoate, lauryl 4-phenylbenzoate, myristyl 4-phenylbenzoate, cyclohexylethyl 4-phenylbenzoate, octyl 4-biphenylacetate, nonyl 4-biphenylacetate, and 4-biphenylacetic acid. Decyl, 4-biphenylacetate lauryl, 4-biphenylacetate myristyl, 4-biphenylacetate tridecyl, 4-biphenylacetate pentadecyl, 4-biphenylacetate cetyl, 4-biphenylacetate cyclopentyl, 4-biphenylacetate cyclohexylmethyl, 4-biphenylacetate hexyl , 4-Cyclohexylmethyl biphenylacetate can be exemplified.

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

(In the formula, R indicates any of an alkyl group having 3 to 18 carbon atoms and an aliphatic acyl group having 3 to 18 carbon atoms, and X is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and 1 or 2 carbon atoms. Indicates either an alkoxy group or a halogen atom, Y indicates either 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, or a halogen atom. Indicates one of.)
Examples of the compound include phenoxyethyl 4-butoxybenzoate, phenoxyethyl 4-pentyloxybenzoate, phenoxyethyl 4-tetradecyloxybenzoate, an ester of phenoxyethyl 4-hydroxybenzoate and dodecanoic acid, and phenoxyethyl vanillate. Dodecyl ether can be exemplified.

（式中、Ｒは炭素数４乃至２２のアルキル基、炭素数４乃至２２のアルケニル基、シクロアルキルアルキル基、シクロアルキル基のいずれかを示し、Ｘは水素原子、アルキル基、アルコキシ基、ハロゲン原子のいずれかを示し、Ｙは水素原子、アルキル基、アルコキシ基、ハロゲン原子のいずれかを示し、ｎは０又は１を示す。）
前記化合物としては、ｐ－ヒドロキシ安息香酸オクチルの安息香酸エステル、ｐ－ヒドロキシ安息香酸デシルの安息香酸エステル、ｐ－ヒドロキシ安息香酸ヘプチルのｐ－メトキシ安息香酸エステル、ｐ－ヒドロキシ安息香酸ドデシルのo-メトキシ安息香酸エステル、ｐ－ヒドロキシ安息香酸シクロヘキシルメチルの安息香酸エステルを例示できる。 Further, as the component (c), a compound represented by the following general formula (9) can also be used.

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

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

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

（式中、Ｒは炭素数３乃至８のシクロアルキル基又は炭素数４乃至９のシクロアルキルアルキル基を示し、ｎは１乃至３の整数を示す。）
前記化合物としては、１，３－ビス（２－ヒドロキシエトキシ）ベンゼンとシクロヘキサンカルボン酸とのジエステル、１，４－ビス（２－ヒドロキシエトキシ）ベンゼンとシクロヘキサンプロピオン酸とのジエステル、１，３－ビス（２－ヒドロキシエトキシ）ベンゼンとシクロヘキサンプロピオン酸とのジエステルを例示できる。 Further, as the component (c), a compound represented by the following general formula (11) can also be used.

(In the formula, R represents a cycloalkyl group having 3 to 8 carbon atoms or a cycloalkylalkyl group having 4 to 9 carbon atoms, and n represents an integer of 1 to 3).
Examples of the compound include a diester of 1,3-bis (2-hydroxyethoxy) benzene and cyclohexanecarboxylic acid, a diester of 1,4-bis (2-hydroxyethoxy) benzene and cyclohexanepropionic acid, and 1,3-bis. An example is an example of a diester of (2-hydroxyethoxy) benzene and cyclohexanepropionic acid.

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

(In the formula, R represents an alkyl group having 3 to 17 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and a cycloalkylalkyl group having 5 to 8 carbon atoms, and X is a hydrogen atom and an alkyl having 1 to 5 carbon atoms. A group, a methoxy group, an ethoxy group, and a halogen atom are indicated, and n indicates an integer of 1 to 3).
Examples of the compound include a diester of 4-phenylphenol ethylene glycol ether and cyclohexanecarboxylic acid, a diester of 4-phenylphenol diethylene glycol ether and lauric acid, a diester of 4-phenylphenol triethylene glycol ether and cyclohexanecarboxylic acid, and 4 -Diester of phenylphenol ethylene glycol ether and octanoic acid, diester of 4-phenylphenol ethylene glycol ether and nonanoic acid, diester of 4-phenylphenol ethylene glycol ether and decanoic acid, 4-phenylphenol ethylene glycol ether and myristine An example is an example of a diester with an acid.

The reversible thermochromic composition of the present invention is a compatible compound containing the above-mentioned components (a), (b) and (c) as essential components, and the ratio of each component is the concentration, discoloration temperature, discoloration morphology and each component. In general, the component ratio at which the desired characteristics can be obtained is 0.1 to 100, preferably 0.1 to 50, and more preferably 0.1 to 50 for the component (b) with respect to the component 1. Is in the range of 0.5 to 20, (c) component 5 to 200, preferably 5 to 100, and more preferably 10 to 100 (all of the above ratios are parts by mass).

Further, various light stabilizers can be added as needed.
The light stabilizer is contained in order to prevent photodegradation of the reversible thermochromic composition composed of the components (a), (b) and (c), and is 0.3 with respect to 1% by mass of the component (a). It is contained in an amount of about 24% by mass, preferably 0.3 to 16% by mass. Further, among the light stabilizers, the ultraviolet absorber effectively blocks the ultraviolet rays contained in sunlight and the like, and prevents photodegradation caused by the excited state due to the optical reaction of the component (a). Further, antioxidants, singlet oxygen quenchers, superoxide anion quenchers, ozone quenchers and the like suppress the oxidation reaction by light.
The light stabilizer may be used alone or in combination of two or more.

The reversible thermosetting composition is used as a reversible thermosetting pigment by being dispersed in a thermoplastic resin or a thermosetting resin, or by being encapsulated in microcapsules.
The microencapsulation is a conventionally known interfacial polymerization method, inSitu polymerization method, in-liquid curing coating method, phase separation method from an aqueous solution, phase separation method from an organic solvent, melting dispersion cooling method, and suspension in air. There are a coating method, a spray drying method, etc., which are appropriately selected according to the application. Further, a secondary resin film may be further provided on the surface of the microcapsules depending on the purpose to impart durability, or the surface characteristics may be modified for practical use.
The microcapsule pigment is preferably in the range of inclusions / wall film = 7/1 to 1/1 (mass ratio), and when the ratio of the wall film is within the above range, the color density at the time of color development and It is possible to prevent a decrease in sharpness, and more preferably, inclusions / wall film = 6/1 to 1/1 (mass ratio).
By encapsulating in the microcapsules, a chemically and physically stable pigment can be formed, and a particle size in the range of 0.01 to 50 μm, preferably 0.1 to 30 μm, and more preferably 0.5 to 20 μm is practical. Meet the 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 Mountech, and the projected area circle equivalent diameter (Heywood diameter) is calculated from the area of the particle area. It is a value calculated and measured as the average particle diameter of particles corresponding to equal volume spheres based on the value.
If the particle size of all or most of the particles exceeds 0.2 μm, it is equivalent to an equal volume sphere by the Coulter method using a particle size distribution measuring device (manufactured by Beckman Coulter Co., Ltd., product name: Multisizer 4e). It is also possible to measure as the average particle size of the particles of.

The discoloration of the reversible thermochromic pigment will be described.
When the reversible thermochromic pigments A and B reach the complete color development temperature (t ₁ ) by lowering the temperature from the decolorized state, they are completely in the color development state, and when the temperature rises from the color development state, they reach the complete decolorization temperature (t ₄ ). It is a pigment that becomes completely decolorized when it reaches it.
By having the complete color development temperature (t ₁ ) of the other reversible thermochromic pigment B on the higher temperature side than the complete color development temperature (t ₁ ) of one reversible thermochromic pigment A, the discoloration of the thermochromic pigment at the time of temperature rise Since the state can be visually discriminated and the reversible thermochromic pigment B is a pigment having fluorescence at the time of color development, each color before and after the color change is rich in vividness.
The hysteresis characteristics in the color concentration-temperature curve of the reversible thermochromic pigment will be described below with reference to the graph of FIG.
In FIG. 2, the vertical axis represents the color density and the horizontal axis represents the temperature. The change in color density due to temperature change progresses along the arrow. Here, A is a point indicating the concentration at the temperature t ₄ (hereinafter referred to as the complete decolorization temperature) at which the completely decolorized state is reached, and B is the temperature t ₃ (hereinafter referred to as the decolorization start temperature) at which the decolorization starts. C is a point indicating the density at the temperature t ₂ at which color development starts (hereinafter referred to as the color development start temperature), and D is a point indicating the temperature at which the color reaches a completely developed state t ₁ (hereinafter referred to as color development start temperature). , Called the complete color development temperature).
Further, the length of the line segment EF is a measure indicating the contrast of discoloration, and the length of the line segment HG is a temperature range indicating the degree of hysteresis (hereinafter referred to as a hysteresis width ΔH), and the larger the ΔH value is, the more. , It is easy to maintain each state before and after discoloration.
Here, the difference between t ₄ and t ₃ or the difference between t ₂ and t ₁ (Δt) is a measure showing the sensitivity of discoloration.

As an example, to be specifically described by the color density-temperature curve of FIG. 3, the reversible thermochromic pigment B having the other fluorescence on the higher temperature side than the complete decoloring temperature (t ₄ ) of one reversible thermochromic pigment A. [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 satisfied. When the temperature is raised from the state of the colored (1) having the color developed together with the color, the reversible thermochromic pigment A is decolorized and has the fluorescence when the temperature reaches the complete decoloring temperature (t ₄ ). When the color becomes colored (2) and reaches the temperature of the complete decoloring temperature ( _t'4 ), the reversible thermochromic pigment B is decolorized, so that the color change from the fluorescent colored (2) to colorless is visually recognized. The color temperature.
When the temperature reaches the complete color development temperature (t ₁ = t ' ₁ ) due to the temperature decrease, the reversible thermochromic pigment A and the reversible thermochromic pigment B develop color and return to the fluorescent colored (1).
By adding a non-color-changing colorant, the color change of the fluorescent colored (1), the fluorescent colored (2), and the colored (3) is visually recognized, and the fluorescent non-coloring property is observed. Since the colored (3) is also fluorescent when the colorant of No. 3 is used, three vivid handwritings can be visually recognized.

Further, as another example, specifically described by the color density-temperature curve of FIG. 4, the reversible heat having the fluorescence of the other on the higher temperature side than the complete decoloring temperature (t ₄ ) of one reversible thermochromic pigment A. In order to satisfy the complete decoloring temperature ( _t'4 ) of the discoloring pigment B, when the temperature is raised from the fluorescent colored (1) state in which both the reversible thermochromic pigments A and B are colored, the color is completely depleted. When the color temperature (t ₄ ) is reached, the reversible thermochromic pigment A is decolorized to become a fluorescent colored (2), and when the temperature reaches the complete decolorization temperature ( _t'4 ), the reversible thermochromic pigment A is discolored. Since the sex pigment B is decolorized, a color change from the fluorescent colored (2) to colorless is visually recognized.
When the temperature reaches the perfect color development temperature (t ' ₁ ) by lowering the temperature, the reversible thermochromic pigment B develops color and returns to the fluorescent colored (2), and further lowers the temperature to reach the complete color development temperature (t ₁ ). When the temperature is reached, the reversible thermochromic pigment A develops color and returns to the fluorescent colored (1).
By adding a non-color-changing colorant, the color change of the fluorescent colored (1), the fluorescent colored (2), and the colored (3) is visually recognized, and the fluorescent non-coloring property is observed. Since the colored (3) is also fluorescent when the colorant of No. 3 is used, three vivid handwritings can be visually recognized.

Further, as another example, specifically described by the color density-temperature curve of FIG. 5, the reversible heat having the fluorescence of the other on the higher temperature side than the complete decoloring temperature (t ₄ ) of one reversible thermochromic pigment A. In order to satisfy the complete decoloring temperature ( _t'4 ) of the discoloring pigment B, when the temperature is raised from the fluorescent colored (1) state in which both the reversible thermochromic pigments A and B are colored, the color is completely depleted. When the color temperature (t ₄ ) is reached, the reversible thermochromic pigment A is decolorized to become a fluorescent colored (2), and when the temperature reaches the complete decolorization temperature ( _t'4 ), the reversible thermochromic pigment A is discolored. Since the sex pigment B is decolorized, a color change from the fluorescent colored (2) to colorless is visually recognized.
When the temperature reaches the perfect color development temperature (t ' ₁ ) by lowering the temperature, the reversible thermochromic pigment B develops color and returns to the fluorescent colored (2), and further lowers the temperature to reach the complete color development temperature (t ₁ ). When the temperature is reached, the reversible thermochromic pigment A develops color and returns to the fluorescent colored (1).
By adding a non-color-changing colorant, the color change of the fluorescent colored (1), the fluorescent colored (2), and the colored (3) is visually recognized, and the fluorescent non-coloring property is observed. Since the colored (3) is also fluorescent when the colorant of No. 3 is used, three vivid handwritings can be visually recognized.

Further, as another example, specifically described by the color density-temperature curve of FIG. 6, reversible heat having fluorescence on the higher temperature side than the complete decoloring temperature (t ₄ ) of one reversible thermochromic pigment A. In order to satisfy the complete decoloring temperature ( _t'4 ) of the discoloring pigment B, when the temperature is raised from the fluorescent colored (1) state in which both the reversible thermochromic pigments A and B are colored, the color is completely depleted. When the color temperature (t ₄ ) is reached, the reversible thermochromic pigment A is decolorized to become a fluorescent colored (2), and when the temperature reaches the complete decolorization temperature ( _t'4 ), the reversible thermochromic pigment A is discolored. Since the sex pigment B is decolorized, a color change from the fluorescent colored (2) to colorless is visually recognized.
When the temperature reaches the perfect color development temperature (t1) by lowering the temperature, the reversible thermochromic pigment A develops color and becomes colored (3), and when the temperature is further lowered and reaches the temperature of the complete color development temperature ( _t'1 ), it is reversible. The thermochromic pigment B develops color and returns to the colored (1) having fluorescence.
By adding a non-color-changing colorant, the color changes of the fluorescent colored (1), the fluorescent colored (2), the colored (3), and the colored (4) are visually recognized and fluorescent. Since the colored (4) is also fluorescent when a non-discolorable colorant having the above is used, four vivid handwritings can be visually recognized.

By having the complete decoloring temperature (t ' ₄ ) of the reversible thermochromic pigment B on the temperature side of 10 ° C. or more higher than the complete decoloring temperature (t ₄ ) of the reversible thermochromic pigment A, the color change is clarified. It is visible and is preferably 15 ° C. or higher, more preferably 20 ° C. or higher.
Further, by having the reversible thermochromic pigment B completely decolorizing temperature ( _t'4 ) on the side 10 to 70 ° C. higher than the complete decoloring temperature (t ₄ ) of the reversible thermochromic pigment A, the color change. Is easily expressed, preferably 15 to 60 ° C, more preferably 20 to 50 ° C.
When the color is changed by the frictional heat generated by the friction body described later, the reversible heat is 15 to 40 ° C., preferably 20 to 35 ° C. higher than the complete decoloring temperature (t ₄ ) of the reversible thermochromic pigment A. By having the completely decolorizing temperature ( _t'4 ) of the discolorating pigment B, it is easy to develop a color change by frictional heat.
Further, the complete decolorization temperature (t ₄ ) of the reversible thermochromic pigment A is 50 ° C. or higher, preferably 55 ° C. or higher, more preferably 60 ° C. or higher, and the complete color development temperature (t ₁ ) is 0 ° C. or lower, preferably 0 ° C. or higher. 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. This makes it easier to maintain the discolored state at room temperature.

Next, an ink composition containing the reversible thermochromic pigment will be described.
The reversible thermochromic pigment is dispersed in a vehicle for writing tools containing water and / or an organic solvent and, if necessary, various additives, and is used as an ink for writing tools such as marking pens, ballpoint pens, fountain pens, and brush pens. can.
Examples of the various additives include resins, viscosity regulators, dispersants, antisettling agents, defoamers, penetrants, pH regulators, moisturizers, fungicides, preservatives, rust inhibitors and the like.

Among them, examples of the stationery vehicle used for the stationery ink include an oil-based vehicle containing an organic solvent, or an aqueous vehicle containing water and, if necessary, an organic solvent.
Examples of the organic solvent include ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, ethylene glycol monomethyl ether, and ethylene glycol. Examples include monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone and the like. Can be done.

If necessary, dyes and pigments can be used in combination with the ink composition of the present invention.
As the dye, acid dyes, basic dyes, and direct dyes that can be dissolved in an aqueous medium can all be used.
Pigments include inorganic pigments such as carbon black, ultramarine, titanium dioxide pigments, azo pigments, phthalocyanine pigments, indigo pigments, thioindigo pigments, slene pigments, quinacridone pigments, anthracinone pigments, throne pigments, and diketopyrrolopyrrole pigments. Examples thereof include organic pigments such as pigments, dioxazine pigments, perylene pigments, perinone pigments, and isoindolinone pigments, and fluorescent pigments.
Further, metal pigments obtained by treating aluminum powder or the surface of aluminum powder with a coloring resin, metallic glossy pigments obtained by forming a metal vapor deposition film on a transparent or colored transparent film, phosphorescent pigments, natural mica, synthetic mica, glass pieces, and alumina as core materials. It is also possible to use a pearl pigment or the like in which the surface of the transparent film piece is coated with a metal oxide such as titanium oxide.

Examples of the ink for writing tools include a shear thinning ink containing a shear thinning agent in a vehicle, and a cohesive ink containing a water-soluble polymer flocculant in a vehicle and suspending a pigment in a loosely aggregated state. be able to.
By adding the shear thinning agent, it is possible to suppress the aggregation and sedimentation of the pigment and also to suppress the bleeding of the handwriting, so that a good handwriting can be formed.
Further, when the writing tool filled with the ink is in the form of a ballpoint pen, ink leakage from the gap between the ball and the tip when not in use can be prevented, and ink backflow when the writing tip is left facing upward (upright). Can be prevented.
Examples of the shear reducing viscosity imparting agent include xanthan gum, welan gum, succinoglycan (average molecular weight of about 1 to 8 million), which is an organic acid-modified heteropolysaccharide whose constituent monosaccharides are glucose and galactose, guar gum, locust bean gum and the like. Polymers with a molecular weight of 100,000 to 150,000 containing derivatives, hydroxyethyl cellulose, alginic acid alkyl esters, and methacrylic acid alkyl esters as the main components, and thickening with gelling ability extracted from seaweeds such as glucomannan, agar, and caragenin. Polysaccharides, benzylene sorbitol and benzylene xylitol or derivatives thereof, crosslinkable acrylic acid polymers, inorganic fine particles, polyglycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether, polyoxypropylene alkyl Nonionic surfactants having an HLB value of 8 to 12, such as ethers, polyoxyethylene alkyl phenyl ethers, and fatty acid amides, and salts of dialkyl or dialkenyl sulfosuccinic acid. Examples thereof include a mixture of N-alkyl-2-pyrrolidone and an anionic surfactant, and a mixture of polyvinyl alcohol and an acrylic resin.

Examples of the water-soluble polymer flocculant include polyvinylpyrrolidone, polyethylene oxide, and water-soluble polysaccharides.
Examples of the water-soluble polysaccharide include traganth gum, guar gum, pullulan, cyclodextrin, and water-soluble cellulose derivative, and specific examples of the water-soluble cellulose derivative include methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, and hydroxypropyl methyl cellulose. And so on.

By using a comb-shaped polymer dispersant having a carboxyl group in the side chain together with the polymer flocculant, the dispersibility of loose aggregates of the microcapsule pigment by the polymer flocculant can be improved.
The comb-type polymer dispersant having a carboxyl group in the side chain is not particularly limited as long as it is a comb-type polymer compound having a plurality of carboxyl groups in the side chain, but the side chain has a plurality of carboxyl groups. Acrylic polymer compounds having a

Further, by containing the organic nitrogen-sulfur compound, it is possible to further suppress the precipitation of the microcapsule pigment due to vibration when the ink composition is filled in a writing tool and put into practical use.
This further improves the dispersibility in which the loose aggregates of the microcapsule pigment are dispersed by the comb-shaped polymer dispersant having a carboxyl group in the side chain.
As the organic nitrogen sulfur compound, a compound selected from a thiazole-based compound, an isothiazole-based compound, a benzothiazole-based compound, and a benzoisothiazole-based compound is used.
Specifically, as the organic nitrogen-sulfur compound, 2- (4-thiazolin) -benzimidazole (TBZ), 2- (thiocyanatemethylthio) -1,3-benzothiazole (TCMTB), 2-methyl-4-isothiazolin- One or more compounds selected from 3-one, 5-chloro-2-methyl-4-isothiazolin-3-one are used, preferably 2- (4-thiazolin) -benzimidazole (TBZ), 2 One or more compounds selected from -methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one are used.
Examples of the organic nitrogen-sulfur compound include Permachem Asia Co., Ltd., trade names: Topside 88, 133, 170, 220, 288, 300, 400, 500, 600, 700Z. Examples thereof include 800, 950, manufactured by Hokuko Sangyo Co., Ltd., trade names: Hokuster HP, E50A, Hokuside P200, 6500, 7400, MC, 369, and R-150.
The mass ratio of the comb-shaped polymer dispersant having a carboxyl group in the side chain to the organic nitrogen-sulfur compound is 1: 1 to 1:10, preferably 1: 1 to 1: 5, which satisfies the above range. This makes it possible to sufficiently exhibit the dispersibility of the loose aggregates of the microcapsule pigment and the suppression of sedimentation of the microcapsule pigment due to vibration.

Further, when a water-soluble resin applied to impart adhesion and viscosity of the brush to the paper surface is added, the ink containing the comb-shaped polymer dispersant having a carboxyl group in the side chain and the organic nitrogen-sulfur compound described above is added. The function of increasing the stability of the microcapsule pigment is further improved.
Examples of the water-soluble resin include alkyd resin, acrylic resin, styrene maleic acid copolymer, cellulose derivative, polyvinylpyrrolidone, polyvinyl alcohol, dextrin and the like, and polyvinyl alcohol is preferably used.
Further, the polyvinyl alcohol is more preferably used because the partially saponified polyvinyl alcohol having a saponification degree of 70 to 89 mol% is highly soluble even in the acidic region of the ink.
The amount of the water-soluble resin added is in the range of 0.3 to 3.0% by mass, preferably 0.5 to 1.5% by mass, in the ink.

When the ink is filled in a ball pen and used, a higher fatty acid such as oleic acid, a nonionic surfactant having a long-chain alkyl group, a polyether-modified silicone oil, a thioarophosphoric acid tri (alkoxycarbonylmethyl ester), or the like. Phosphoric acid triesters such as thio-phosphoric acid tri (alkoxycarbonylethyl ester), phosphoric acid monoesters of polyoxyethylene alkyl ethers or polyoxyethylene alkylaryl ethers, phosphorus of polyoxyethylene alkyl ethers or polyoxyethylene alkylaryl ethers. It is preferable to add a phosphoric acid diester or a lubricant such as a metal salt thereof, an ammonium salt, an amine salt or an alkanol amine salt to prevent wear of the ball receiving seat.

In addition, if necessary, resins such as acrylic resin, styrene maleic acid copolymer, cellulose derivative, polyvinylpyrrolidone, polyvinyl alcohol, and dextrin can be added to impart stickiness and viscosity to the paper surface, and sodium carbonate and sodium phosphate can be added. , Inorganic salts such as sodium dehydroacetate, pH adjusters such as organic basic compounds such as water-soluble amine compounds, benzotriazole, tolyltriazole, dicyclohexylammonium nitrate, diisopropylammonium nitrate, rust preventives such as saponin, coal acid, 1,2-Benziazolin 3-one sodium salt, sodium benzoate, sodium dehydroacetate, potassium sorbate, propyl paraoxybenzoate, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, etc. Preservatives or antifungal agents, ureas, nonionic surfactants, reduced or non-reduced starch hydrolysates, oligosaccharides such as trehalose, sucrose, cyclodextrin, glucose, dextrin, sorbit, mannit, sodium pyrophosphate, etc. Wetting agents, defoaming agents, dispersants, fluorosurfactants and nonionic surfactants that improve the permeability of ink may be added.

It can contain a reversible thermochromic pigment of preferably 5 to 40% by mass, more preferably 10 to 40% by mass, still more preferably 10 to 30% by mass with respect to the total mass of the ink. When the content of the pigment is in the above range, the desired color development density can be achieved, and the deterioration of the ink outflow property can be prevented.

The multicolor discolorable water-based ink composition for writing tools of the present invention is prepared by adding Pigment A and Pigment B, and if necessary, various additives in an aqueous medium containing water and a water-soluble organic solvent, and stirring the mixture.
For inks with shear thinning, pigment A, pigment B, and various additives are added to an aqueous medium, stirred and dissolved, and further, a shear thinning agent is added to a solvent prepared separately. Is prepared by directly adding a dispersion liquid or a shear thinning agent and stirring the mixture.

A ballpoint pen and a marking pen for accommodating the ink will be described.
When filling a ballpoint pen, the structure and shape of the ballpoint pen itself are not particularly limited. For example, the barrel has an ink storage tube filled with shear-reducing viscosity ink, and the ink storage tube has a ball at the tip. An example is a ballpoint pen that communicates with a ballpoint pen tip attached to the ink and has a liquid stopper for preventing backflow in close contact with the end face of the ink.
The ball pen tip will be described in more detail. A tip formed by holding a ball in a ball holding portion in which the vicinity of the tip of a metal pipe is pressed and deformed inward from an outer surface, or a metal material is cut by a drill or the like. A chip formed by holding a ball in a ball holding portion, a chip provided with a resin ball receiving seat inside a metal or plastic chip, or a ball held by the chip forward by a spring body. The urged one can be applied.
The ball is 0.3 to 2.0 mm, preferably 0.3 to 1.5 mm, more preferably 0.3 to 1.0 mm of cemented carbide, stainless steel, ruby, ceramic, resin, rubber or the like. A diameter of about the same can be applied.
As the ink accommodating tube for accommodating the ink, for example, a molded body made of a thermoplastic resin such as polyethylene, polypropylene, polyethylene terephthalate, or nylon, or a metal tubular body is used.
In addition to directly connecting the chip to the ink storage tube, the ink storage tube and the chip may be connected via a connecting member.
The ink storage tube may be in the form of a refill in which the refill is housed in a shaft tube made of resin, metal, or the like, or the shaft tube itself with a chip attached to the tip thereof is used as an ink storage body. Ink may be filled directly into the barrel.
Further, when the ink composition is housed in the infestation type ballpoint pen, the structure and shape of the infestation type ballpoint pen are not particularly limited, and the shaft is in a state where the writing tip portion provided on the ballpoint pen refill is exposed to the outside air. Any structure can be used as long as it is housed in a cylinder and the writing tip protrudes from the opening of the shaft cylinder by the operation of the retracting mechanism.
Examples of the operation method of the haunting mechanism include a knock type, a rotary type, and a slide type.
The knock type has a knock portion on the rear end portion of the shaft cylinder or the side surface of the shaft cylinder, and the ballpoint pen tip is retracted from the opening at the front end end of the shaft cylinder by pressing the knock portion, or a clip portion provided on the shaft cylinder. By pressing the ballpoint pen tip, a configuration in which the ballpoint pen tip appears and disappears from the opening at the front end of the barrel can be exemplified.
The rotary type can exemplify a configuration in which a rotating portion is provided at the rear portion of the barrel, and the ballpoint pen tip is retracted from the opening at the front end of the barrel by rotating the rotating portion.
The slide type has a slide portion on the side surface of the barrel, and the ballpoint pen tip can be retracted from the front end opening of the barrel by operating the slide, or the clip portion provided on the barrel can be slid. An example is an example of a configuration in which the ballpoint pen tip appears and disappears from the opening at the front end of the barrel.
The haunting type ballpoint pen is a composite type haunting ballpoint pen in which a plurality of ballpoint pen refills are housed in a shaft cylinder, and the writing tip of any of the ballpoint pen refills appears and disappears from the front end opening of the shaft cylinder by the operation of the hoisting mechanism. You may.

The rear end of the ink stored in the ink storage tube is filled with an ink backflow preventive body.
The ink backflow prevention body composition comprises a non-volatile liquid or a non-volatile liquid.
Specifically, vaseline, spindle oil, castor oil, olive oil, refined mineral oil, liquid paraffin, polybutene, α-olefin, α-olefin oligomer or co-oligomer, dimethyl silicone oil, methylphenyl silicone oil, amino-modified silicone oil, Examples thereof include polyether-modified silicone oil and fatty acid-modified silicone oil, and one or more of them can be used in combination.
The non-volatile liquid and / or the non-volatile liquid is preferably thickened to a suitable viscosity by adding a thickener, and the thickener is silica whose surface is hydrophobically treated and the surface is methylated. Fine particle silica, aluminum silicate, swelling mica, clay-based thickeners such as bentonite and montmorillonite treated with hydrophobicity, fatty acid metal soaps such as magnesium stearate, calcium stearate, aluminum stearate, zinc stearate, trivendilidene sorbitol, Examples thereof include fatty acid amide, amide-modified polyethylene wax, hydrogenated castor oil, a dextrin-based compound such as fatty acid dextrin, and a cellulose-based compound.
Further, the liquid ink backflow preventive body and the solid ink backflow preventive body can be used in combination.

When the marking pen is filled, the structure and shape of the marking pen itself are not particularly limited. A marking pen made of a marking pen, which is formed by mounting a marking pen tip made of the same material directly or via a relay member on a shaft tube and impregnating the ink storage body of the marking pen in which the ink storage body and the tip are connected with a cohesive ink. An example is a marking pen in which a chip and an ink accommodating tube are arranged via a valve body that is opened by pressing the chip, and ink is directly accommodated in the ink accommodating tube.
The chip is a porous member of continuous ventilation holes selected from a conventional general-purpose pore ratio of about 30 to 70%, such as a resin processed body of a fiber, a fused processed body of a heat-meltable fiber, and a felt body. One end is processed into a shape suitable for the purpose such as a bullet shape, a rectangle shape, a chisel shape, etc. and put into practical use.
The ink occlusion body is formed by bundling crimped fibers in the longitudinal direction, and is incorporated in a covering body such as a plastic cylinder or a film to adjust the porosity to approximately 40 to 90%. Will be done.
Further, although a general-purpose pumping type can be used for the valve body, it is preferable that the valve body is set to a spring pressure that can be pressed and released by writing pressure.

Further, the form of the ballpoint pen or marking pen is not limited to the above-mentioned one, and a double-headed writing tool may be equipped with a tip having a different form or a pen tip for drawing out inks of different colors.

The handwriting obtained by writing on the writing surface using the writing instrument containing the writing instrument ink composition can be discolored by a heating tool or a cooling tool.
Examples of the heating tool include an energization heating discoloring tool equipped with a resistance heating element, a heating discoloring tool filled with hot water, and a hair dryer. However, a friction member is preferable as a means capable of discoloring by a simple method. Used.
As the friction member, an elastic body such as an elastomer or a plastic foam, which has a high elastic feeling and can generate appropriate friction at the time of rubbing to generate frictional heat, is suitable.
Although it is possible to rub the handwriting using an eraser, the above-mentioned friction member in which almost no eraser residue is generated is preferably used because the eraser residue is generated at the time of rubbing.
As the material of the friction member, a silicone resin, a SEBS resin (styrene ethylene butadiene styrene block copolymer), a polyester resin, or the like is used.
As the friction member, a writing tool set can be obtained by combining a writing tool and a member (friction body) having an arbitrary shape, but the writing tool is provided with a friction member, which is excellent in portability.
In the case of a writing tool provided with a cap, the place where the friction member is provided is not particularly limited, but for example, when the cap itself is formed of the friction member, the barrel itself is formed of the friction member, or a clip is provided. The clip itself can be formed of a friction member, or a friction member can be provided at the tip end portion (top) of the cap or the rear end portion of the barrel (the portion where the writing tip portion is not provided).
In the case of a haunting type writing tool, the place where the friction member is provided is not particularly limited, but for example, the barrel itself may be formed of the friction member, or the clip itself may be formed of the friction member when the clip is provided. A friction member can be provided in the vicinity of the shaft cylinder opening, the rear end portion of the shaft cylinder (the portion where the writing tip portion is not provided), or the knock portion.
Examples of the cooling tool include a cold-heat discoloring tool using a Pertier element, a cold-heat discoloring tool filled with a refrigerant such as cold water and ice pieces, and an application of a refrigerator or a freezer.

Examples are described below. The part in the embodiment is a mass part.
Example 1
Preparation of reversible thermochromic pigment (a) 9-Ethyl (3-methylbutyl) amino-spiro [12H-benzo (a) xanthene-12,1'(3'H) isobenzofuran] -3'-on 1 as a component Part, (b) 8 parts of bis (3-methyl-4-hydroxyphenyl) sulfide, 1,1-bis (4'-hydroxyphenyl) hexafluoropropane 5 parts, (c) component 4-benzyl capricate A reversible thermochromic composition a composed of 50 parts of oxyphenylethyl was encapsulated in microcapsules to prepare a reversible thermochromic pigment A.
The average particle size of the reversible thermochromic pigment A is 2.0 μm, the complete decolorization temperature (t ₄ ) is 64 ° C., and the complete color development temperature (t ₁ ) is -14 ° C. It turns colorless.
(A) Part 1,6-bis (2-ethyloxyphenyl) -4- (4-bis (4-methylphenyl) aminophenyl) pyridine as a component, and 2,2-bis (4') as a component (b). A reversible thermochromic composition b consisting of 5 parts of -hydroxyphenyl) hexafluoropropane and 50 parts of a diester of pimelic acid and 2- (4-benzyloxyphenyl) ethanol as a component (c) is encapsulated in a microcapsule and reversible. The thermochromic pigment B was prepared.
The average particle size of the microcapsules B is 2.0 μm, the complete decolorization temperature ( _t'4 ) is 78 ° C., the complete color development temperature ( _t'1 ) is -11 ° C., and the microcapsules are fluorescent due to temperature changes. The color changes from orange to colorless.

Preparation of multicolor discolorable ink composition (see Fig. 4)
10 parts of the reversible heat-discoloring pigment A, 10 parts of the reversible heat-discoloring pigment B, 0.33 parts of xanthan gum (shear reducing viscosity imparting agent), 10 parts of urea, 10 parts of glycerin, a nonionic penetrating agent [manufactured by San Nopco Ltd. , Product name: Nopco SW-WET-366] 0.55 parts, Modified silicone antifoaming agent [manufactured by San Nopco Ltd., Product name: Nopco 8034] 0.13 parts, Antifungal agent [manufactured by Zeneca Co., Ltd., Product name: Proxel XL-2] A multicolor discolorable ink composition consisting of 0.13 parts and 58.86 parts of water was prepared.

Preparation of Writing Tool 0.97 g of the ink composition was suction-filled in a polypropylene pipe having an inner diameter of 4.4 mm, and a 0.7 mm stainless steel ball was connected to a ballpoint pen tip held at the tip via a resin holder.
Next, from the rear part of the polypropylene pipe, an ink backflow preventive body (liquid plug) having viscoelasticity containing polybutene as a main component is filled, and further, the tail plug is fitted to the rear part of the pipe to form a toe shaft cylinder and a rear shaft cylinder. After assembling and fitting the cap, deaeration treatment was performed by centrifugation to obtain a multicolor discolorable ballpoint pen.
A SEBS resin is attached to the top of the cap as a friction member.

Discoloration behavior of the brush stroke The brush stroke obtained by writing with the ball pen exhibits a bright vermilion color in which pigment A and pigment B are mixed at room temperature (25 ° C.), and is rubbed using a friction body attached to the cap. Then, when the temperature reaches 64 ° C, the pigment A is completely decolorized (t ₄ ) and the bright orange handwriting by the pigment B is visually recognized, and when the temperature is further heated to 78 ° C, the pigment B is completely decolorized (t'). ₄ ) It becomes colorless.
When cooled from this state to -11 ° C, the pigment B completely develops color ( _t'1 ) and a bright orange handwriting is visually recognized, and when the temperature reaches -14 ° C, the pigment A completely develops color (t ₁ ). Then, a bright vermilion handwriting in which the pigment A and the pigment B were mixed was visually recognized.
The state changes that reversibly change to colorless, vivid vermilion and vivid orange, can be appropriately visually discriminated in order by heating and lowering, and there are abundant variations in the stepwise color change.
Use the ball pen to form bright red "homework" letters on the notebook, and after the homework is finished, rub it with a friction body to change the color to bright orange "homework" letters. It was ideal for rubbing to make the letters "homework" colorless, checking if the homework was done, erasing it when not needed, and rewriting.

Example 2
Preparation of reversible thermochromic pigment (a) As a component, 3- (4-diethylamino-2-hexyloxyphenyl) -3- (1-ethyl-2-methylindole-3-yl) -4-azaphthalide, (2 parts), ( (B) 8 parts of bis (3-methyl-4-hydroxyphenyl) sulfide as a component, 5 parts of 1,1-bis (4'-hydroxyphenyl) hexafluoropropane, and (c) 4-benzyloxyphenylethyl capricate as a component. A reversible thermochromic composition a composed of 50 parts was encapsulated in microcapsules to prepare a reversible thermochromic pigment A.
The average particle size of the reversible thermochromic pigment A is 2.0 μm, the complete decolorization temperature (t4) is 64 ° C., the complete color development temperature (t1) is −14 ° C., and the color changes from blue to colorless due to a temperature change. do.
(A) 1.5 parts of 2,6-bis (2-ethyloxyphenyl) -4- (4-dimethylaminophenyl) -pyridine as a component, and 2,2-bis (4'-hydroxyphenyl) as a component (b) ) Hexafluoropropane 5 parts, (c) Reversible thermochromic composition b consisting of 50 parts of diester of pimelic acid and 2- (4-benzyloxyphenyl) ethanol as a component is encapsulated in microcapsules. Pigment B was prepared.
The average particle size of the microcapsules B is 2.0 μm, the complete decolorization temperature (t'4) is 78 ° C., the complete color development temperature (t'1) is -11 ° C., and the microcapsules are fluorescent due to temperature changes. The color changes from yellow to colorless.

Preparation of multicolor discolorable ink composition (see Fig. 4)
5 parts of the reversible thermochromic pigment A, 10 parts of the reversible thermochromic pigment B, 5 parts of glycerin, antifungal agent [manufactured by Zeneca Co., Ltd., trade name: Proxel XL-2] 0.7 parts, silicone defoaming agent [ San Nopco Ltd., trade name: SN deformer 381] 0.1 part, water 71.2 parts, hydroxyethyl cellulose [Union Carbide Japan Co., Ltd., trade name: cellosize WP-09L, water-soluble polymer flocculant] Eight parts of a 5 mass% aqueous solution was mixed to prepare a multicolor discolorable ink composition.

Preparation of writing instrument After impregnating the ink composition in a fiber focusing ink occlusion body (pore ratio of about 80%) in which a polyester sliver is coated with a synthetic resin film, the ink composition is impregnated into the barrel and attached to the tip of the barrel. A multicolor discolorable marking pen was constructed by assembling it in contact with a resin-processed pen body of polyester fibers (pore ratio of about 50%).
SEBS resin is attached to the rear of the barrel as a friction member.

Discoloration behavior of the brush stroke The brush stroke obtained by writing with the marking pen exhibits a bright green color in which pigment A and pigment B are mixed at room temperature (25 ° C.), and a friction body attached to the barrel is used. When rubbed, the pigment A is completely decolorized (t ₄ ) at 64 ° C, and the bright yellow brush strokes by the pigment B are visually recognized, and when the temperature is further rubbed at 78 ° C, the pigment B is completely decolorized (t). ' ₄ ) It becomes colorless.
When cooled from this state to -11 ° C, the pigment B is completely colored ( _t'1 ) and a bright yellow handwriting is visually recognized, and when the temperature is -14 ° C, the pigment A is completely colored (t ₁ ). Then, a bright green handwriting in which the pigment A and the pigment B were mixed was visually recognized.
The state change that reversibly changes color to colorless, such as bright green and bright yellow, can be appropriately visually discriminated in order by heating and lowering, and there are abundant variations in the stepwise color change.
The marking pen is used to form bright green highlights on the text of the textbook, and the friction body is used to rub to change the color to bright yellow highlights, and then rub to make the highlights colorless. It was ideal for checking the memorized part (green) and the memorized part (yellow), and erasing and rewriting when unnecessary.

Example 3
Preparation of reversible thermochromic pigment (a) Part 3,3-bis (4-diethylamino-2-ethoxyphenyl) -4-azaphthalide as a component, (b) 1,1-bis (4'-hydroxyphenyl) as a component ) A reversible thermochromic pigment A was prepared by encapsulating a reversible thermochromic composition a composed of 8 parts of n-decane, 25 parts of myristyl alcohol and 25 parts of butyl stearate as components (c) in microcapsules.
The average particle size of the reversible thermochromic pigment A is 2.0 μm, the complete decolorization temperature (t4) is 15 ° C., the complete color development temperature (t1) is 7 ° C., and the color changes from blue-green to colorless due to a temperature change. do.
(A) Part 2,6-bis (2,4-diethyloxyphenyl) -4- (4-diethylaminophenyl) -pyridine as a component, and 1,1-bis (4-hydroxyphenyl) hexa as a component (b) A reversible thermochromic pigment B was prepared by encapsulating a reversible thermochromic composition b consisting of 8 parts of fluoropropane, 25 parts of 9-heptadecanone and 25 parts of cetyl alcohol as a component (c) in microcapsules.
The reversible thermochromic pigment A has an average particle size of 2.0 μm, a complete decolorization temperature (t'4) of 34 ° C., and a complete color development temperature (t'1) of 28 ° C., and is fluorescent due to temperature changes. The color changes from yellow to colorless.

Preparation of multicolor discolorable ink composition (see Fig. 5)
10 parts of the reversible heat-discoloring pigment A, 10 parts of the reversible heat-discoloring pigment B, 0.33 parts of xanthan gum (shear reducing viscosity imparting agent), 10 parts of urea, 10 parts of glycerin, a nonionic penetrating agent [manufactured by San Nopco Ltd. , Product name: Nopco SW-WET-366] 0.55 parts, Modified silicone antifoaming agent [manufactured by San Nopco Ltd., Product name: Nopco 8034] 0.13 parts, Antifungal agent [manufactured by Zeneca Co., Ltd., Product name: Proxel XL-2] A multicolor discolorable ink composition consisting of 0.13 parts and 58.86 parts of water was prepared.

Preparation of Writing Tool 0.97 g of the ink composition was suction-filled in a polypropylene pipe having an inner diameter of 4.4 mm, and a 0.7 mm stainless steel ball was connected to a ballpoint pen tip held at the tip via a resin holder.
Next, from the rear part of the polypropylene pipe, an ink backflow preventive body (liquid plug) having viscoelasticity containing polybutene as a main component is filled, and further, the tail plug is fitted to the rear part of the pipe to form a toe shaft cylinder and a rear shaft cylinder. After assembling and fitting the cap, deaeration treatment was performed by centrifugation to obtain a multicolor discolorable ballpoint pen.

Discoloration behavior of handwriting The handwriting obtained by writing with the ballpoint pen exhibits a bright yellow color due to pigment B at room temperature (25 ° C), and when heated by touch from this state, pigment B becomes 34 ° C. It was completely decolorized ( _t'4 ) and became colorless, and the handwriting was no longer visible.
When left at room temperature (25 ° C.) in this state, the pigment B completely developed color ( _t'1 ) when the temperature dropped to 28 ° C., and a bright yellow handwriting appeared again.
Further, the brush stroke is left in the refrigerator (5 ° C.) for a while, and when the temperature reaches 7 ° C., the pigment A completely develops a color (t ₁ ), and the blue-green color of the pigment A and the fluorescent yellow color of the pigment B are mixed. The bright yellow-green handprint that became was visually recognized.
The state change that reversibly changes to bright yellow, colorless, and bright yellow-green can be appropriately visually discriminated in order by heating and lowering, and there are abundant variations in the stepwise color change.
When a bright yellow picture is drawn using the ball pen and heated by touching the finger, the picture disappears, and the bright yellow picture appears again at room temperature (25 ° C), and the picture is further cooled to make it vivid. It was possible to make a yellow-green picture, which was ideal for magic applications.

Example 4
(A) 1 part of 3,3-bis (4-diethylamino-2-ethoxyphenyl) -4-azaphthalide as a component, 1,1-bis (4'-hydroxyphenyl) n-decane 8 parts as a component (b), (C) A reversible thermochromic pigment A was prepared by encapsulating a reversible thermochromic composition a composed of 25 parts of 9-heptadecanone and 25 parts of cetyl alcohol as a component in microcapsules.
The average particle size of the reversible thermochromic pigment A is 2.0 μm, the complete decolorization temperature (t4) is 35 ° C., the complete color development temperature (t1) is 28 ° C., and the color changes from blue-green to colorless due to a temperature change. do.
(A) As a component, 2- (di-n-butylamino) -8- (di-n-amylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 ′ (3 ′ H) -isobenzofuran] -3'-on 1 part, (b) component 1,1-bis (4-hydroxyphenyl) hexafluoropropane 8 parts, (c) component stearyl stearate 50 parts The reversible thermochromic composition b comprising the same was encapsulated in microcapsules to prepare a reversible thermochromic pigment B.
The average particle size of the reversible thermochromic pigment A is 2.0 μm, the complete decolorization temperature (t4) is 58 ° C., the complete color development temperature (t1) is 43 ° C., and the pink color has fluorescence due to the temperature change. Discolors from to colorless.

Preparation of multicolor discolorable ink composition (see Fig. 5)
5 parts of the reversible thermochromic pigment A, 10 parts of the reversible thermochromic pigment B, 5 parts of glycerin, antifungal agent [manufactured by Zeneca Co., Ltd., trade name: Proxel XL-2] 0.7 parts, silicone defoaming agent [ San Nopco Ltd., trade name: SN deformer 381] 0.1 part, water 71.2 parts, hydroxyethyl cellulose [Union Carbide Japan Co., Ltd., trade name: cellosize WP-09L, water-soluble polymer flocculant] Eight parts of a 5 mass% aqueous solution was mixed to prepare a multicolor discolorable ink composition.

Preparation of Writing Tools After impregnating the ink composition in a fiber focusing ink occlusion body (pore ratio of about 80%) in which a polyester sliver is coated with a synthetic resin film, the ink composition is impregnated into the barrel and attached to the tip of the barrel. A multicolor marking pen was constructed by assembling it in contact with a resin-processed pen body made of polyester fibers (pore ratio of about 50%).
SEBS resin is attached to the rear of the barrel as a friction member.

Discoloration behavior of handwriting The handwriting obtained by writing with the marking pen exhibits a bright purple color at room temperature (25 ° C), and when heated by rubbing with a rubbing body from this state, pigment A becomes 35 ° C. The color is completely decolorized (t ₄ ), and the bright pink color due to the pigment B is visually recognized. When the temperature further rises to 58 ° C., the pigment B is completely decolorized (t ' ₄ ), and the handwriting is visually recognized. Will not be done.
After that, when cooled, the temperature drops to 43 ° C., the pigment B is completely colored ( _t'1 ), and a bright pink brush stroke is visually recognized, and further, when the temperature is 28 ° C., the pigment A is completely colored (t'1). In t ₁ ), a bright purple brush stroke in which the blue-green color of the pigment A and the bright pink color of the pigment B were mixed was visually recognized.
The state changes that reversibly change to colorless, such as bright purple and bright pink, can be appropriately visually discriminated in order by heating and lowering, and there are abundant variations in the stepwise color change.
Use the marking pen to draw a bright purple picture, and when heated, it becomes a bright pink color, when it is further heated, it becomes colorless, and when left unattended, it changes from a bright pink color to a bright yellow-green picture. It was ideal for magic applications.

Example 5
Preparation of reversible thermochromic pigment (a) As a component, 3- (4-diethylamino-2-hexyloxyphenyl) -3- (1-ethyl-2-methylindole-3-yl) -4-azaphthalide, (2 parts), ( B) 8 parts of bis (3-methyl-4-hydroxyphenyl) sulfide, 5 parts of 1,1-bis (4'-hydroxyphenyl) hexafluoropropane as components, and 50 parts of 4-methylbenzyl palmitate as (c) components. A reversible thermochromic composition consisting of the above was encapsulated in microcapsules to prepare a reversible thermochromic pigment A.
The average particle size of the reversible thermochromic pigment A is 2.0 μm, the complete decolorization temperature (t4) is 43 ° C., the complete color development temperature (t1) is -3 ° C., and the color changes from blue to colorless due to a temperature change. do.
(A) Part 2,6-bis (2-ethyloxyphenyl) -4- (4-dimethylaminophenyl) -pyridine as a component, and 1,1-bis (4-hydroxyphenyl) hexafluoro as a component (b) A reversible thermochromic pigment B is prepared by encapsulating a reversible thermochromic composition consisting of 5 parts of propane and 50 parts of a diester of pimelic acid and 2- (4-benzyloxyphenyl) ethanol as a component (c) in a microcapsule. did.
The average particle size of the microcapsules B is 2.0 μm, the complete decolorization temperature (t4) is 78 ° C, and the complete color development temperature (t1) is -11 ° C. Discolors.

Preparation of multicolor discolorable ink composition (see FIG. 6)
5 parts of the reversible heat-discoloring pigment A, 15 parts of the reversible heat-discoloring pigment B, 0.33 parts of xanthan gum (shear reducing viscosity imparting agent), 10 parts of urea, 10 parts of glycerin, a nonionic penetrating agent [manufactured by San Nopco Ltd. , Product name: Nopco SW-WET-366] 0.55 parts, Modified silicone antifoaming agent [manufactured by San Nopco Ltd., Product name: Nopco 8034] 0.13 parts, Antifungal agent [manufactured by Zeneca Co., Ltd., Product name: Proxel XL-2] A multicolor discolorable ink composition consisting of 0.13 parts and 58.86 parts of water was prepared.

Preparation of Writing Tool 0.97 g of the ink composition was suction-filled in a polypropylene pipe having an inner diameter of 4.4 mm, and a 0.7 mm stainless steel ball was connected to a ballpoint pen tip held at the tip via a resin holder.
Next, from the rear part of the polypropylene pipe, an ink backflow preventive body (liquid plug) having viscoelasticity containing polybutene as a main component is filled, and further, the tail plug is fitted to the rear part of the pipe to form a toe shaft cylinder and a rear shaft cylinder. After assembling and fitting the cap, deaeration treatment was performed by centrifugation to obtain a multicolor discolorable ballpoint pen.
A SEBS resin is attached to the top of the cap as a friction member.

Discoloration of handwriting The handwriting obtained by writing with the ball pen exhibits a bright green color at room temperature (25 ° C), and when rubbed with a rubbing body attached to a cap, the pigment A is completely removed at 43 ° C. After decoloring (t ₄ ), bright yellow handwriting by pigment B is visually recognized, and when the temperature rises to 78 ° C due to further rubbing, pigment B is completely decolorized ( _t'4 ) and colorless. become.
When cooled from this state to -3 ° C, pigment A completely develops color (t ₁ ) and blue color is visually recognized, and when the temperature further decreases to -11 ° C, pigment B completely develops color (t ' ₁ ). ), And it becomes the original bright green handwriting.
The state change that reversibly changes color to colorless, such as bright green, bright yellow, and blue, can be appropriately visually distinguished in order by heating and lowering, and there are abundant variations in the stepwise color change. rice field.
It should be noted that the ballpoint pen can be used to form bright green letters on the notebook, and important parts can be rubbed with a friction body to change the color to bright yellow letters. In addition, when the wrong character was formed or the wrong part was made yellow, it could be rubbed to make the character colorless and rewritten, which was ideal for distinguishing important parts.
Furthermore, by changing the color of the characters to blue using a cold pen, it is possible to subdivide important parts.
Furthermore, by combining the ball pen and the yellow transparent sheet, bright green characters are formed on the notebook using the ball pen, and the part to be memorized is rubbed with a friction body to change the color to bright yellow characters. When the yellow transparent sheet was placed, the yellow letters became invisible, which was ideal for memorization. In addition, when the wrong character was formed or the wrong part was made yellow, the character could be rubbed to make the character colorless and rewritten, which was excellent in convenience.

Example 6
Preparation of reversible thermochromic pigment (a) 2- (di-n-butylamino) -8- (di-n-amylamino) -4-methyl-spirino [5H- [1] benzopyrano (2,3-) as a component g) Pyrimidine-5,1'(3'H) -isobenzofuran] -3'-one 1 part, (b) 1,1-bis (4-hydroxyphenyl) hexafluoropropane 5 parts as a component, (c) A reversible thermochromic pigment A was prepared by encapsulating a reversible thermochromic composition consisting of 50 parts of 4-methylbenzyl palmitate as a component in microcapsules.
The reversible thermochromic pigment A has an average particle size of 2.0 μm, a complete decolorization temperature (t4) of 43 ° C., a complete color development temperature (t1) of -3 ° C., and a pink color having fluorescence due to a temperature change. Discolors from to colorless.
(A) Part 1,6-bis (2,4-diethyloxyphenyl) -4- (4-bis (4-methylphenyl) aminophenyl) pyridine as a component, and 2,2-bis (b) as a component. A reversible thermochromic composition consisting of 8 parts of 4'-hydroxyphenyl) hexafluoropropane and 50 parts of a diester of pimelic acid and 2- (4-benzyloxyphenyl) ethanol as a component (c) is encapsulated in microcapsules. A reversible thermochromic pigment B was prepared.
The average particle size of the microcapsules B is 2.0 μm, the complete decolorization temperature (t4) is 78 ° C, and the complete color development temperature (t1) is -11 ° C. Discolors.

Preparation of multicolor discolorable ink composition (see FIG. 6)
7.5 parts of the reversible thermochromic pigment A, 7.5 parts of the reversible thermochromic pigment B, 5 parts of glycerin, antifoaming agent [manufactured by Zeneca Co., Ltd., trade name: Proxel XL-2] 0.7 parts, silicone-based Antifoaming agent [manufactured by San Nopco Ltd., trade name: SN Deformer 381] 0.1 part, 71.2 parts of water, hydroxyethyl cellulose [manufactured by Union Carbide Japan Co., Ltd., trade name: cellosize WP-09L, highly water-soluble Molecular aggregating agent] 8 parts of a 5% by mass aqueous solution was mixed to prepare a multicolor discolorable ink composition.

Preparation of writing instrument After impregnating the ink composition in a fiber focusing ink occlusion body (pore ratio of about 80%) in which a polyester sliver is coated with a synthetic resin film, the ink composition is impregnated into the barrel and attached to the tip of the barrel. A multicolor discolorable marking pen was constructed by assembling it in contact with a resin-processed pen body of polyester fibers (pore ratio of about 50%).
SEBS resin is attached to the rear of the barrel as a friction member.

Discoloration of handwriting The handwriting obtained by writing with the marking pen exhibits a bright vermilion color at room temperature (25 ° C), and when rubbed with a friction body attached to the barrel, pigment A becomes 43 ° C. The color is completely decolorized (t ₄ ), and the bright orange handwriting by the pigment B is visually recognized, and when the temperature rises to 78 ° C due to further rubbing, the pigment B is completely decolorized ( _t'4 ). , Becomes colorless.
When cooled from this state to -3 ° C, the pigment A completely develops a color (t ₁ ) and a bright pink color is visually recognized, and when the temperature further decreases to -11 ° C, the pigment B completely develops a color (t 1). t ' ₁ ) to return to the original bright vermilion handwriting.
The state change that reversibly changes to vivid vermilion, vivid orange, and vivid pink and colorless can be appropriately visually distinguished in order by heating and lowering, and there are abundant variations in gradual color change. It was a thing.
In addition, the marking pen is used to form a bright vermilion highlight on the characters of the textbook, and the friction body is used to rub it to change the color to a bright orange highlight, and then rub it to make the highlight colorless. It was possible to check the memorized part (vermilion) and the memorized part (orange), and erase it when it was not needed, which was ideal for rewriting.
Furthermore, by changing the highlight to a bright pink color using a cold pen, it is possible to reliably distinguish the part to be memorized.

Example 7
Preparation of reversible thermochromic pigment (a) Part 3,3-bis (4-diethylamino-2-ethoxyphenyl) -4-azaphthalide as a component, (b) 1,1-bis (4'-hydroxyphenyl) as a component ) A reversible thermochromic pigment A was prepared by encapsulating a reversible thermochromic composition consisting of 5 parts of n-decane and 50 parts of 4-methylbenzyl palmitate as a component (c) in microcapsules.
The average particle size of the reversible thermochromic pigment A is 2.0 μm, the complete decolorization temperature (t4) is 43 ° C., the complete color development temperature (t1) is -3 ° C., and the temperature changes from bluish green to colorless. Discolors.
(A) As a component, 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 part, (b) component 1,1-bis (4-hydroxyphenyl) hexafluoropropane 5 part, (c) component pyrimidine and 2- A reversible thermochromic pigment B was prepared by encapsulating a reversible thermochromic composition consisting of 50 parts of a diester with (4-benzyloxyphenyl) ethanol in a microcapsule.
The average particle size of the microcapsules B is 2.0 μm, the complete decolorization temperature (t4) is 78 ° C., the complete color development temperature (t1) is -11 ° C., and the color changes from pink to colorless, which is fluorescent due to temperature changes. Discolors to.

Preparation of multicolor discolorable ink composition (see FIG. 6)
Reversible thermochromic pigment A5 part, reversible thermochromic pigment B15 part, yellow dye [Kinoline Yellow WS300, C.I., manufactured by Daiwa Kasei Co., Ltd. I. 47005] 0.5 parts, xanthan gum (shear reducing viscosity imparting agent) 0.33 parts, urea 10 parts, glycerin 10 parts, nonionic permeability imparting agent [manufactured by San Nopco Ltd., trade name: Nopco SW-WET-366 ] 0.55 parts, modified silicone antifoaming agent [manufactured by San Nopco Ltd., trade name: Nopco 8034] 0.13 parts, antifungal agent [manufactured by Zeneca Co., Ltd., trade name: Proxel XL-2] 0. A multicolor discolorable ink composition consisting of 13 parts and 58.86 parts of water was prepared.

Preparation of Writing Tool 0.97 g of the ink composition was suction-filled in a polypropylene pipe having an inner diameter of 4.4 mm, and a 0.7 mm stainless steel ball was connected to a ballpoint pen tip held at the tip via a resin holder.
Next, from the rear part of the polypropylene pipe, an ink backflow preventive body (liquid plug) having viscoelasticity containing polybutene as a main component is filled, and further, the tail plug is fitted to the rear part of the pipe to form a toe shaft cylinder and a rear shaft cylinder. After assembling and fitting the cap, deaeration treatment was performed by centrifugation to obtain a multicolor discolorable ballpoint pen.
A SEBS resin is attached to the top of the cap as a friction member.

Discoloration of the brush stroke The brush stroke obtained by writing with the ball pen exhibits a bright purple color at room temperature (25 ° C), and when rubbed with a friction body attached to the cap, the pigment A is completely removed at 43 ° C. After decoloring (t ₄ ), the bright orange brushstrokes of pigment B and the yellow dye are visible, and when the temperature rises to 78 ° C due to further rubbing, pigment B is completely decolorized ( _t'4 ). And it turns yellow.
When cooled from this state to -3 ° C, the pigment A completely develops color (t ₁ ) and yellowish green is visually recognized, and when the temperature further decreases to -11 ° C, the pigment B completely develops color (t'). ₁ ) Then, it becomes the original bright purple handwriting.
The state change that reversibly changes to bright purple, bright orange, yellow, and yellow-green can be appropriately visually distinguished in order by heating and lowering, and there are abundant variations in the stepwise color change. there were.
You can draw bright purple letters and pictures with the ball pen, rub them with a friction body to change the color to bright orange letters and pictures, and then rub them to make the letters and pictures yellow. , Was perfect for message cards.
Furthermore, it was possible to change the color of letters and pictures to yellowish green using a cold pen, and it was possible to obtain a highly variable message card.

t ₁ complete color development temperature t ₂ color development start temperature t ₃ decolorization start temperature t ₄ complete decolorization temperature

Claims (6)

A reaction medium that reversibly causes an electron transfer reaction between (a) an electron-donating color-developing organic compound, (b) an electron-accepting compound, and (c) the above-mentioned (a) and (b) components in a specific temperature range. The reversible thermochromic pigment A containing the reversible thermochromic composition a, (a) an electron-donating color-developing organic compound, (b) an electron-accepting compound, and (c) the above-mentioned (a). , (B) A reversible thermochromic pigment B containing a reversible thermochromic composition b comprising a reaction medium for reversibly causing an electron transfer reaction by a component in a specific temperature range, and a medium, the reversible heat. The color-changing pigments A and B are completely in the color-developing state when the temperature drops from the decolorized state to the complete color-developing temperature (t ₁ ), and are completely in the color-developing state when the temperature rises from the color-developing state to the complete decolorization temperature (t ₄ ). It is a pigment that is in a decolorizing state, and the complete decoloring temperature (t ₄ ) of the other reversible thermochromic pigment B is set to a temperature 10 ° C. or higher higher than the complete decoloring temperature (t ₄ ) of the reversible thermochromic pigment A. A multicolor discolorable ink composition for writing tools, wherein the reversible thermochromic pigment B is a pigment having fluorescence at the time of color development. The first aspect of claim 1, wherein the (a) electron-donating color-developing organic compound in the reversible thermochromic pigment B is a compound selected from a pyridine compound, a quinazoline compound, a bisquinazoline compound, and a diazarodamine lactone compound. Multicolor discolorable ink composition for writing tools. Complete decolorization temperature (t) of the reversible thermochromic pigment A ₄ ) To the higher temperature side of 10 to 70 ° C., the complete decolorization temperature of the reversible thermochromic pigment B (t) ₄ ) The multicolor discolorable ink composition for writing tools according to claim 1 or 2. Complete decolorization temperature (t) of the reversible thermochromic pigment A ₄ ) Is 50 ° C. or higher, and the complete color development temperature (t) ₁ ) Is 0 ° C. or lower, and the complete color development temperature (t) of the reversible thermochromic pigment B ₁ ) Is 0 ° C. or lower, the multicolor discolorable ink composition for writing tools according to any one of claims 1 to 3. A writing tool containing the multicolor discolorable ink composition for a writing tool according to any one of claims 1 to 4. The writing tool according to claim 5, which comprises a friction body.

Images