JP2019112549A - Multicolor discoloration ink composition for writing instrument and writing instrument using the same - Google Patents

Abstract

To provide a multicolor discoloration ink composition for writing instrument rich in vividness of each color before and after discoloration, and high in commercial value, and writing instrument using the same.SOLUTION: There are provided a multicolor discoloration ink composition for writing instrument consisting of at least a reversible heat discoloration pigment A, a reversible heat discoloration pigment B, and a medium, in which the reversible heat discoloration pigments A and B are pigments becoming color development state completely when they reach complete color development temperature (t) by decreasing a temperature from a decolored state, and becoming the decolored state completely when they reach a compete decolored temperature (t) by increasing the temperature from a color development state, there is complete discolored temperature (t) of the reversible heat discoloration pigment B in higher temperature side than the complete discolored temperature (t) of the reversible heat discoloration pigment B, and the reversible heat discoloration pigment B is a pigment having fluorescence during color development, and writing instrument accommodating the ink composition.SELECTED DRAWING: Figure 3

Description

  The present invention relates to a multicolor discoloring aqueous ink composition for writing instruments and a writing instrument using the same. More specifically, the present invention relates to a multicolor discoloring water-based ink composition for writing instruments which can provide a handwriting exhibiting various color changes by temperature change, and a writing instrument using the same.

DESCRIPTION OF RELATED ART Conventionally, the ink composition for writing instruments from which the handwriting which exhibits several color by temperature change is obtained is disclosed (for example, refer patent document 1).
The handwriting obtained by writing with the writing instrument filled with the ink composition is colored (1) to colored (2), further colored (3), or colored (1) to colored (2) depending on temperature change. Furthermore, it exhibits a multicolor color change to colorless.

Unexamined-Japanese-Patent No. 2004-149726

  The present invention pursues the color change of the handwriting obtained by the ink composition for writing instruments exhibiting the color change of multiple colors as described above, and obtains a writing instrument high in commercial value, rich in the vividness of each color before and after the color change. It is an object of the present invention to provide a multicolor discoloring ink composition for writing instruments and a writing instrument using the same.

The present invention reversibly performs the electron transfer reaction by (i) electron donating color forming organic compound, (ii) electron accepting compound, and (iii) the components (i) and (ii) in a specific temperature range. A reversible thermochromic pigment A comprising a reversible thermochromic composition a comprising a reaction medium to be generated, and (i) an electron donating color developing organic compound, (ii) an electron accepting compound, (iii) A reversible thermochromic pigment B comprising a reversible thermochromic composition b comprising a reaction medium capable of causing electron transfer reactions by the components (i) and (ii) in a specific temperature range reversibly, and at least a medium The reversibly thermochromic pigments A and B are completely colored when reaching the full coloration temperature (t ₁ ) by temperature decrease from the color fading state, and completely color fading temperature (t ₄ ) by temperature rise from the color developing state Shows a hysteresis curve that completely disappears when it reaches Is to pigment has a complete decoloring temperature of the reversible thermochromic pigment A (t ₄₎ from the hot side of the other reversible thermochromic pigment B complete decoloring temperature (t _4), and, reversibly thermochromic The color pigment B is a pigment having a fluorescent property at the time of color development as a multicolor discoloring ink composition for a writing instrument.
Furthermore, (i) the electron-donating coloring organic compound in the reversible thermochromic pigment B is a compound selected from a pyridine type compound, a quinazoline type compound, a biskinazoline type compound, and a diazarhodamine lactone type compound Having the complete decolorization temperature (t ₄ ) of the reversible thermochromic pigment B at a temperature higher by 10 ° C. or more than the complete decolorization temperature (t ₄ ) of the reversible thermochromic pigment A, the above-mentioned reversible thermochromic pigment Having the complete bleaching temperature (t ₄ ) of the reversible thermochromic pigment B on the higher temperature side by 10 to 70 ° C. than the complete bleaching temperature (t ₄ ) of A, the complete bleaching temperature of the reversible thermochromic pigment A The requirement is that (t ₄ ) is 50 ° C. or more, the complete color development temperature (t ₁ ) is 0 ° C. or less, and the complete color development temperature (t ₁ ) of the reversible thermochromic pigment B is 0 ° C. or less Do.
Furthermore, a writing instrument containing the multicolor discoloring ink composition for a writing instrument, a writing instrument containing the multicolor discoloring ink composition for the writing instrument and having a friction body are required.

The present invention has one of the reversible thermochromic pigment complete decoloring temperature (t ₄₎ from the hot side of the other reversible thermochromic pigment complete decoloring temperature (t _4), and, thermochromic The pigment B is a pigment having fluorescence during color development, and is rich in the vividness of each color before and after discoloration, and a multicolor discoloring ink composition for a writing instrument capable of obtaining a writing instrument having a high commercial value, and Can provide a writing instrument.

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 which has color memory property. Color density-temperature curve (pigment A: fine line, pigment B: thick line) of the reversible thermochromic pigment A and the reversible thermochromic pigment B contained in the multicolor discoloration ink composition for writing instrument according to one embodiment of the present invention Indicates Color density-temperature curve of the reversible thermochromic pigment A and the reversible thermochromic pigment B contained in the multicolor discoloring ink composition for writing instruments according to another embodiment of the present invention (pigment A: fine line, pigment B: thick line ). Color density-temperature curve of the reversible thermochromic pigment A and the reversible thermochromic pigment B contained in the multicolor discoloring ink composition for writing instruments according to another embodiment of the present invention (pigment A: fine line, pigment B: thick line ). Color density-temperature curve of the reversible thermochromic pigment A and the reversible thermochromic pigment B contained in the multicolor discoloring ink composition for writing instruments according to another embodiment of the present invention (pigment A: fine line, pigment B: thick line ).

The reversibly thermochromic compositions a and b are (i) electron-donating color-developing organic compounds, (ii) electron-accepting compounds, and (iii) reaction media for determining the onset temperature of the color reaction of the both. Examples thereof include reversibly thermochromic compositions of a heat-discoloring type (color-disappearing by heating and color development by cooling) containing at least three essential components.
The reversible thermochromic composition discolors before and after a predetermined temperature (discoloration point), decolorizes in the temperature range above the high temperature side discoloration point, and colors in the temperature range below the low temperature side discoloration point Present, only one of the two states is present in a particular temperature range, and the other state is maintained while the heat or cold required for the state to appear is applied. However, it has a characteristic that the hysteresis width (ΔH) is relatively small (see FIG. 1), which returns to its original state when the heat or cold is not applied.
In addition, a large hysteresis characteristic is shown, that is, the shape of the curve plotting the change in coloring density due to temperature change falls from the high temperature side rather than the color change temperature range contrary to the case where the temperature is raised from the low temperature side The color changes according to a route that is largely different from that in the case where coloration occurs, and the color development state in the low temperature range below the full color development temperature (t ₁ ) or the color disappearance state in the high temperature range above the complete color disappearance temperature (t ₄ ) , Reversible heat of heat-decoloring type (color-disappearing by heating and color-developing by cooling) having color memory in a specific temperature range [temperature range between t _{2 and} t ₃ (substantial two-phase holding temperature range)] Color changing compositions can also be applied (see FIG. 2).

The components (i), (ii) and (iii) will be specifically described below.
The component (i) of the present invention, that is, the electron-donating coloring organic compound is a component that determines the color, and is a compound that gives electrons to the component (ii) that is a developer and develops a color.
Examples of the electron donating color forming organic compound include phthalide compounds, fluoran compounds, styrinoquinoline compounds, pyridine compounds, quinazoline compounds, bisquinazoline compounds, and diazarhodamine lactone compounds, and among them, since they have fluorescence during color development The pyridine compound, the quinazoline compound, the biskinazoline compound, and the diazarhodamine lactone type compound are used, and the pyridine compound is used suitably.
As said pyridine type 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-duralidinyl) -2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (4-methylphenyl) -2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (4-Methyloxyphenyl) -2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (4-Methyloxyphenyl) -2,6-bis (4-morpholinophenyl) -pyridine,
4- (4-fluorophenyl) -2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (4-N-octyloxyphenyl-N-methylamino) -2,6-diphenylpyridine,
4- (4-chlorophenyl) -2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (4-nitrophenyl) -2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (4-N-2-cyanoethyl-N-methylaminophenyl) -2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (2,5-Dimethyloxyphenyl) -2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (4-diethylaminophenyl) -2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (4-biphenylyl) -2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (4-Pyrrolidinylphenyl) -2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (4-isoindolinylphenyl) -2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (4-N-2-cyanoethyl-N-methylaminophenyl) -2,6-diphenylpyridine,
4- (4-N-methyl-N-phenylaminophenyl) -2,6-diphenylpyridine,
4- (4-N-chloroethyl-N-methylaminophenyl) -2,6-diphenylpyridine,
4- (4-N-ethyloxyethyl-N-methylaminophenyl) -2,6-diphenylpyridine,
2,6-Bis (2 ', 4'-dimethyloxyphenyl) -4- (4'-dimethylaminophenyl) -pyridine,
2,6-Bis (2 ', 4'-diethyloxyphenyl) -4- (4'-dimethylaminophenyl) -pyridine,
2,6-Bis (2 ', 4'-dipropyloxyphenyl) -4- (4'-dimethylaminophenyl) -pyridine,
2,6-Bis (2 ', 4'-dibutyloxyphenyl) -4- (4'-dimethylaminophenyl) -pyridine,
2,6-Bis (2 ', 4'-dipentyloxyphenyl) -4- (4'-dimethylaminophenyl) -pyridine,
2,6-Bis (2 ', 4'-dihexyloxyphenyl) -4- (4'-dimethylaminophenyl) -pyridine,
2,6-Bis (2 ', 4'-dimethyloxyphenyl) -4- (4'-diethylaminophenyl) -pyridine,
2,6-Bis (2 ', 4'-diethyloxyphenyl) -4- (4'-diethylaminophenyl) -pyridine,
2,6-Bis (2 ', 4'-dipropyloxyphenyl) -4- (4'-diethylaminophenyl) -pyridine,
2,6-Bis (2 ', 4'-dibutyloxyphenyl) -4- (4'-diethylaminophenyl) -pyridine,
2,6-Bis (2 ', 4'-dipentyloxyphenyl) -4- (4'-diethylaminophenyl) -pyridine,
2,6-Bis (2 ', 4'-dihexyloxyphenyl) -4- (4'-diethylaminophenyl) -pyridine,
2,6-Bis (2 ', 4'-dimethyloxyphenyl) -4- (4'-dipropylaminophenyl) -pyridine,
2,6-Bis (2 ', 4'-diethyloxyphenyl) -4- (4'-dipropylaminophenyl) -pyridine,
2,6-Bis (2 ', 4'-dipropyloxyphenyl) -4- (4'-dipropylaminophenyl) -pyridine,
2,6-Bis (2 ', 4'-dibutyloxyphenyl) -4- (4'-dipropylaminophenyl) -pyridine,
2,6-Bis (2 ', 4'-dipentyloxyphenyl) -4- (4'-dipropylaminophenyl) -pyridine,
2,6-Bis (2 ', 4'-dihexyloxyphenyl) -4- (4'-dipropylaminophenyl) -pyridine,
2,6-Bis (2 ', 4'-dimethyloxyphenyl) -4- (4'-dibutylaminophenyl) -pyridine,
2,6-Bis (2 ', 4'-diethyloxyphenyl) -4- (4'-dibutylaminophenyl) -pyridine,
2,6-Bis (2 ', 4'-dipropyloxyphenyl) -4- (4'-dibutylaminophenyl) -pyridine,
2,6-Bis (2 ', 4'-dibutyloxyphenyl) -4- (4'-dibutylaminophenyl) -pyridine,
2,6-Bis (2 ', 4'-dipentyloxyphenyl) -4- (4'-dibutylaminophenyl) -pyridine,
2,6-Bis (2 ', 4'-dihexyloxyphenyl) -4- (4'-dibutylaminophenyl) -pyridine,
Etc.

As the quinazoline compound,
2- (4'-dimethylaminophenyl) -4-methyloxy-quinazoline,
2- (4'-dimethylaminophenyl) -4-phenyloxy-quinazoline, 2- (4'-dimethylaminophenyl) -4- (4'-nitrophenyloxy) -quinazoline,
2- (4'-dimethylaminophenyl) -4-phenylthio-quinazoline,
2- (4'-N-phenyl-N-methylaminophenyl) -4-phenyloxy-quinazoline,
2- (4'-piperidinophenyl) -4-phenoxy-quinazoline,
2- (4'-dimethylaminophenyl) -4- (4 "-chlorophenyloxy) -quinazoline,
2- (4'-dimethylaminophenyl) -4- (4 "-methyloxyphenyloxy) -quinazoline,
2- (4'-dimethylaminophenyl) -4- (N-phenyl-N-methylamino) -quinazoline,
2- (4'-dimethylaminophenyl) -4-morpholino-quinazoline,
2- (4'-diethylaminophenyl) -4-phenyl-quinazoline,
2- (4'-diethylaminophenyl) -4-methyl-quinazoline,
2- (1'-ethyl-2 ', 2', 4'-trimethyl-tetrahydroquinolin-6'-yl) -4-phenyloxy-quinazoline,
2- (1'-ethyl-2 ', 2', 4'-trimethyl-tetrahydroquinolin-6'-yl) -4-methyloxy-quinazoline,
2- (1 ', 2', 2 ', 4'-tetramethyl-tetrahydroquinolin-6'-yl) -4-phenyloxy-quinazoline,
2- (1'-ethyl-2'-methyl-tetrahydroquinolin-6'-yl) -4-phenyloxy-quinazoline,
2- (1 ', 3'-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,
Etc.

Examples of the biskinazoline compound include
4,4 '-(Ethylenedioxy) -bis [2- (4-diethylaminophenyl) -quinazoline],
4,4 '-[Propylenedioxy (1,3)]-bis [2- (4-diethylaminophenyl) -quinazoline],
4,4 '-[Butylenedioxy (1,3)]-bis [2- (4-diethylaminophenyl) -quinazoline],
4,4 '-[Butylenedioxy (1,4)]-bis [2- (4-diethylaminophenyl) -quinazoline],
4,4 '-(oxydiethylene) -bis [2- (4-diethylaminophenyl) -quinazoline],
4,4'-Ethylene-bis [2- (4-piperidinophenyl) -quinazoline] 4,4'-ethylene-bis [2- (4-di-n-propylaminophenyl) -quinazoline],
4,4 '-(Ethylenedioxy) -bis [2- (4-di-n-butylaminophenyl) -quinazoline],
4,4'-cyclohexylene-bis [2- (4-diethylaminophenyl) -quinazoline],
Etc.

Examples of the diazarhodamine lactone compounds include
2- (Dimethylamino) -8- (dimethylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran] -3 '-On,
2- (diethylamino) -8- (diethylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran] -3'- on,
2- (di-n-propylamino) -8- (di-n-propylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3') H)-Isobenzofuran] -3'-one,
2- (di-n-butylamino) -8- (di-n-butylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3') H)-Isobenzofuran] -3'-one,
2- (di-n-butylamino) -8- (dimethylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -iso Benzofuran] -3'-one,
2- (di-n-butylamino) -8- (diethylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran ] -3'-on,
2- (di-n-butylamino) -8- (N-ethyl-N-i-butylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -Isobenzofuran] -3'-one,
2- (di-n-butylamino) -8- (N-ethyl-N-i-amylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -Isobenzofuran] -3'-one,
2- (di-n-butylamino) -8- (N-ethyl-Nn-hexylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -Isobenzofuran] -3'-one,
2- (di-n-butylamino) -8- (di-n-amylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) ) -Isobenzofuran] -3'-one,
2- (di-n-butylamino) -8- (n-octylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -Isobenzofuran] -3'-one,
2- (Dimethylamino) -8- (diethylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran] -3' -On,
2- (diethylamino) -8- (dimethylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran] -3' -On,
2- (morpholino) -8- (diethylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran] -3'- on,
2- (Piperidino) -8- (diethylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran] -3'- on,
2- (N-Methylpiperazino) -8- (diethylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran] -3 '-On,
2- (Pyrrolidino) -8- (diethylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran] -3'- on,
2- (diethylamino) -8- (diethylamino) -4-methyl-4 ', 5', 6 ', 7'-tetrachloro-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5, 1 '(3'H) -isobenzofuran] -3'-one,
2- (diethylamino) -8- (diethylamino) -spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran] -3'-one,
2- (di-n-butylamino) -8- (di-n-butylamino) -spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -iso Benzofuran] -3'-one,
2- (N-ethyl-N-i-amylamino) -8- (N-ethyl-N-i-amylamino) -spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '( 3'H) -Isobenzofuran] -3'-one,
2- (di-n-butylamino) -8- (diethylamino) -spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran] -3' -On,
2- (di-n-butylamino) -8- (N-ethyl-N-i-amylamino) -spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) ) -Isobenzofuran] -3'-one,
2- (Piperidino) -8- (ethylamino) -4-methyl-7-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran ] -3'-on,
2- (di-n-butylamino) -8- (diethylamino) -4-methyl-7-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) ) -Isobenzofuran] -3'-one,
2- (di-n-butylamino) -8- (diethylamino) -4-methyl-7-ethyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) ) -Isobenzofuran] -3'-one,
2- (di-n-butylamino) -8- (diethylamino) -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran ] -3'-on,
2- (di-n-butylamino) -8- (di-n-butylamino) -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3') H)-Isobenzofuran] -3'-one,
2- (di-n-butylamino) -8- (N-ethyl-N-i-amylamino) -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -Isobenzofuran] -3'-one,
2- (Piperidino) -8- (diethylamino) -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran] -3'- on,
2- (N-Methyl-N-cyclohexylamino) -8- (diethylamino) -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H)- Isobenzofuran] -3'-one,
2- (Dimethylamino) -8- (diethylamino) -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran] -3' -On,
2- (i-amylamino) -8- (diethylamino) -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran] -3 '-On,
2- (pyrrolidino) -8- (diethylamino) -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran] -3'- on,
2- (N-Methylpiperazino) -8- (diethylamino) -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran] -3 '-On,
2- (morpholino) -8- (diethylamino) -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran] -3'- on,
2- (N-Methyl-N-benzylamino) -8- (diethylamino) -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H)- Isobenzofuran] -3'-one,
2- [di (2-methoxyethyl) amino] -8- (diethylamino) -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H)- Isobenzofuran] -3'-one,
2- (di-n-butylamino) -8- (diethylamino) -4- (4-methoxyphenyl) -spiro [5H- [1] benzopyrano (2,3-d) pyrimidine-5,1 '(3') H)-Isobenzofuran] -3'-one,
2- (di-n-butylamino) -8- (diethylamino) -4- (4-chlorophenyl) -spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) ) -Isobenzofuran] -3'-one,
2- (di-n-butylamino) -8- (diethylamino) -4- (4-methylphenyl) -spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3') H)-Isobenzofuran] -3'-one,
2- [di (2-ethoxyethyl) amino] -8- (dimethylamino) -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -Isobenzofuran] -3'-one,
2- (diethylamino) -8-[(2-methylphenyl) amino] -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -iso Benzofuran] -3'-one,
2- (2,6-Dimethylmorpholino) -8- (diethylamino) -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran ] -3'-on,
2- (dicyclohexylamino) -8- (dimethylamino) -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran] -3 '-On,
2- (Dibutylamino) -8-[(4-chlorophenyl) amino] -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -iso Benzofuran] -3'-one,
Etc.

As the electron accepting compound of the component (ii), a compound group having an active proton, a pseudo-acidic compound group (a compound group which is not an acid but acts as an acid in the composition to cause the component (i) to develop color) There is a compound group having an electron vacancy.
Examples of compounds having an active proton include monophenols to polyphenols as compounds having a phenolic hydroxyl group, and further, as a substituent thereof, an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, a carboxy group and an ester thereof Or those having an amido group, a halogen group and the like, and bis-type and tris-type phenols and the like, and phenol-aldehyde condensation resins and the like. Moreover, the metal salt of the compound which has the said phenolic hydroxyl group may be sufficient.
Specific examples are given below.
Phenol, o-cresol, tertiary butyl catechol, nonylphenol, n-octylphenol, n-dodecylphenol, n-stearylphenol, p-chlorophenol, p-bromophenol, o-phenylphenol, n-butyl n-hydroxybenzoate P-hydroxybenzoic acid n-octyl, resorcine, dodecyl gallate, 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) 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', there are 4'-dihydroxybenzophenone, and the like.
The compound having a phenolic hydroxyl group can exhibit the most effective thermochromic properties, but aromatic carboxylic acids and aliphatic carboxylic acids having 2 to 5 carbon atoms, carboxylic acid metal salts, acidic phosphoric acid esters and the like It may be a compound selected from metal salts, 1,2,3-triazole and derivatives thereof.

The component (iii) of the reaction medium which causes the electron transfer reaction by the components (i) and (ii) to occur reversibly in the specific temperature range will be described.
Examples of the component (iii) include alcohols, esters, ketones, ethers and acid amides.
When the compound is applied to microencapsulation and secondary processing, low molecular weight substances evaporate out of the capsule when subjected to high heat treatment, and therefore, have 10 or more carbon atoms in order to be stably retained in the capsule The compounds are preferably used.
As the alcohols, aliphatic monovalent saturated alcohols having 10 or more carbon atoms are effective, and specifically, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl Alcohol, heptadecyl alcohol, octadecyl alcohol, eicosyl alcohol, docosyl alcohol and the like can be mentioned.

  As the esters, esters having 10 or more carbon atoms are effective, and any combination of a monovalent carboxylic acid having an aliphatic and alicyclic or aromatic ring with a monovalent alcohol having an aliphatic and alicyclic or aromatic ring And esters obtained from any combination of an aliphatic and alicyclic or aromatic polyvalent carboxylic acid and an aliphatic and alicyclic or aromatic monovalent alcohol. Or an ester obtained from any combination of a monovalent carboxylic acid having an aromatic ring and a polyhydric alcohol having an aliphatic and alicyclic or aromatic ring, and specific examples thereof include ethyl caprylate, octyl caprylate and capryl Stearyl acid, myristyl caprate, docosyl caprate, 2-ethylhexyl laurate, n-decyl laurate, myris 3-Methylbutyl benzoate, cetyl myristate, isopropyl palmitate, neopentyl palmitate, nonyl palmitate, cyclohexyl palmitate, n-butyl stearate, 2-methylbutyl stearate, 3,5,5-trimethylhexyl stearate, stearin N-undecyl acid, pentadecyl stearate, stearyl stearate, cyclohexylmethyl stearate, isopropyl behenate, hexyl behenate, lauryl behenate, behenyl behenate, cetyl benzoate, stearyl p-tert-butylbenzoate, dimyristyl phthalate , Distearyl phthalate, Dimyristyl Oxalate, Dicetyl Oxalate, Dicetyl Malonate, Dilauryl Succinate, Dilauryl Glutarate, Diundecyl Adipate, Azelaic Acid Lauryl, di- (n-nonyl) sebacate, dineopentyl 1,18-octadecylmethylenedicarboxylate, ethylene glycol dimyristate, propylene glycol dilaurate, propylene glycol distearate, hexylene glycol dipalmitate, 1,5-pentane Diol distearate, 1,2,6-hexanetrioltrimyristate, 1,4-cyclohexanediol didecyl, 1,4-cyclohexanedimethanol dimyristate, xylene glycol dicaprylate, xylene glycol distearate, etc. It can be mentioned.

Also, esters of saturated fatty acids and branched fatty alcohols, unsaturated fatty acids or esters of branched fatty acids with branched or substituted saturated fatty acids, aliphatic alcohols having 16 or more carbon atoms, cetyl butyrate, stearyl butyrate and Ester compounds selected from behenyl butyrate are also effective.
Specifically, 2-ethylhexyl butyrate, 2-ethylhexyl behenate, 2-ethylhexyl myristate, 2-ethylhexyl caprate, 3,5,5-trimethylhexyl laurate, 3,5,5-trimethylhexyl palmitate, 3,5,5-trimethylhexyl stearate, 2-methylbutyl caproate, 2-methylbutyl caprylate, 2-methylbutyl caprate, 1-ethylpropyl palmitate, 1-ethylpropyl stearate, 1-ethylpropyl behenate, 1-ethylhexyl laurate, 1-ethylhexyl myristate, 1-ethylhexyl palmitate, 2-methylpentyl caproate, 2-methylpentyl caprylate, 2-methyl pentyl caprate, 2-methyl pentyl laurate, 2-methyl stearate Methi Butyl, 2-methylbutyl stearate, 3-methylbutyl stearate, 1-methylheptyl stearate, 2-methylbutyl behenate, 3-methylbutyl behenate, 1-methylheptyl stearate, 1-methylheptyl behenate, caproic acid 1 -Ethylpentyl, 1-ethylpentyl palmitate, 1-methylpropyl stearate, 1-methyloctyl stearate, 1-methylhexyl stearate, 1,1-dimethylpropyl laurate, 1-methylpentyl caprate, palmitic acid 2-Methylhexyl, 2-Methylhexyl Stearate, 2-Methylhexyl Behenate, 3,7-Dimethyloctyl Laurate, 3,7-Dimethyloctyl Myristate, 3,7-Dimethyloctyl Palmitate, Stearic Acid 3, 7-Jime Octyl, 3,7-dimethyloctyl behenate, stearyl sterate oleate, behenyl oleate, stearyl linoleate, behenyl linoleate, 3,7-dimethyloctyl erucate, stearyl erbate, isostearyl erbate, cetyl isostearate, isostearin Stearyl acid, 2-methylpentyl 12-hydroxystearate, 2-ethylhexyl 18-bromostearate, isostearyl 2-ketomyristate, 2-ethylhexyl 2-fluoromyristate, cetyl butyrate, stearyl butyrate, behenyl butyrate and the like Be

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

A fatty acid ester compound obtained from an odd aliphatic monohydric alcohol having 9 or more carbon atoms and an aliphatic carboxylic acid having an even carbon number, n-pentyl alcohol or n-heptyl alcohol, and an even aliphatic carboxylic acid having 10 to 16 carbon atoms Fatty acid ester compounds having 17 to 23 carbon atoms in total obtained from acids are also effective.
Specifically, n-pentadecyl acetate, n-tridecyl butyrate, n-pentadecyl butyrate, n-undecyl caproate, n-tridecyl caproate, n-pentadecyl caproate, n-nonyl caprylate, n-undecyl caprylate, Caprylic acid n-tridecyl, caprylic acid n-pentadecyl, caprate n-heptyl, caprate n-nonyl, caprate n-undecyl, caprate n-tridecyl, caprate n-pentadecyl, caprate n-pentadecyl, laurate n-pentyl, laurate 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 phosphite, n-pentyl palmitate, n-heptyl palmitate, n-nonyl palmitate, n-undecyl palmitate, n-tridecyl palmitate, n-pentadecyl palmitate, n-nonyl stearate, stearic acid n-undecyl, n-tridecyl stearate, n-pentadecyl stearate, n-nonyl eicosanoic acid, n-undecillic eicosanoic acid, n-tridecyl eicosanoic acid, n-pentadecyl eicosanoic acid, n-nonyl behenate, n-behenic acid Undecyl, n-tridecyl behenate, n-pentadecyl behenate and the like can be mentioned.

As ketones, aliphatic ketones having a total carbon number of 10 or more are effective, and 2-decanone, 3-decanone, 4-decanone, 2-undecanone, 3-undecanone, 4-undecanone, 5-undecanone, 2 -Dodecanone, 3-dodecanone, 4-dodecanone, 5-dodecanone, 2-tridecanone, 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-haeneicosanone, 2-docosanone, laurone, stearone and the like.
Furthermore, arylalkyl ketones having 12 to 24 carbon atoms in total, such as n-octadecanophenone, n-heptadecanophenone, n-hexadecanophenone, n-pentadecanophenone, n-tetradecane Nophenone, 4-n-dodecaacetophenone, n-tridecanophenone, 4-n-undecanoacetophenone, n-laurophenone, 4-n-decanoacetophenone, n-undecanophenone, 4-n-nonylacetophenone, n-Decanophenone, 4-n-octylacetophenone, n-nonanophenone, 4-n-heptylacetophenone, n-octanophenone, 4-n-hexylacetophenone, 4-n-cyclohexylacetophenone, 4-tert-butylpropiophenone , N-heptaphenone, 4-n-pentylacetofu Non, cyclohexyl phenyl ketone, benzyl -n- butyl ketone, 4-n-butyl acetophenone, n- hexanophenone, 4-isobutyl acetophenone, 1-acetonaphthone, 2-acetonaphthone, cyclopentyl phenyl ketone.

  As ethers, aliphatic ethers having 10 or more carbon atoms in total are effective, and dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, dinonyl ether, didecyl ether, diundecyl ether, didodecyl ether, ditriethyl ether. Decylether, ditetradecylether, dipentadecylether, dihexadecylether, dioctadecylether, decanediol dimethylether, undecanediol dimethylether, dodecanediol dimethylether, tridecanediol dimethylether, decanediol diethylether, undecanediol diethylether, etc. It can be mentioned.

  As acid amides, acetamide, propionic acid amide, butyric acid amide, caproic acid amide, caprylic acid amide, capric acid amide, lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, oleic acid amide , Erucic acid amide, benzamide, caprolic anilide, caprylic anilide, capric acid anilide, lauric acid anilide, anilide myristate, anilide palmitate, anilide stearic acid, anilide behenic acid anilide, anilide oleic acid, anilide erucic acid, caproic acid N -Methylamide, caprylic acid N-methylamide, capric acid N-methylamide, lauric acid N-methylamide, myristic acid N-methylamide, palmitic acid N-methylamide, stearic acid N-methylamide , Behenic acid N-methylamide, oleic acid N-methylamide, erucic acid N-methylamide, lauric acid N-ethylamide, myristic acid N-ethylamide, palmitic acid N-ethylamide, stearic acid N-ethylamide, oleic acid N-ethylamide, laurin Acid N-butylamide, myristic acid N-butylamide, palmitic acid N-butylamide, stearic acid N-butylamide, oleic acid N-butylamide, lauric acid N-octylamide, myristic acid N-octylamide, palmitic acid N-octylamide, Stearic acid N-octylamide, oleic acid N-octylamide, lauric acid N-dodecylamide, myristic acid N-dodecylamide, palmitic acid N-dodecylamide, stearic acid N-dodecylamide, olei Acid N-dodecylamide, dilauric acid amide, dimyristic acid amide, dipalmitic acid amide, distearic acid amide, dioleic acid amide, trilauric acid amide, trimyriistic acid amide, tripalmitic acid amide, tristearic acid amide, trioleic acid Amide, succinic acid amide, adipic acid amide, glutaric acid amide, malonic acid amide, azelaic acid amide, maleic acid amide, succinic acid N-methylamide, adipic acid N-methylamide, glutaric acid N-methylamide, malonic acid N-methylamide, Azelaic acid N-methylamide, succinic acid N-ethylamide, adipic acid N-ethylamide, glutaric acid N-ethylamide, malonic acid N-ethylamide, azelaic acid N-ethylamide, succinic acid N-butylamide, adipic acid N- Butylamide, glutaric acid N-butylamide, malonic acid N-butylamide, adipic acid N-octylamide, adipic acid N-dodecylamide and the like can be mentioned.

〔式中、Ｒ_１は水素原子又はメチル基を示し、ｍは０〜２の整数を示し、Ｘ_１、Ｘ_２のいずれか一方は−（ＣＨ_２）_ｎＯＣＯＲ_２又は−（ＣＨ_２）_ｎＣＯＯＲ_２、他方は水素原子を示し、ｎは０〜２の整数を示し、Ｒ_２は炭素数４以上のアルキル基又はアルケニル基を示し、Ｙ_１及びＹ_２は水素原子、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。 Moreover, the compound shown by following General formula (1) can also be used as said (iii) component.

[Wherein, R ₁ represents a hydrogen atom or a methyl group, m represents an integer of 0 to ₂ , and either one of X ₁ and X ₂ represents — (CH ₂ ) _n OCOR ₂ or — (CH ₂ ) _n COOR ₂ , the other represents a hydrogen atom, n represents an integer of 0 to 2, R ₂ represents an alkyl group having 4 or more carbon atoms or an alkenyl group, Y ₁ and Y _{2 each} represent a hydrogen atom, 1 to 4 carbon atoms And an alkyl group, a methoxy group or a halogen, and r and p each represents an integer of 1 to 3. ]
Among the compounds represented by the above formula (1), when R ₁ is a hydrogen atom, it is preferable because a reversible thermochromic composition having a wider hysteresis width can be obtained, and R ₁ is a hydrogen atom, and , M is more preferably 0.
Among the compounds represented by the formula (1), more preferably a compound represented by the following general formula (2) is used.

R in the formula represents an alkyl group having 8 or more carbon atoms or an alkenyl group, preferably an alkyl group having 10 to 24 carbon atoms, and more preferably an alkyl group having 12 to 22 carbon atoms.
Specifically as the compound, 4-benzyloxyphenylethyl octanoate, 4-benzyloxyphenylethyl nonanoate, 4-benzyloxyphenylethyl decanoate, 4-benzyloxyphenylethyl undecanoate, dodecanoic acid -4-benzyloxyphenylethyl, 4-benzyloxyphenylethyl tridecanoate, 4-benzyloxyphenylethyl tetradecanoate, 4-benzyloxyphenylethyl pentadecanoate, 4-benzyloxyphenylethyl hexadecanoate, heptadecanoic acid Examples thereof include 4-benzyloxyphenylethyl and 4-benzyloxyphenylethyl octadecanoate.

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

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

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

(Wherein, X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, or a halogen atom, m represents an integer of 1 to 3 and n represents an integer of 1 to 20)
Examples of the compound include a diester of malonic acid and 2- [4- (4-chlorobenzyloxy) phenyl] ethanol, a diester of succinic acid and 2- (4-benzyloxyphenyl) ethanol, succinic acid and 2- (4-benzyloxyphenyl) ethanol. [4- (3-Methylbenzyloxy) phenyl)] diester with ethanol, diester of glutaric acid with 2- (4-benzyloxyphenyl) ethanol, glutaric acid with 2- [4- (4-chlorobenzyloxy)] Phenyl) diester with ethanol, diester of adipic acid and 2- (4-benzyloxyphenyl) ethanol, diester of pimelic acid and 2- (4-benzyloxyphenyl) ethanol, suberic acid and 2- (4- Diester with benzyloxyphenyl) ethanol, suberic acid and 2- [4- (3-methyl] Dibenzyloxy) phenyl)] diester with ethanol, diester of suberic acid and 2- [4- (4-chlorobenzyloxy) phenyl)] ethanol, suberic acid and 2- [4- (2,4-dichlorobenzyloxy) ) Phenyl) diester with ethanol, diester of azelaic acid and 2- (4-benzyloxyphenyl) ethanol, diester of sebacic acid and 2- (4-benzyloxyphenyl) ethanol, 1, 10-decanedicarboxylic acid And diesters of 2- (4-benzyloxyphenyl) ethanol, diesters of 1,18-octadecanedicarboxylic acid and 2- (4-benzyloxyphenyl) ethanol, 1,18-octadecanedicarboxylic acid and 2- [4- (2-Methylbenzyloxy) phenyl)] with ethanol It can be exemplified ether.

（式中、Ｒは炭素数１乃至２１のアルキル基又はアルケニル基を示し、ｎは１乃至３の整数を示す。）
前記化合物としては、１，３−ビス（２−ヒドロキシエトキシ）ベンゼンとカプリン酸とのジエステル、１，３−ビス（２−ヒドロキシエトキシ）ベンゼンとウンデカン酸とのジエステル、１，３−ビス（２−ヒドロキシエトキシ）ベンゼンとラウリン酸とのジエステル、１，３−ビス（２−ヒドロキシエトキシ）ベンゼンとミリスチン酸とのジエステル、１，４−ビス（ヒドロキシメトキシ）ベンゼンと酪酸とのジエステル、１，４−ビス（ヒドロキシメトキシ）ベンゼンとイソ吉草酸とのジエステル、１，４−ビス（２−ヒドロキシエトキシ）ベンゼンと酢酸とのジエステル、１，４−ビス（２−ヒドロキシエトキシ）ベンゼンとプロピオン酸とのジエステル、１，４−ビス（２−ヒドロキシエトキシ）ベンゼンと吉草酸とのジエステル、１，４−ビス（２−ヒドロキシエトキシ）ベンゼンとカプロン酸とのジエステル、１，４−ビス（２−ヒドロキシエトキシ）ベンゼンとカプリル酸とのジエステル、１，４−ビス（２−ヒドロキシエトキシ）ベンゼンとカプリン酸とのジエステル、１，４−ビス（２−ヒドロキシエトキシ）ベンゼンとラウリン酸とのジエステル、１，４−ビス（２−ヒドロキシエトキシ）ベンゼンとミリスチン酸とのジエステルを例示できる。 Furthermore, the compound shown by following General formula (5) can also be used as said (iii) component.

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

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

(Wherein, X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, m represents an integer of 1 to 3 and n represents 1 to 20) Indicates an integer of
Examples of the 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, a diester of 1,10-decanedicarboxylic acid and 2-phenoxyethanol, 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。 Furthermore, the compound shown by following General formula (7) can also be used as said (iii) component.

(Wherein R represents an alkyl group having 4 to 22 carbon atoms, a cycloalkyl alkyl group, a cycloalkyl group, or an alkenyl group having 4 to 22 carbon atoms, and X represents a hydrogen atom or an alkyl having 1 to 4 carbon atoms R 1 represents any of a group, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom, and n represents 0 or 1.)
Examples of the compound include decyl 4-phenylbenzoate, lauryl 4-phenylbenzoate, myristyl 4-phenylbenzoate, cyclohexylethyl 4-phenylbenzoate, octyl 4-biphenylacetate, nonyl 4-biphenylacetate, 4-biphenylacetic acid Decyl, 4-biphenyl acetate lauryl, 4-biphenyl acetate myristyl, 4-biphenyl acetate tridecyl, 4-biphenyl acetate pentadecyl, 4-biphenyl acetate cetyl, 4-biphenyl acetate cyclopentyl, 4-biphenyl acetate cyclohexylmethyl, 4-biphenyl acetate hexyl And 4-biphenylcyclohexyl methyl acetate 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。 Furthermore, the compound shown by following General formula (8) can also be used as said (iii) component.

(Wherein R represents an alkyl group having 3 to 18 carbon atoms or an aliphatic acyl group having 3 to 18 carbon atoms, and X represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, 1 or 2 carbon atoms And Y represents a hydrogen atom or a methyl group, Z represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 or 2 carbon atoms, a halogen atom Show one of the
Examples of the compound include phenoxyethyl 4-butoxybenzoate, phenoxyethyl 4-pentyloxybenzoate, phenoxyethyl 4-tetradecyloxybenzoate, an ester of phenoxyethyl 4-hydroxybenzoate and dodecanoic acid, phenoxyethyl vanilliate 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。 Furthermore, the compound shown by following General formula (9) can also be used as said (iii) component.

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

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

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

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

(Wherein 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 The diester of (2-hydroxyethoxy) benzene and cyclohexane propionic acid can be exemplified.

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

(Wherein R represents an alkyl group having 3 to 17 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a cycloalkyl alkyl group having 5 to 8 carbon atoms, and X represents a hydrogen atom or an alkyl having 1 to 5 carbon atoms Group, a methoxy group, an ethoxy group, a halogen atom, and n is 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, 4 -A diester of phenylphenol ethylene glycol ether and octanoic acid, a diester of 4-phenylphenol ethylene glycol ether and nonanoic acid, a diester of 4-phenylphenol ethylene glycol ether and decanoic acid, 4-phenylphenol ethylene glycol ether and myristin An example is a diester with an acid.

  The reversible thermochromic composition of the present invention is a compatibilizer comprising the above components (A), (B) and (C) as essential components, and the ratio of each component is the concentration, color change temperature, color change form or each component However, the component ratio which generally gives the desired properties is preferably 0.1 to 100, more preferably 0.1 to 50, based on component (1). Is in the range of 0.5 to 20, (c) component 5 to 200, preferably 5 to 100, more preferably 10 to 100 (the above proportions are all parts by mass).

Furthermore, various light stabilizers can be added as necessary.
The said light stabilizer is contained in order to prevent the photodegradation of the reversible thermochromic composition which consists of (i), (ii), and (iii) components, and it is 0.3 with respect to 1 mass% of (ii) components. It is contained in a proportion of 24 to 24% by mass, preferably 0.3 to 16% by mass. Further, among the light stabilizers, the ultraviolet light absorber effectively cuts the ultraviolet light contained in sunlight and the like to prevent the light deterioration caused by the excited state due to the light reaction of the component (i). Further, antioxidants, singlet oxygen quenchers, superoxide anion quenchers, ozone quenchers, etc. inhibit the oxidation reaction by light.
The light stabilizers may be used alone or in combination of two or more.

The reversibly thermochromic composition is used as a reversibly thermochromic pigment by dispersing in a thermoplastic resin or thermosetting resin, or by enclosing it in microcapsules.
Incidentally, microcapsulation can be performed by conventionally known interfacial polymerization method, in situ polymerization method, in-liquid curing coating method, phase separation method from aqueous solution, phase separation method from organic solvent, melting dispersion cooling method, suspension in air There are a coating method, a spray drying method and the like, which are appropriately selected according to the application. Furthermore, depending on the purpose, a secondary resin film may be further provided on the surface of the microcapsule to impart durability, or the surface characteristics may be modified to be put to practical use.
The microcapsule pigment preferably has a range of inclusion / wall film = 7/1 to 1/1 (mass ratio), and when the ratio of wall film is in the above range, the color density at the time of color development and A drop in sharpness can be prevented, and more preferably, the inclusion / wall film = 6/1 to 1/1 (mass ratio).
The inclusion in the microcapsule makes it possible to constitute a chemically and physically stable pigment, and the particle diameter is in the range of 0.01 to 50 μm, preferably 0.1 to 30 μm, more preferably 0.5 to 20 μm. Meet the sex.
In addition, the measurement of an average particle diameter determines the area | region of particle | grains using the image analysis type | mold particle size distribution measurement software "Mcview" made by MUNTECH Co., Ltd., and the projected area circle equivalent diameter (Heywood diameter) It is a value calculated and measured as an average particle diameter of particles of equivalent volume sphere according to the value.
When the particle diameter of all particles or most of the particles exceeds 0.2 μm, equivalent volume sphere equivalent is obtained by Coulter method using a particle size distribution measuring device (product name: Multisizer 4e manufactured by Beckman Coulter Co., Ltd.) It is also possible to measure as the average particle size of the particles of

The color change of the reversible thermochromic pigment will be described.
The reversibly thermochromic pigments A and B are completely colored when reaching the full color development temperature (t ₁ ) by the temperature decrease from the decoloring state, and are completely color fading temperature (t ₄ ) by the temperature increase from the color developing state It is a pigment that becomes completely decolored when it reaches it.
By having one complete coloring temperature of the reversible thermochromic pigment A (t ₁₎ than in the high-temperature side of the other reversible thermochromic pigment B complete coloring temperature (t _1), discoloration of the thermochromic pigment at Atsushi Nobori While being able to visually identify the state, the reversibly thermochromic pigment B is a pigment having fluorescence during color development, and thus is rich in the vividness of each color before and after the color change.
The hysteresis characteristics of the color density-temperature curve of the reversibly thermochromic pigment will be described below with reference to the graph of FIG.
In FIG. 2, the vertical axis represents color density, and the horizontal axis represents temperature. The change in color density due to the temperature change proceeds along the arrow. Here, A is a point indicating the density at a temperature t ₄ (hereinafter referred to as a complete bleaching temperature) which reaches a completely erased state, and B is a temperature t ₃ (hereinafter, a bleaching initiation temperature) at which the bleaching starts and referred) is a point showing the density at, C is the temperature t _{2 (hereinafter} to start color development, is a point showing the density at a referred to as a coloring starting temperature), D is the temperature t _{1 (hereinafter} to reach completely colored state , The color development temperature (referred to as the full color development temperature).
Further, the length of the line segment EF is a scale indicating the contrast of the color change, and the length of the line segment HG is a temperature width indicating the degree of hysteresis (hereinafter referred to as hysteresis width ΔH). , It is easy to hold each state before and after the color change.
Here, the difference between t ₄ and t ₃ or the difference between t ₂ and t ₁ (Δt) is a measure of the sensitivity of color change.

More specifically, referring to the color density-temperature curve of FIG. 3 as an example, a reversible thermochromic pigment B having the fluorescence of the other on the higher temperature side than the complete bleaching temperature (t ₄ ) of one reversible thermochromic pigment A. [The reversible thermochromic pigment B is described as (t ') to distinguish it from the reversible thermochromic pigment A] in order to satisfy the complete decolorization temperature (t' ₄ ) of When the temperature is raised from the colored (1) state having fluorescence, in which both are colored, the reversibly thermochromic pigment A disappears to have fluorescence when reaching the temperature of the complete bleaching temperature (t ₄ ) It becomes colored (2), and the reversible thermochromic pigment B is decolored when reaching the temperature of the completely decoloring temperature (t ' ₄ ), so a color change from the colored (2) having fluorescence to colorlessness is visually recognized Ru.
When the temperature reaches the temperature of the full color development (t ₁ = t ′ ₁ ) due to temperature decrease, the reversible thermochromic pigment A and the reversible thermochromic pigment B develop color and return to the colored (1) having fluorescence.
In addition, the color change of fluorescent colored (1), fluorescent colored (2), and colored (3) can be visually recognized by adding a non-coloring colorant, and the fluorescent non-colored When the coloring agent of (1) is used, colored (3) also has fluorescence, so that three bright handwritings can be visually recognized.

As another example, the color density-temperature curve of FIG. 4 will be specifically described. The reversible heat having the other fluorescent property on the higher temperature side than the complete decoloring temperature (t ₄ ) of one of the reversible thermochromic pigments A In order to satisfy the complete decoloring temperature (t ' ₄ ) of the discoloring pigment B, when the temperature is increased from the colored (1) state having fluorescence, in which the reversible thermochromic pigments A and B both develop color, the complete decoloring When the temperature of color temperature (t ₄ ) is reached, the reversible thermochromic pigment A is decolorized to become fluorescent (2), and when the temperature of completely decoloring temperature (t ' ₄ ) is reached, reversible thermal discoloration Since the color pigment B decolorizes, a color change from fluorescent (2) to colorless is observed.
Incidentally, when the temperature reaches the temperature of the full coloring temperature (t ' ₁ ) due to the temperature decrease, the reversible thermochromic pigment B is colored to return to the colored (2) having fluorescence, and the temperature is further lowered to reach the full coloring temperature (t ₁ ). When the temperature is reached, the reversible thermochromic pigment A develops color and returns to the colored (1) having fluorescence.
In addition, the color change of fluorescent colored (1), fluorescent colored (2), and colored (3) can be visually recognized by adding a non-coloring colorant, and the fluorescent non-colored When the coloring agent of (1) is used, colored (3) also has fluorescence, so that three bright handwritings can be visually recognized.

As another example, the color density-temperature curve of FIG. 5 will be specifically described. The reversible heat having the other fluorescent property on the higher temperature side than the complete decoloring temperature (t ₄ ) of one of the reversible thermochromic pigments A In order to satisfy the complete decoloring temperature (t ' ₄ ) of the discoloring pigment B, when the temperature is increased from the colored (1) state having fluorescence, in which the reversible thermochromic pigments A and B both develop color, the complete decoloring When the temperature of color temperature (t ₄ ) is reached, the reversible thermochromic pigment A is decolorized to become fluorescent (2), and when the temperature of completely decoloring temperature (t ' ₄ ) is reached, reversible thermal discoloration Since the color pigment B decolorizes, a color change from fluorescent (2) to colorless is observed.
Incidentally, when the temperature reaches the temperature of the full coloring temperature (t ' ₁ ) due to the temperature decrease, the reversible thermochromic pigment B is colored to return to the colored (2) having fluorescence, and the temperature is further lowered to reach the full coloring temperature (t ₁ ). When the temperature is reached, the reversible thermochromic pigment A develops color and returns to the colored (1) having fluorescence.
In addition, the color change of fluorescent colored (1), fluorescent colored (2), and colored (3) can be visually recognized by adding a non-coloring colorant, and the fluorescent non-colored When the coloring agent of (1) is used, colored (3) also has fluorescence, so that three bright handwritings can be visually recognized.

Furthermore, as another example, specifically explained by the color density-temperature curve of FIG. 6, the reversible heat having the other fluorescence on the higher temperature side than the complete bleaching 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 increased from the colored (1) state having fluorescence, in which the reversible thermochromic pigments A and B both develop color, the complete decoloring When the temperature of color temperature (t ₄ ) is reached, the reversible thermochromic pigment A is decolorized to become fluorescent (2), and when the temperature of completely decoloring temperature (t ' ₄ ) is reached, reversible thermal discoloration Since the color pigment B decolorizes, a color change from fluorescent (2) to colorless is observed.
The reversibly thermochromic pigment A is colored and becomes colored (3) when it reaches the temperature of the full color development temperature (t1) by the temperature decrease, and it is reversible when it reaches the temperature of the full color development temperature (t ' ₁ ). The thermochromic pigment B develops color and returns to the colored (1) having fluorescence.
In addition, the color change of fluorescent colored (1), fluorescent colored (2), colored (3) and colored (4) is visually recognized by adding a non-coloring colorant, and the fluorescent When the non-discoloring coloring agent having (1) is used, the colored (4) also has fluorescence, so that four bright handwritings can be visually recognized.

The color change is made clear by having the complete decolorization temperature (t ' ₄ ) of the reversible thermochromic pigment B on the high temperature side by 10 ° C. or more higher than the complete decolorization temperature (t ₄ ) of the reversible thermochromic pigment A It is visible, preferably 15 ° C. or more, more preferably 20 ° C. or more.
Furthermore, the color change is achieved by having the complete decolorization temperature (t ′ ₄ ) of the reversible thermochromic pigment B on the high temperature side by 10 to 70 ° C. than the complete decolorization temperature (t ₄ ) of the reversible thermochromic pigment A Is preferably 15 to 60.degree. C., more preferably 20 to 50.degree.
When the color is changed by the frictional heat generated by the friction body described later, the temperature 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 complete decoloring temperature (t ′ ₄ ) of the discoloring pigment B, it is easy to cause a color change to be developed by frictional heat.
Further, the complete decoloring temperature (t ₄ ) of the reversibly thermochromic pigment A is 50 ° C. or higher, preferably 55 ° C. or higher, more preferably 60 ° C. or higher, and the full color development temperature (t ₁ ) is 0 ° C. or lower, preferably Is −5 ° C. or less, more preferably −10 ° C. or less, and the complete color development temperature (t ₁ ) of the reversible thermochromic pigment B is 0 ° C. or less, preferably −5 ° C. or less, more preferably −10 ° C. or less By being present, it becomes easy to hold the discolored state at normal temperature.

Next, an ink composition containing the reversibly thermochromic pigment will be described.
The reversibly thermochromic pigment is dispersed in a vehicle for a writing instrument containing water and / or an organic solvent and various additives as required, and used as an ink for a writing instrument such as a marking pen, a ballpoint pen, a fountain pen, a writing pen, etc. it can.
Examples of the various additives include resins, viscosity modifiers, dispersants, anti-settling agents, antifoaming agents, penetrants, pH adjusters, moisturizers, fungicides, preservatives, rust inhibitors and the like.

Among them, as a vehicle for a writing instrument used for an ink for a writing instrument, an oil-based vehicle containing an organic solvent, or an aqueous vehicle containing water and, if necessary, an organic solvent can be mentioned.
As the organic solvent, ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, ethylene glycol monomethyl ether, ethylene glycol 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, etc. It can gel.

In the ink composition of the present invention, dyes and pigments may be used in combination, if necessary.
As the dye, acid dyes, basic dyes and direct dyes which can be dissolved in an aqueous medium can all be used.
The pigments include carbon black, ultramarine blue, inorganic pigments such as titanium dioxide pigments, azo pigments, phthalocyanine pigments, indigo pigments, thioindigo pigments, threne pigments, quinacridone pigments, anthraquinone pigments, throne pigments, diketopyrrolopyrrole pigments Organic pigments and fluorescent pigments such as pigments, dioxazine pigments, perylene pigments, perinone pigments and isoindolinone pigments can be exemplified.
Furthermore, metal powder obtained by treating the surface of aluminum powder or aluminum powder with a coloring resin, metal luster pigment having a metal deposition film formed on a transparent or colored transparent film, phosphorescent pigment, natural mica as a core material, synthetic mica, glass flake, alumina A pearl pigment etc. which coated the surface of a transparency film piece with metal oxides, such as titanium oxide, can also be used.

Examples of the ink for writing instruments 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 loose aggregation state. be able to.
By adding the shear thinning agent, it is possible to suppress aggregation and sedimentation of the pigment, and to suppress bleeding of the handwriting, so that good handwriting can be formed.
Furthermore, when the writing instrument 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 is prevented, or backflow of the ink when the writing tip is left facing up (standing up) Can be prevented.
As the shear thinning agent, xanthan gum, welan gum, succinoglycan (average molecular weight about 1,000,000 to 8,000,000) whose constituent monosaccharide is an organic acid modified heteropolysaccharide of glucose and galactose, guar gum, locust bean gum and the like Derivatives, hydroxyethyl cellulose, alginic acid alkyl esters, polymers with a molecular weight of 100,000 to 150,000 mainly composed of alkyl esters of methacrylic acid, thickening agents with gelling ability extracted from seaweeds such as glucomannan, agar or carrageenan Polysaccharides, benzylidene sorbitol and benzylidene xylitol or derivatives thereof, crosslinkable acrylic acid polymers, inorganic fine particles, polyglycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyethylene glycol fatty acid esters, poly Carboxymethyl ethylene alkyl ethers, polyoxypropylene alkyl ethers, polyoxyethylene alkyl phenyl ether, nonionic HLB value, such as fatty acid amide is 8-12 surfactants, salts of dialkyl or dialkenyl sulfosuccinic acid. A mixture of N-alkyl-2-pyrrolidone and an anionic surfactant, and a mixture of polyvinyl alcohol and an acrylic resin can be exemplified.

Examples of the water soluble polymer flocculant include polyvinyl pyrrolidone, polyethylene oxide, water soluble polysaccharides and the like.
Examples of the water-soluble polysaccharides include tragacanth gum, guar gum, pullulan, cyclodextrin, water-soluble cellulose derivatives and the like, and specific examples of water-soluble cellulose derivatives include methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methylcellulose, hydroxypropyl methyl cellulose Etc.

By using a comb-type polymer dispersant having a carboxyl group in a side chain together with the polymer flocculant, the dispersibility of loose aggregates of microcapsule pigments by the polymer flocculant can be improved.
The comb polymer dispersant having a carboxyl group in the side chain is not particularly limited as long as it is a comb polymer compound having a plurality of carboxyl groups in the side chain, but a plurality of carboxyl groups in the side chain An acrylic polymer compound having the following formula is preferable, and as the compound, Solsparse 43000, a trade name of Nippon Lubrizol Corporation, can be exemplified.

Furthermore, by containing the organic nitrogen sulfur compound, when the ink composition is filled in a writing instrument and put to practical use, sedimentation of the microcapsule pigment due to vibration can be further suppressed.
This is to further improve the dispersibility in which loose aggregates of microcapsule pigments are dispersed by a comb polymer dispersant having a carboxyl group at a side chain.
As the organic nitrogen sulfur compound, a compound selected from thiazole compounds, isothiazole compounds, benzothiazole compounds and benzisothiazole compounds is used.
Specifically as the organic nitrogen sulfur compound, 2- (4-thiazoyl) -benzimidazole (TBZ), 2- (thiocyanatomethylthio) -1,3-benzothiazole (TCMTB), 2-methyl-4-isothiazoline- One or two or more compounds selected from 3-one, 5-chloro-2-methyl-4-isothiazolin-3-one are used, preferably 2- (4-thiazoyl) -benzimidazole (TBZ), 2 One or two or more compounds selected from -methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one are used.
As the organic nitrogen and sulfur compound, manufactured by Permachem Asia Ltd., trade names: Topside 88, 133, 170, 220, 288, 300, 400, 500, 600, 700Z, Hokuster Sangyo Co., Ltd. product name, Hokuster HP, E50A, Hokuside P200, 6500, 7400, MC, 369, R-150 can be exemplified.
The mass ratio of the comb 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, and the above range is satisfied. This makes it possible to sufficiently develop the dispersibility of loose aggregates of microcapsule pigments and the suppression of sedimentation of microcapsule pigments by vibration.

Furthermore, when a water-soluble resin to be applied to impart adhesion and viscosity to the paper surface of the handwriting is added, in the ink containing the comb-type polymer dispersant having a carboxyl group in the above-mentioned side chain and the organic nitrogen sulfur compound The function of enhancing 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, polyvinyl pyrrolidone, polyvinyl alcohol, dextrin and the like, preferably polyvinyl alcohol.
Furthermore, the polyvinyl alcohol is more preferably used because the partially saponified polyvinyl alcohol having a degree of saponification of 70 to 89 mol% is soluble in the acid region of the ink.
The amount of water-soluble resin added is 0.3 to 3.0% by mass, preferably 0.5 to 1.5% by mass, in the ink.

  When the ink is used by filling in a ballpoint pen, higher fatty acids such as oleic acid, nonionic surfactants having a long chain alkyl group, polyether modified silicone oil, thiophosphorous acid tri (alkoxycarbonylmethyl ester) or Thiophosphorous acid triester such as thiophosphorous acid tri (alkoxycarbonylethyl ester), phosphoric acid monoester of polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether, phosphorus of polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether Preferably, a lubricant such as an acid diester or their metal salt, ammonium salt, amine salt or alkanolamine salt is added to prevent abrasion of the ball receiving seat.

  In addition, if necessary, resins such as acrylic resin, styrene maleic acid copolymer, cellulose derivative, polyvinyl pyrrolidone, polyvinyl alcohol, dextrin, etc. are added to impart adhesion and viscosity to the surface of the paper, or sodium carbonate and sodium phosphate PH adjusters such as inorganic salts such as sodium acetate, organic basic compounds such as water-soluble amine compounds, etc., corrosion inhibitors such as benzotriazole, tolyltriazole, dicyclohexylammonium nitrite, diisopropyl ammonium nitrite, saponin, etc. Sodium salt of 1, 2-benzthiazolin 3-one, sodium benzoate, sodium dehydroacetate, potassium sorbate, propyl p-hydroxybenzoate, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine Preservative or Are fungicides, urea, nonionic surfactants, reduced or non-reduced starch hydrolysates, oligosaccharides such as trehalose, sucrose, cyclodextrin, glucose, dextrin, sorbit, mannite, sodium pyrophosphate and other wetting agents A defoaming agent, a dispersing agent, a fluorine-based surfactant for improving the permeability of the ink, or a nonionic surfactant may be added.

  Preferably, 5 to 40% by mass, more preferably 10 to 40% by mass, and still more preferably 10 to 30% by mass of the reversible thermochromic pigment can be contained based on the total mass of the ink. When the content of the pigment is in the above-mentioned range, a desired color density can be achieved, and further, a decrease in ink outflow can be prevented.

The multicolor discoloring aqueous ink composition for writing instruments of the present invention is prepared by charging and stirring the pigment A and the pigment B, if necessary, various additives, in an aqueous medium containing water and a water-soluble organic solvent.
In addition, with respect to the ink having a shear thinning viscosity, the pigment A and the pigment B, various additives are added to an aqueous medium, stirred, dissolved, and further, a shear thinning additive in a solvent separately prepared therefrom The dispersion is prepared by directly dispersing and dispersing the dispersed solution or a shear thinning agent.

The ballpoint pen which accommodates the said ink, and a marking pen are demonstrated.
When filling a ballpoint pen, the structure and shape of the ballpoint pen itself are not particularly limited, and, for example, it has an ink storage tube in which a shear thinning ink is filled in a cylinder, and the ink storage tube has a ball tip It is in communication with the ballpoint pen tip attached to the above, and further, a ballpoint pen in which a backflow prevention liquid stopper is in close contact with the end face of the ink can be exemplified.
The ballpoint pen tip will be described in more detail. A tip obtained by holding a ball in a ball holding portion obtained by pressing and deforming the vicinity of the tip of a metal pipe inward from the outer surface, or cutting a metal material with a drill or the like A chip formed by holding the ball in the ball holding portion formed by the chip, a chip provided with a ball seat made of resin inside the metal or plastic chip, or a ball held by the chip forwardly by a spring body It is possible to apply an energized one or the like.
The ball is made of cemented carbide, stainless steel, ruby, ceramic, resin, rubber, etc. 0.3 to 2.0 mm, preferably 0.3 to 1.5 mm, more preferably 0.3 to 1.0 mm A diameter grade can apply.
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 as the ink storage tube for storing the ink.
The chip may be directly connected to the ink storage tube, or the ink storage tube and the chip may be connected via a connection member.
The ink storage tube may store the refill in a cylinder made of resin, metal or the like as a form of refill, or the cylinder itself having a tip mounted on a tip thereof as an ink container. The ink may be filled directly into the barrel.
When the ink composition is housed in a retractable ballpoint pen, the structure and shape of the retractable ballpoint pen are not particularly limited, and the shaft in a state where the writing tip provided on the ballpoint pen refill is exposed to the air Any structure may be used as long as it is housed in the cylinder and the writing tip projects from the barrel opening by the operation of the retracting mechanism.
Examples of the operation method of the advancing and retracting mechanism include a knocking type, a rotating type, and a sliding type.
The knock type has a knock portion at the rear end of the shaft cylinder or the side surface of the shaft cylinder, and the ball pen tip is made to protrude and retract from the front end opening of the shaft cylinder by pressing the knock portion, or a clip portion provided on the shaft cylinder An example of the configuration in which the ballpoint pen tip is brought out of and brought out of the front end opening of the barrel by pressing.
The rotary type can be exemplified by a configuration having a rotating portion at the rear of the barrel and turning the rotating portion to allow the ballpoint pen tip to come out of the barrel front end opening.
The slide type has a slide portion on the side surface of the shaft cylinder, and by operating the slide, the ballpoint pen tip is made to protrude and retract from the front end opening of the shaft cylinder, or by sliding the clip portion provided on the shaft cylinder. The structure which makes a ball-point pen tip rise and fall from a barrel front end opening can be illustrated.
The retractable ballpoint pen is a composite type of retractable ballpoint pen in which a plurality of ballpoint pen refills are accommodated in a shaft cylinder, and the writing tip of any ballpoint pen refill is projected and retracted from the front end opening of the shaft cylinder by the operation of the movement mechanism. May be

An ink backflow prevention body is filled in the rear end of the ink stored in the ink storage tube.
The ink backflow preventive 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, oligomer or co-oligomer of α-olefin, dimethyl silicone oil, methylphenyl silicone oil, amino modified silicone oil, Polyether modified silicone oil, fatty acid modified silicone oil and the like can be mentioned, and one or more kinds 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 may be silica whose surface is hydrophobically treated, and the surface is methylated. Fine particle silica, aluminum silicate, swellable mica, clay-based thickeners such as bentonite or montmorillonite treated with hydrophobic treatment, magnesium stearate, calcium stearate, fatty acid metal soaps such as aluminum stearate, zinc stearate etc., tribenzylidene sorbitol, Examples include dextrin compounds such as fatty acid amide, amide modified polyethylene wax, hydrogenated castor oil, fatty acid dextrin, and cellulose compounds.
Furthermore, the liquid ink backflow preventive may be used in combination with a solid ink backflow preventive.

When filling the marking pen, the structure and shape of the marking pen itself are not particularly limited. For example, a fiber processed body in which an ink occlusion body consisting of a fiber bundle is incorporated in a shaft cylinder and a capillary gap is formed A marking pen in which the ink storage body of the marking pen in which the ink storage body and the tip are connected is attached to the ink storage body directly or through a relay member, An example is a marking pen or the like in which the chip and the ink storage pipe are disposed via the valve body opened by pressing the chip, and the ink is directly stored in the ink storage pipe.
The chip is a porous member of interconnected pores whose porosity is generally selected from the range of about 30 to 70%, such as resin-processed body of fiber, fusion-processed body of heat-meltable fiber, felt body, etc. One end is processed into a shape according to the purpose, such as a shell shape, a rectangular shape, or a chisel shape, and is put to practical use.
The ink storage material is formed by collecting crimped fibers in the longitudinal direction, and is incorporated in a covering such as a plastic cylinder or a film so that the porosity is adjusted to a range of about 40 to 90%. Be done.
Moreover, although the said valve body can use a general purpose pumping type form conventionally, what was set to the spring pressure which can be pressed and released by pen pressure is suitable.

  Furthermore, the forms of the ballpoint pen and the marking pen are not limited to those described above, and may be a double-ended writing instrument equipped with tips of different forms or with pen tips for deriving inks of different colors.

In addition, the handwriting obtained by writing on a to-be-written surface using the writing instrument which accommodated the said ink composition for writing instruments can be discolored with a heating tool or a cooling tool.
Examples of the heating tool include electric heating color changing tools equipped with resistance heating elements, heating color changing tools filled with warm water or the like, and application of a hair dryer, but preferably, the friction member is a means capable of changing colors by a simple method. Used.
As the friction member, an elastic body such as an elastomer, a plastic foam or the like which is rich in elasticity and can generate appropriate friction upon rubbing to generate frictional heat is preferable.
Although it is possible to rub the handwriting using an eraser, since the scraps are generated at the time of friction, the above-mentioned friction member which hardly generates the scraps is preferably used.
As a material of the said friction member, silicone resin, SEBS resin (styrene ethylene butadiene styrene block copolymer), polyester-type resin etc. are used.
Although the said friction member can also obtain a writing tool set combining an arbitrary-shaped member (friction body) of another body with a writing instrument, it is excellent in portability by providing a friction member in a writing instrument.
In the case of a writing instrument provided with a cap, the place where the friction member is provided is not particularly limited. For example, when the cap itself is formed of a friction member, the barrel itself is formed of a friction member, or a clip is provided The clip itself can be formed by a friction member, or a friction member can be provided at the cap tip (top) or at the rear end of the barrel (the part where the writing tip is not provided).
In the case of a writing-in / recess-type writing tool, the place where the friction member is provided is not particularly limited. For example, the barrel itself is formed by the friction member, or when the clip is provided, the clip itself is formed by the friction member, A friction member can be provided in the vicinity of the barrel opening, in the rear end of the barrel (the portion where the writing front end is not provided) or in the knock portion.
Examples of the cooling tool include a cold-heat discoloring tool utilizing a Peltier element, a cold-heating discoloring tool filled with a coolant such as cold water or ice pieces, a refrigerator, or a freezer.

Examples are described below. In the examples, parts are parts by mass.
Example 1
Preparation of Reversible Thermochromic Pigment (A) 9-ethyl (3-methylbutyl) amino-spiro [12H-benzo (a) xanthene-12,1 '(3'H) isobenzofuran] -3'-one 1 as component Part, 8 parts of bis (3-methyl-4-hydroxyphenyl) sulfide as component (ii), 5 parts of 1,1-bis (4'-hydroxyphenyl) hexafluoropropane, 4-benzyl caprate as component (iii) A reversible thermochromic pigment A was prepared by encapsulating the reversible thermochromic composition a consisting of 50 parts of oxyphenylethyl in microcapsules.
The average particle diameter of the reversible thermochromic pigment A is 2.0 μm, the complete bleaching temperature (t ₄ ) is 64 ° C., and the full coloring temperature (t ₁ ) is −14 ° C. It turns colorless.
1 part of 2,6-bis (2-ethyloxyphenyl) -4- (4-bis (4-methylphenyl) aminophenyl) pyridine as component (i), 2,2-bis (4 ') as component (ii) Reversible thermochromic composition b comprising 5 parts of (hydroxyphenyl) hexafluoropropane and 50 parts of diester of (p) pimelic acid and 2- (4-benzyloxyphenyl) ethanol as component (c) is encapsulated in microcapsules and reversible A thermochromic pigment B was prepared.
The average particle size of the microcapsules B is 2.0 μm, the complete color elimination temperature (t ′ ₄ ) is 78 ° C., the complete color development temperature (t ′ ₁ ) is −11 ° C., and fluorescence is exhibited due to temperature change. It changes from orange to colorless.

Preparation of multicolor discoloring ink composition (see FIG. 4)
10 parts of the reversible thermochromic pigment A, 10 parts of the reversible thermochromic pigment B, 0.33 parts of xanthan gum (shear reducing agent), 10 parts of urea, 10 parts of glycerin, nonionic permeabilizer [Sannopco Co., Ltd. Trade name: Nopco SW-WET-366] 0.55 parts, modified silicone antifoaming agent (Sannopco Co., Ltd., trade name: Nopco 8034) 0.13 parts, mildew proofing agent (Zeneca Co., Ltd. product, Trade name: Proxel XL-2] A multi-color discoloring ink composition was prepared, consisting of 0.13 parts of water and 58.86 parts of water.

Preparation of Writing Instrument 0.97 g of the ink composition was suction-filled in a polypropylene pipe having an inner diameter of 4.4 mm, and connected to a ballpoint pen tip holding a 0.7 mm stainless steel ball at its tip via a resin holder.
Next, the back of the polypropylene pipe is filled with an ink backflow preventive (liquid plug) having visco-elastic properties mainly composed of polybutene, and the tail plug is further fitted to the rear of the pipe. After assembling the cap and fitting the cap, the degassing treatment was performed by centrifugation to obtain a multicolor discoloring ballpoint pen.
An SEBS resin is attached to the top of the cap as a friction member.

Discoloration behavior of the handwriting The handwriting obtained by writing with the above-mentioned ballpoint pen has a bright faded color in which the pigment A and the pigment B become mixed at room temperature (25 ° C.) Then, at 64 ° C., the pigment A is completely decolored (t ₄ ) and bright orange handwriting by the pigment B is visually recognized, and when heated to 78 ° C., the pigment B is completely decolored (t ′ ₄ ) It becomes colorless.
When cooled from this state to -11 ° C, pigment B is completely colored (t ' ₁ ) and bright orange handwriting is visually recognized, and when it is further -14 ° C, pigment A is completely colored (t ₁ ) Thus, a bright amber-colored handwriting in which the pigment A and the pigment B were mixed was visually recognized.
The state change of reversibly changing to the vivid amber color, the vivid orange color, and the achromatic color can be properly visually discriminated in order by heating and temperature lowering, and is rich in stepwise color change variations.
In addition, the ballpoint pen is used to form bright amber "homework" characters in the notebook, and after homeworking is performed, it is rubbed using a friction body to change into bright orange "homework" characters, It was possible to rub off and make the word "homework" colorless, and it was most suitable for use to check whether the homework was over, erase it when not necessary, and re-write.

Example 2
Preparation of Reversible Thermochromic Pigment (A) 2 parts of 3- (4-diethylamino-2-hexyloxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide as a component (A) B) 8 parts of bis (3-methyl-4-hydroxyphenyl) sulfide as a component, 5 parts of 1,1-bis (4'-hydroxyphenyl) hexafluoropropane, 4-benzyloxyphenylethyl caprate as a component (iii) A reversible thermochromic pigment A was prepared by encapsulating 50 parts of the reversible thermochromic composition a in microcapsules.
The average particle diameter of the reversibly thermochromic pigment A is 2.0 μm, the complete bleaching temperature (t4) is 64 ° C., the complete coloring temperature (t1) is -14 ° C., and the color changes from blue to colorless due to temperature change. Do.
1.5 parts of 2,6-bis (2-ethyloxyphenyl) -4- (4-dimethylaminophenyl) -pyridine as component (i), 2,2-bis (4'-hydroxyphenyl) as component (ii) 2.) A reversible thermochromic composition comprising, in microcapsules, a reversible thermochromic composition b comprising 5 parts of hexafluoropropane and 50 parts of a diester of pimelic acid and 2- (4-benzyloxyphenyl) ethanol as component (iii). Pigment B was prepared.
The average particle diameter of the microcapsules B is 2.0 μm, the complete color elimination temperature (t'4) is 78 ° C., the complete color development temperature (t'1) is -11 ° C., and fluorescence is exhibited due to temperature change. Change from yellow to colorless.

Preparation of multicolor discoloring ink composition (see FIG. 4)
5 parts of the above-mentioned reversible thermochromic pigment A, 10 parts of reversible thermochromic pigment B, 5 parts of glycerin, 0.7 parts of mildew proofing agent (manufactured by ZENECA, product name: Proxel XL-2), silicone antifoam agent [ Sannopco Co., Ltd. product name: SN deformer 381] 0.1 parts, water 71.2 parts, hydroxyethyl cellulose [Union Carbide Japan Co., Ltd. product name: trade name: Cellosize WP-09 L, water soluble polymer flocculant] A multicolor discoloring ink composition was prepared by mixing 8 parts of a 5% by mass aqueous solution.

Preparation of Writing Instrument After impregnating the ink composition in a fiber-focused ink storage material (porosity about 80%) coated with a polyester sliver with a synthetic resin film, the ink composition is accommodated in a barrel and mounted at the tip of the barrel. The multi-colored discolored marking pen was constructed in contact with the resin-processed pen body (having a porosity of about 50%) of the polyester fiber.
An SEBS resin is attached to the rear of the shaft cylinder as a friction member.

Discoloring behavior of the handwriting The handwriting obtained by writing with the above marking pen has a bright green color in which the pigment A and the pigment B are mixed at room temperature (25 ° C.), and the friction body attached to the barrel is used When it is rubbed, pigment A is completely decolored (t ₄ ) at 64 ° C., bright yellow handwriting by pigment B is visually recognized, and when it is further rubbed at 78 ° C., pigment B is completely decolored (t ' ₄ ) It becomes colorless.
When cooled from this state to -11 ° C, pigment B is completely colored (t ' ₁ ) and bright yellow handwriting is visually recognized, and further, at -14 ° C, 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 of reversibly changing to the vivid green, the vivid yellow, and the achromatic color can be properly discriminated in order by heating and temperature lowering, and is rich in stepwise color change variations.
In addition, a bright green highlight is formed on the text of the textbook using the marking pen, and it is rubbed using the friction body to turn it into a bright yellow highlight, and it is further rubbed to make the highlight colorless. It was most suitable for the use that can be done, check the memorized part (green) and the memorized part (yellow), and erase it when not necessary and re-write.

Example 3
Preparation of Reversible Thermochromic Pigment (I) 1 part of 3,3-bis (4-diethylamino-2-ethoxyphenyl) -4-azaphthalide as component, (I) 1,1-bis (4'-hydroxyphenyl) as component A reversible thermochromic pigment A was prepared by encapsulating in a microcapsule a reversible thermochromic composition a comprising 8 parts of n-decane, 25 parts of myristyl alcohol as component (C) and 25 parts of butyl stearate.
The average particle diameter of the reversibly thermochromic pigment A is 2.0 μm, the complete bleaching temperature (t 4) is 15 ° C., the complete coloring temperature (t 1) is 7 ° C. Do.
1 part of 2,6-bis (2,4-diethyloxyphenyl) -4- (4-diethylaminophenyl) -pyridine as component (i), 1,1-bis (4-hydroxyphenyl) hexa as component (ii) A reversible thermochromic pigment B was prepared by encapsulating in a microcapsule a reversible thermochromic composition b consisting of 8 parts of fluoropropane, 25 parts of 9-heptadecanone as a (iii) component and 25 parts of cetyl alcohol.
The average particle diameter of the reversibly thermochromic pigment A is 2.0 μm, the complete decoloring temperature (t'4) is 34 ° C., and the complete color forming temperature (t'1) is 28 ° C. The color changes from yellow to colorless.

Preparation of multicolor discoloring ink composition (see FIG. 5)
10 parts of the reversible thermochromic pigment A, 10 parts of the reversible thermochromic pigment B, 0.33 parts of xanthan gum (shear reducing agent), 10 parts of urea, 10 parts of glycerin, nonionic permeabilizer [Sannopco Co., Ltd. Trade name: Nopco SW-WET-366] 0.55 parts, modified silicone antifoaming agent (Sannopco Co., Ltd., trade name: Nopco 8034) 0.13 parts, mildew proofing agent (Zeneca Co., Ltd. product, Trade name: Proxel XL-2] A multi-color discoloring ink composition was prepared, consisting of 0.13 parts of water and 58.86 parts of water.

Preparation of Writing Instrument 0.97 g of the ink composition was suction-filled in a polypropylene pipe having an inner diameter of 4.4 mm, and connected to a ballpoint pen tip holding a 0.7 mm stainless steel ball at its tip via a resin holder.
Next, the back of the polypropylene pipe is filled with an ink backflow preventive (liquid plug) having visco-elastic properties mainly composed of polybutene, and the tail plug is further fitted to the rear of the pipe. After assembling the cap and fitting the cap, the degassing treatment was performed by centrifugation to obtain a multicolor discoloring ballpoint pen.

Discoloration behavior of the handwriting The handwriting obtained by writing with the above-mentioned ballpoint pen exhibits a bright yellow color by the pigment B at room temperature (25 ° C.), and when heated by a finger touch from this state, the pigment B becomes 34 ° C. The color completely disappeared (t ' ₄ ) and became colorless, and the handwriting was not visible.
If left at room temperature (25 ° C.) in this state, again bright yellow color of handwriting temperature when becomes to 28 ℃ lowered pigment B completely colored (t _'1) is revealing.
Further, the handwriting left for a while to the refrigerator (5 ° C.) was converted, comprising the pigment A to 7 ° C. is completely colored (t _1), yellow color mixing with fluorescent blue-green pigment B of Pigment A The bright yellowish green handwriting became visible.
The state change in which the bright yellow, the colorless, and the bright yellow-green are reversibly changed can be properly discriminated in order by heating and temperature lowering, and is rich in stepwise color change variations.
In addition, a bright yellow picture is drawn using the ballpoint pen, and the picture disappears when heated by finger touch, and a bright yellow picture appears again at room temperature (25 ° C.), and the picture is cooled and vivid. Yellowish-green painting, which is ideal for magic applications.

Example 4
1 part of 3,3-bis (4-diethylamino-2-ethoxyphenyl) -4-azaphthalide as component (i), 8 parts of 1,1-bis (4'-hydroxyphenyl) n-decane as component (ii), (Iii) A reversible thermochromic pigment A was prepared by encapsulating a reversible thermochromic composition a comprising 25 parts of 9-heptadecanone and 25 parts of cetyl alcohol as the component in microcapsules.
The average particle diameter of the reversibly thermochromic pigment A is 2.0 μm, the complete bleaching temperature (t4) is 35 ° C., and the complete color development temperature (t1) is 28 ° C. Do.
2- (di-n-butylamino) -8- (di-n-amylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 as component (i) 1 part of (3′H) -isobenzofuran] -3′-one, 8 parts of 1,1-bis (4-hydroxyphenyl) hexafluoropropane as component (ii), 50 parts of stearyl stearate as component (iii) The reversible thermochromic composition b was encapsulated in microcapsules to prepare a reversible thermochromic pigment B.
The average particle diameter of the reversibly thermochromic pigment A is 2.0 μm, the complete bleaching temperature (t4) is 58 ° C., the complete coloring temperature (t1) is 43 ° C., and the pink color having fluorescence by temperature change Discolors to colorless.

Preparation of multicolor discoloring ink composition (see FIG. 5)
5 parts of the above-mentioned reversible thermochromic pigment A, 10 parts of reversible thermochromic pigment B, 5 parts of glycerin, 0.7 parts of mildew proofing agent (manufactured by ZENECA, product name: Proxel XL-2), silicone antifoam agent [ Sannopco Co., Ltd. product name: SN deformer 381] 0.1 parts, water 71.2 parts, hydroxyethyl cellulose [Union Carbide Japan Co., Ltd. product name: trade name: Cellosize WP-09 L, water soluble polymer flocculant] A multicolor discoloring ink composition was prepared by mixing 8 parts of a 5% by mass aqueous solution.

Preparation of Writing Instrument After impregnating the ink composition in a fiber-focused ink storage material (porosity: about 80%) coated with a polyester sliver with a synthetic resin film, the ink composition is accommodated in a barrel and mounted on the barrel end A multicolor marking pen was constructed in contact with the resin-processed pen body of the polyester fiber (about 50% porosity).
An SEBS resin is attached to the rear of the shaft cylinder as a friction member.

Discoloring behavior of the handwriting The handwriting obtained by writing with the above marking pen has a bright purple color at room temperature (25 ° C), and when heated by rubbing with a friction body from this state, the pigment A becomes 35 ° C. The color is completely decolored (t ₄ ), a bright pink color by pigment B is visually recognized, and when the temperature rises further to 58 ° C., pigment B is completely decolored (t ' ₄ ), and the handwriting is visually recognized It will not be done.
After that, when it is cooled, the temperature drops to 43 ° C., pigment B is completely colored (t ′ ₁ ), bright pink handwriting is visually recognized, and when it is 28 ° C., pigment A is completely colored (( t ₁ ) As a result, a bright purple handwriting in which the bluish green color of pigment A and the bright pink color of pigment B were mixed was visually recognized.
The color change reversibly to a vivid purple color, a bright pink color, and achromatic color can be appropriately determined and recognized sequentially by heating and temperature lowering, and is rich in stepwise color change variations.
In addition, draw a bright purple picture using the above marking pen, become bright pink when heated, and become colorless when heated further, and turn it from bright pink to a bright yellow-green picture Can be used for magic applications.

Example 5
Preparation of Reversible Thermochromic Pigment (A) 2 parts of 3- (4-diethylamino-2-hexyloxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide as a component (A) B) 8 parts of bis (3-methyl-4-hydroxyphenyl) sulfide as a component, 5 parts of 1,1-bis (4'-hydroxyphenyl) hexafluoropropane, 50 parts of 4-methylbenzyl palmitate as a component (iii) The reversibly thermochromic composition A was encapsulated in microcapsules to prepare reversibly thermochromic pigment A.
The average particle diameter of the reversibly thermochromic pigment A is 2.0 μm, the complete bleaching temperature (t4) is 43 ° C., the complete coloring temperature (t1) is −3 ° C., and the temperature changes to blue from colorless Do.
1 part of 2,6-bis (2-ethyloxyphenyl) -4- (4-dimethylaminophenyl) -pyridine as component (i), 1,1-bis (4-hydroxyphenyl) hexafluoro as component (ii) A reversible thermochromic pigment B was prepared by encapsulating in a microcapsule a reversible thermochromic composition comprising 5 parts of propane and 50 parts of a diester of pimelic acid and 2- (4-benzyloxyphenyl) ethanol as component (iii). did.
The average particle size of the microcapsules B is 2.0 μm, the complete decoloring temperature (t 4) is 78 ° C., the complete color forming temperature (t 1) is −11 ° C. Discolor.

Preparation of multicolor discoloring ink composition (see FIG. 6)
5 parts of the above-mentioned reversible thermochromic pigment A, 15 parts of reversible thermochromic pigment B, 0.33 parts of xanthan gum (shear reducing viscosity imparting agent), 10 parts of urea, 10 parts of glycerin Trade name: Nopco SW-WET-366] 0.55 parts, modified silicone antifoaming agent (Sannopco Co., Ltd., trade name: Nopco 8034) 0.13 parts, mildew proofing agent (Zeneca Co., Ltd. product, Trade name: Proxel XL-2] A multi-color discoloring ink composition was prepared, consisting of 0.13 parts of water and 58.86 parts of water.

Preparation of Writing Instrument 0.97 g of the ink composition was suction-filled in a polypropylene pipe having an inner diameter of 4.4 mm, and connected to a ballpoint pen tip holding a 0.7 mm stainless steel ball at its tip via a resin holder.
Next, the back of the polypropylene pipe is filled with an ink backflow preventive (liquid plug) having visco-elastic properties mainly composed of polybutene, and the tail plug is further fitted to the rear of the pipe. After assembling the cap and fitting the cap, the degassing treatment was performed by centrifugation to obtain a multicolor discoloring ballpoint pen.
An SEBS resin is attached to the top of the cap as a friction member.

Discoloration of the handwriting The handwriting obtained by writing with the above-mentioned ballpoint pen has a bright green color at room temperature (25 ° C), and when it is rubbed using a friction body attached to the cap, the pigment A is completely at 43 ° C. Decoloring (t ₄ ), bright yellow handwriting by pigment B is visually recognized, and further rubbing to increase the temperature to 78 ° C., pigment B completely decoloring (t ' ₄ ), colorless become.
From this state, the pigment A is completely developed (t ₁ ) when cooled down to −3 ° C., and blue is visually recognized, and the pigment B is completely developed color when the temperature drops further to −11 ° C. (t ′ ₁ ) And then the original brilliant green handwriting.
State changes that reversibly turn into vivid green, vivid yellow, blue, and achromatic color can be appropriately determined and recognized sequentially by heating and temperature lowering, and are rich in stepwise color change variations. The
In addition, bright green letters can be formed on a notebook using the above-mentioned ballpoint pen, and important places can be rubbed using a friction body to be discolored into bright yellow letters. In addition, when the wrong letter was formed or the wrong place was made yellow, it was possible to rub and make the letter colorless and re-written, and it was optimal for the determination of the important place.
Furthermore, important points can be subdivided by changing the color of the letters to blue using a heat-setting pen.
Furthermore, by combining the ballpoint pen and the yellow transparent sheet, the ballpoint pen is used to form a bright green character on a notebook, and a portion to be recorded is rubbed with a friction body to discolor it into a bright yellow character. When the yellow transparent sheet was placed, the yellow letters were not visible and it was optimal for memorizing applications. In addition, when the wrong letter was formed or the wrong place was made yellow, it was possible to rub it and make the letter colorless and re-write, and the convenience was excellent.

Example 6
Preparation of Reversible Thermochromic Pigment (i) As a component 2- (di-n-butylamino) -8- (di-n-amylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-) g) 1 part of pyrimidine-5,1 '(3'H) -isobenzofuran] -3'-one, 5 parts of 1,1-bis (4-hydroxyphenyl) hexafluoropropane as component (ii), (iii) 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 average particle diameter of the reversibly thermochromic pigment A is 2.0 μm, the complete bleaching temperature (t4) is 43 ° C., the complete coloring temperature (t1) is −3 ° C., and the pink color having fluorescence due to temperature change Discolors to colorless.
1 part of 2,6-bis (2,4-diethyloxyphenyl) -4- (4-bis (4-methylphenyl) aminophenyl) pyridine as component (I), 2,2-bis ( A reversible thermochromic composition comprising 8 parts of 4'-hydroxyphenyl) hexafluoropropane and 50 parts of a diester of (2) pimelic acid and 2- (4-benzyloxyphenyl) ethanol as a component is encapsulated in a microcapsule A reversible thermochromic pigment B was prepared.
The average particle size of the microcapsules B is 2.0 μm, the complete color elimination temperature (t 4) is 78 ° C., the complete color development temperature (t 1) is −11 ° C. Discolor.

Preparation of multicolor discoloring ink composition (see FIG. 6)
7.5 parts of the above-mentioned reversible thermochromic pigment A, 7.5 parts of reversible thermochromic pigment B, 5 parts of glycerin, 0.7 parts of mildew proofing agent (manufactured by ZENECA, trade name: Proxel XL-2), silicone type Antifoaming agent (Sannopco Co., 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, high water solubility Molecular Flocculant] A multicolor discoloring ink composition was prepared by mixing 8 parts of a 5% by mass aqueous solution.

Preparation of Writing Instrument After impregnating the ink composition in a fiber-focused ink storage material (porosity about 80%) coated with a polyester sliver with a synthetic resin film, the ink composition is accommodated in a barrel and mounted at the tip of the barrel. The multi-colored discolored marking pen was constructed in contact with the resin-processed pen body (having a porosity of about 50%) of the polyester fiber.
An SEBS resin is attached to the rear of the shaft cylinder as a friction member.

Discoloration of the handwriting The handwriting obtained by writing with the marking pen has a bright amber color at room temperature (25 ° C), and when it is rubbed using a friction body attached to the barrel, the pigment A becomes 43 ° C. Completely decoloring (t ₄ ), bright orange handwriting by pigment B is visually recognized, and further rubbing, the temperature rises to 78 ° C. and pigment B is completely decolored (t ' ₄ ) Becomes colorless.
From this state, the pigment A is completely developed (t ₁ ) when cooled down to −3 ° C., and a bright pink color is visually recognized, and the pigment B is completely developed color when the temperature is further lowered down to −11 ° C. t ' ₁ ) and it becomes the original bright vermicelli handwriting.
The color change reversibly changing to the bright amber color, bright orange color, bright pink color and colorless color can be determined and recognized properly sequentially by heating and temperature lowering, and there are many variations of stepwise color change It was a thing.
In addition, a bright amber highlight is formed on the text of the textbook using the marking pen, and it is rubbed using a friction body to turn it into a bright orange highlight, and further rubbed to make the highlight colorless. It was most suitable for use where it can be recorded and confirmed (dark blue) and the memorized area (orange), and erase it when unnecessary and re-write.
Furthermore, it is also possible to reliably distinguish the places where it is desired to memorize by turning a highlight into a bright pink color by using a heating pen.

Example 7
Preparation of Reversible Thermochromic Pigment (I) 1 part of 3,3-bis (4-diethylamino-2-ethoxyphenyl) -4-azaphthalide as component, (I) 1,1-bis (4'-hydroxyphenyl) as component A reversible thermochromic pigment A was prepared by encapsulating a reversible thermochromic composition comprising 5 parts of n-decane and 50 parts of 4-methylbenzyl palmitate as a component in microcapsules.
The average particle diameter of the reversibly thermochromic pigment A is 2.0 μm, the complete bleaching temperature (t4) is 43 ° C., and the complete coloring temperature (t1) is −3 ° C. Discolor.
2- (di-n-butylamino) -8- (di-n-amylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 as component (i) 1 part of (3'H) -isobenzofuran] -3'-one, 5 parts of 1,1-bis (4-hydroxyphenyl) hexafluoropropane as component (ii), pimelic acid and 2- (2) as component A reversible thermochromic pigment B was prepared by encapsulating a reversible thermochromic composition consisting of 50 parts of diester with (4-benzyloxyphenyl) ethanol in microcapsules.
The average particle diameter of the microcapsules B is 2.0 μm, the complete decolorization temperature (t 4) is 78 ° C., the complete coloration temperature (t 1) is −11 ° C. To discolor.

Preparation of multicolor discoloring ink composition (see FIG. 6)
5 parts of the reversibly thermochromic pigment A, 15 parts of the reversible thermochromic pigment B, a yellow dye [manufactured by Daiwa Kasei Co., Ltd., quinoline yellow WS 300, C.I. I. 47005] 0.5 parts, xanthan gum (shear reducing agent) 0.33 parts, urea 10 parts, glycerin 10 parts, nonionic permeabilizing agent [Sannopco Co., Ltd., trade name: Nopco SW-WET-366] 0.55 parts, 0.13 parts of a modified silicone antifoaming agent (Sannopco Co., Ltd., trade name: Nopco 8034), and a mildew proofing agent (Zeneca Co., Ltd., trade name: Proxel XL-2) 0. A multi-color discoloring ink composition consisting of 13 parts and 58.86 parts of water was prepared.

Preparation of Writing Instrument 0.97 g of the ink composition was suction-filled in a polypropylene pipe having an inner diameter of 4.4 mm, and connected to a ballpoint pen tip holding a 0.7 mm stainless steel ball at its tip via a resin holder.
Next, the back of the polypropylene pipe is filled with an ink backflow preventive (liquid plug) having visco-elastic properties mainly composed of polybutene, and the tail plug is further fitted to the rear of the pipe. After assembling the cap and fitting the cap, the degassing treatment was performed by centrifugation to obtain a multicolor discoloring ballpoint pen.
An SEBS resin is attached to the top of the cap as a friction member.

Discoloration of the handwriting The handwriting obtained by writing with the above-mentioned ballpoint pen has a bright purple color at room temperature (25 ° C), and when it is rubbed using a friction body attached to a cap, the pigment A is completely at 43 ° C. Decoloring (t ₄ ), bright orange brush marks of pigment B and yellow dye are visually recognized, and further rubbing to increase the temperature to 78 ° C. completely decoloring pigment B (t ' ₄ ) Turn yellow.
From this state, the pigment A is completely colored (t ₁ ) when it is cooled to −3 ° C., yellowish green is visually recognized, and the pigment B is completely colored (t ′) when the temperature is further lowered to −11 ° C. ₁ ) Make your original bright purple handwriting.
State changes that reversibly turn into vivid purple, vivid orange, yellow, and yellowish green can be appropriately determined and recognized sequentially by heating and cooling, and are rich in stepwise color change variations. there were.
In addition, a bright purple letter and picture can be drawn using the above-mentioned ballpoint pen, and it can be rubbed using a friction body to turn it into a bright orange letter and picture, and it can be further rubbed to make letters and pictures yellow. , Was perfect for a message card.
Furthermore, it was possible to turn the letters and pictures into a yellowish green color by using a thermal pen, and it was possible to obtain a highly versatile message card.

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

Claims (7)

(I) A reaction medium which causes electron transfer reaction reversibly in a specific temperature range by (d) electron donating color forming organic compound, (ii) electron accepting compound, and (iii) the above (i) and (ii) components A reversible thermochromic pigment A comprising a reversible thermochromic composition a, and (I) an electron donating color developing organic compound, (ii) an electron accepting compound, and (iii) the above (ii) And (b) a reversible thermochromic pigment B comprising a reversible thermochromic composition b comprising a reaction medium capable of causing an electron transfer reaction by the component to reversibly occur in a specific temperature range, and a medium; The color-changing pigments A and B are completely colored when reaching the full coloration temperature (t ₁ ) by the temperature decrease from the decoloring state, and are completely color when reaching the full color fading temperature (t ₄ ) when the temperature is raised from the color forming state Reversibly thermochromic pigment A A pigment having the complete bleaching temperature (t ₄ ) of the other reversible thermochromic pigment B on the higher temperature side than the complete bleaching temperature (t ₄ ) of the above, and the reversible thermochromic pigment B having fluorescence upon color development A multicolor discoloring ink composition for a writing instrument, characterized in that   The compound according to claim 1, wherein (i) the electron donating color forming organic compound in the reversible thermochromic pigment B is a compound selected from a pyridine compound, a quinazoline compound, a biskinazoline compound, and a diazarhodamine lactone compound. Multicolor discoloring ink composition for writing instruments. For writing instrument of claim 1 or 2 wherein has a complete decoloring temperature (t ₄₎ of the reversible thermochromic pigment B to the high temperature side 10 ° C. or higher than the complete decoloring temperature (t ₄₎ of said reversible thermochromic pigment A Multicolor discoloring ink composition. The multiple decolorization temperature (t ₄ ) according to claim 3, wherein the complete decolorization temperature (t ₄ ) of the reversible thermochromic pigment B is on the higher temperature side by 10 to 70 ° C. than the complete decolorization temperature (t ₄ ) of the reversible thermochromic pigment A Color discoloring ink composition. The complete decoloring temperature (t ₄₎ of the reversible thermochromic pigment A is not less 50 ° C. or more, complete coloring temperature (t ₁₎ is at 0 ℃ or less, complete coloring temperature of the reversible thermochromic pigment B (t ₁ The multicolor discoloring ink composition for a writing instrument according to any one of claims 1 to 4, wherein 0) or less.   A writing instrument containing the multicolor discoloring ink composition for a writing instrument according to any one of claims 1 to 5.   The writing instrument according to claim 6, comprising a friction body.

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