JP2020002276A - Thermochromic ink composition for writing instrument and writing instrument using the same - Google Patents

Abstract

To provide a thermochromic ink composition for writing instrument high in stability of a microcapsule pigment in a water-based medium and capable of increasing a decolorizing temperature in a range capable of decoloration by friction heat by setting the decoloration temperature at 110°C or lower even when a (iii) component with high melting point is used, and a writing instrument using the same.SOLUTION: There is provided a water-based ink composition, which is a thermochromic ink composition for writing instrument, using a reversible thermochromic microcapsule pigment, as a color agent, by including a reversible thermochromic composition composed of (i) an electron-donative coloring organic compound, (ii) an electron-accepting compound and (iii) a reaction medium which controls color reactions of the (i) and (ii) in a microcapsule, in which the (iii) component has melting point in a range of 80°C to 130°C, and is in a range of 60 to 90 mass% in total amount of the reversible thermochromic composition. There is provided a writing instrument housing the ink composition.SELECTED DRAWING: Figure 4

Description

  The present invention relates to a thermochromic ink composition for a writing instrument and a writing instrument using the same. More specifically, the present invention relates to a thermochromic ink composition for writing implements in which handwriting is not inadvertently erased even in a high temperature environment, and a writing implement using the same.

An aqueous ink composition having a decoloring temperature of about 50 to 65 ° C. is applied to a friction heat decolorable writing instrument currently on the market (for example, see Patent Document 1). Therefore, when a written notebook or the like is left in a high temperature state such as in an automobile in summer, the color may be erased, and it is desired to increase the color erasing temperature.
In addition, the reversible thermochromic microcapsule pigments using three components (a), (b), and (c) as coloring agents are widely used in the frictional heat decolorable writing implement. Because of its low solubility, the component (c) having a higher melting point is preferred.
However, if the color erasing temperature is raised in consideration of the stability of the component (c) in an aqueous medium, the melting point of the applicable component (c) becomes too high, so that erasure with frictional heat is impossible. Or, it becomes difficult, so that the decoloring temperature needs to be 110 ° C. or less, which is the upper limit of the generation of frictional heat.

Japanese Patent No. 4312987

  According to the present invention, the stability of the microcapsule pigment in an aqueous medium is high and the frictional heat is reduced by setting the decoloring temperature to 110 ° C. or less even when a high melting point component (c) is used. An object of the present invention is to provide a thermochromic ink composition for writing implements capable of increasing the decoloring temperature within a range where decoloring is possible, and a writing implement using the same.

The present invention provides a reversible thermochromic composition comprising (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reaction medium for controlling the color reaction of (a) and (b). An aqueous ink composition using, as a colorant, a reversible thermochromic pigment in which a hydrophobic composition is encapsulated in microcapsules, wherein the component (c) has a melting point in the range of 80 ° C to 130 ° C, The requirement is a thermochromic ink composition for writing implements in the range of 60 to 90% by mass of the total amount of the color changing composition.
Further, the decolorizing temperature of the reversible thermochromic pigment is 75 ° C. or more and 110 ° C. or less, and the reversible thermochromic pigment (colorant A) has a decoloring temperature of 40 ° C. or more and 70 ° C. or less. be used in combination discoloring pigment (colorant B), the hue of the colorant B is different from the hue of the colorant a, two types of color erasure temperature T _a, in two steps at _{T B (T a> T B} ) It is required that a hue change occurs and that the colorant be added in a range of 10 to 40% by mass based on the total amount of the ink composition.
Further, a writing implement incorporating the thermochromic ink composition for a writing implement according to any of the above is a requirement, comprising a friction member that discolors handwriting by frictional heat with the writing implement, wherein the friction member is from two types. becomes, due to friction with the paper, one emits a frictional heat in the range of T _a from T _B, the other is a requirement that as it emits more frictional heat T _a.

According to the present invention, even when a high melting point component (c) having low solubility in an aqueous medium is used, the colorless temperature can be set to 110 ° C. or lower, which can be exhibited by frictional heat. The stability of the microcapsule pigment is high, and the decolorization temperature can be raised within the range where decolorization by frictional heat is possible, and handwriting that is difficult to decolor when left in a high temperature state such as in an automobile A thermochromic ink composition for a writing instrument that can be formed stably over a long period of time, and a writing instrument using the same.
Furthermore, a thermochromic ink composition for a writing instrument having a higher commercial value can be formed because a two-stage color changing ink having high ink stability and changing color from coloring (1) to coloring (2) and further to decoloring can be constituted. It becomes a writing instrument using.

It is a graph explaining the hysteresis characteristic in the color density-temperature curve of a reversible thermochromic composition. 4 is a graph illustrating a hysteresis characteristic in a color density-temperature curve of a reversible thermochromic composition having a color memory property. The color density-temperature curves of the high-temperature decoloring side colorant group A and the low-temperature decoloring side colorant group B contained in the thermochromic ink composition for writing implements of one embodiment of the present invention (A: thick line, B: thin line) ). Color density-temperature curve (A: thick line, B) of the high-temperature decoloring side colorant group A and the low-temperature decoloring side colorant group B contained in the thermochromic ink composition for a writing instrument of another embodiment of the present invention. : Thin line). Color density-temperature curves of the high-temperature decoloring side colorant group A and the low-temperature decoloring side colorant group B contained in the thermochromic ink composition for writing implements of other examples of the present invention (A: thick line, B: (Thin line). Color density-temperature curves of the high-temperature decoloring side colorant group A and the low-temperature decoloring side colorant group B contained in the thermochromic ink composition for writing implements of other examples of the present invention (A: thick line, B: (Thin line).

  As the colorant, a reversible thermochromic composition comprising (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reaction medium which determines the temperature at which the color reaction of the two occurs. A reversible thermochromic pigment encapsulated in microcapsules is used.

The reversible thermochromic composition undergoes a color change before and after a predetermined temperature (color change point) as a boundary, a decolored state in a temperature range above the high temperature color change point, and a color development state in a temperature range below the low temperature color change point. Present, only one of the two states exists in a specific temperature range, and the other state is maintained while the heat or cold required for the state to develop is applied. However, it returns to its original state when the application of the heat or the cold is stopped, and has a characteristic that the hysteresis width (ΔH) is relatively small (see FIG. 1).
In addition, it shows a large hysteresis characteristic, that is, the shape of the curve plotting the change in the coloring density due to the temperature change is lower than the color change temperature range from the higher temperature side in contrast to the case where the temperature is increased from a lower temperature side than the color change temperature range. The color changes along a route that is significantly different from that in the case where the color is developed, and the color development state in a low temperature range below the full color development temperature (t ₁ ) or the decoloration state in a high temperature range above the complete decolorization temperature (t ₄ ) is obtained. Reversible heat of a heat decoloring type (color decolored by heating and colored by cooling) having a color memory property in a specific temperature range [temperature range between t _{2 and} t ₃ (substantially two-phase holding temperature range)] Discolorable compositions can also be applied (see FIG. 2).
In the present invention, “when the handwriting is thermally decolored” when the reversible thermochromic composition is used refers to a state in which the temperature is equal to or higher than a complete decoloring temperature (t ₄ ).

Hereinafter, the components (a), (b), and (c) will be specifically described.
The component (a), that is, the electron-donating color-forming organic compound, is a component that determines color and is a compound that gives an electron to the component (b) as a color developer and develops a color.
Examples of the electron-donating color-forming organic compound include a phthalide compound, a fluoran compound, a styrinoquinoline compound, a pyridine compound, a quinazoline compound, a bisquinazoline compound, and a diazarhodamine lactone compound. As the pyridine compound, a pyridine compound, a quinazoline compound, a bisquinazoline compound, a diazarhodamine lactone compound are used, and a pyridine compound is preferably used.
As the pyridine compound,
4- (4'-methylbenzylaminophenyl) -pyridine,
2,6-diphenyl-4- (4'-dimethylaminophenyl) -pyridine,
2,6-diphenyl-4- (4'-N-phenyl-N-methylaminophenyl) -pyridine,
2,6-bis (2'-methyloxyphenyl) -4- (4'-dimethylaminophenyl) -pyridine,
2,6-bis (2'-ethyloxyphenyl) -4- (4'-dimethylaminophenyl) -pyridine,
2,6-bis (2'-propyloxyphenyl) -4- (4'-dimethylaminophenyl) -pyridine,
2,6-bis (2'-butyloxyphenyl) -4- (4'-dimethylaminophenyl) -pyridine,
2,6-bis (2'-pentyloxyphenyl) -4- (4'-dimethylaminophenyl) -pyridine,
2,6-bis (2'-hexyloxyphenyl) -4- (4'-dimethylaminophenyl) -pyridine,
2,6-bis (2'-heptyloxyphenyl) -4- (4'-dimethylaminophenyl) -pyridine,
2,6-bis (2'-octyloxyphenyl) -4- (4'-dimethylaminophenyl) -pyridine,
2,6-bis (2'-methyloxyphenyl) -4- (4'-diethylaminophenyl) -pyridine,
2,6-bis (2'-ethyloxyphenyl) -4- (4'-diethylaminophenyl) -pyridine,
2,6-bis (2'-propyloxyphenyl) -4- (4'-diethylaminophenyl) -pyridine,
2,6-bis (2'-butyloxyphenyl) -4- (4'-diethylaminophenyl) -pyridine,
2,6-bis (2'-pentyloxyphenyl) -4- (4'-diethylaminophenyl) -pyridine,
2,6-bis (2'-hexyloxyphenyl) -4- (4'-diethylaminophenyl) -pyridine,
2,6-bis (2'-heptyloxyphenyl) -4- (4'-diethylaminophenyl) -pyridine,
2,6-bis (2'-octyloxyphenyl) -4- (4'-diethylaminophenyl) -pyridine,
2,6-bis (2'-methyloxyphenyl) -4- (4'-N-phenyl-N-methylaminophenyl) -pyridine,
2,6-bis (2'-ethyloxyphenyl) -4- (4'-N-phenyl-N-methylaminophenyl) -pyridine,
2,6-bis (2'-butyloxyphenyl) -4- (4'-N-phenyl-N-methylaminophenyl) -pyridine,
2,6-bis (2'-hexyloxyphenyl) -4- (4'-N-phenyl-N-methylaminophenyl) -pyridine,
2,6-bis (2'-octyloxyphenyl) -4- (4'-N-phenyl-N-methylaminophenyl) -pyridine,
2,6-bis (2'-methyloxyphenyl) -4- (4'-N-chloroethyl-N-methylaminophenyl) -pyridine,
2,6-bis (2'-ethyloxyphenyl) -4- (4'-N-chloroethyl-N-methylaminophenyl) -pyridine,
2,6-bis (2'-butyloxyphenyl) -4- (4'-N-chloroethyl-N-methylaminophenyl) -pyridine,
2,6-bis (2'-hexyloxyphenyl) -4- (4'-N-chloroethyl-N-methylaminophenyl) -pyridine,
2,6-bis (2'-octyloxyphenyl) -4- (4'-N-chloroethyl-N-methylaminophenyl) -pyridine,
2,6-bis (2'-methyloxyphenyl) -4- (4'-N-ethyloxyethyl-N-methylaminophenyl) -pyridine,
2,6-bis (2'-ethyloxyphenyl) -4- (4'-N-ethyloxyethyl-N-methylaminophenyl) -pyridine,
2,6-bis (2'-butyloxyphenyl) -4- (4'-N-ethyloxyethyl-N-methylaminophenyl) -pyridine,
2,6-bis (2'-hexyloxyphenyl) -4- (4'-N-ethyloxyethyl-N-methylaminophenyl) -pyridine,
2,6-bis (2'-octyloxyphenyl) -4- (4'-N-ethyloxyethyl-N-methylaminophenyl) -pyridine,
2,6-bis (2'-methyloxyphenyl) -4- (4'-dibutylaminophenyl) -pyridine,
2,6-bis (2'-ethyloxyphenyl) -4- (4'-dibutylaminophenyl) -pyridine,
2,6-bis (2'-butyloxyphenyl) -4- (4'-dibutylaminophenyl) -pyridine,
2,6-bis (2'-hexyloxyphenyl) -4- (4'-dibutylaminophenyl) -pyridine,
2,6-bis (2'-octyloxyphenyl) -4- (4'-dibutylaminophenyl) -pyridine,
2,6-bis (2'-methyloxyphenyl) -4- (4'-N-isobutyl-N-ethylaminophenyl) -pyridine,
2,6-bis (2'-ethyloxyphenyl) -4- (4'-N-isobutyl-N-ethylaminophenyl) -pyridine,
2,6-bis (2'-propyloxyphenyl) -4- (4'-N-isobutyl-N-ethylaminophenyl) -pyridine,
2,6-bis (2'-butyloxyphenyl) -4- (4'-N-isobutyl-N-ethylaminophenyl) -pyridine,
2,6-bis (2'-pentyloxyphenyl) -4- (4'-N-isobutyl-N-ethylaminophenyl) -pyridine,
2,6-bis (2'-hexyloxyphenyl) -4- (4'-N-isobutyl-N-ethylaminophenyl) -pyridine,
2,6-bis (2'-heptyloxyphenyl) -4- (4'-N-isobutyl-N-ethylaminophenyl) -pyridine,
2,6-bis (2'-octyloxyphenyl) -4- (4'-N-isobutyl-N-ethylaminophenyl) -pyridine,
2,6-bis (2'-nonyloxyphenyl) -4- (4'-N-isobutyl-N-ethylaminophenyl) -pyridine,
2,6-bis (4'-methyloxyphenyl) -4- (4'-dimethylaminophenyl) -pyridine,
2,6-dimethyl-3,5-biscarboethoxy-4- (4'-dimethylaminophenyl) -pyridine,
2- (2'-octyloxyphenyl) -4- (4'-dimethylaminophenyl) -6-phenyl-pyridine,
2,6-diethyloxy-4- (4'-diethylaminophenyl) -pyridine 4- (4-methyloxyphenyl) -2,6-bis (4-dimethylaminophenyl) -pyridine,
4-phenyl-2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (4-methylphenyl) -2,6-bis (4-dimethylaminophenyl) -pyridine,
2,4,6-tris (4-dimethylaminophenyl) -pyridine,
4- (2-chloro-4-dimethylaminophenyl) -2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (3-nitrophenyl) -2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (4-methyloxycarbonylphenyl) -2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (4-dimethylaminophenyl) -2,6-bis (2-thienyl) -pyridine,
4- (4-dimethylaminophenyl) -2,6-bis (2-furyl) -pyridine,
4- (2-chloro-4-dimethylaminophenyl) -2,6-bis (2-thienyl) -pyridine,
4- [4- (1-piperidinyl) phenyl] -2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (4-morpholinophenyl) -2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (9-julolidinyl) -2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (4-methylphenyl) -2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (4-methyloxyphenyl) -2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (4-methyloxyphenyl) -2,6-bis (4-morpholinophenyl) -pyridine,
4- (4-fluorophenyl) -2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (4-N-octyloxyphenyl-N-methylamino) -2,6-diphenylpyridine,
4- (4-chlorophenyl) -2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (4-nitrophenyl) -2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (4-N-2-cyanoethyl-N-methylaminophenyl) -2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (2,5-dimethyloxyphenyl) -2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (4-diethylaminophenyl) -2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (4-biphenylyl) -2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (4-pyrrolidinylphenyl) -2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (4-isoindolinylphenyl) -2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (4-N-2-cyanoethyl-N-methylaminophenyl) -2,6-diphenylpyridine,
4- (4-N-methyl-N-phenylaminophenyl) -2,6-diphenylpyridine,
4- (4-N-chloroethyl-N-methylaminophenyl) -2,6-diphenylpyridine,
4- (4-N-ethyloxyethyl-N-methylaminophenyl) -2,6-diphenylpyridine,
2,6-bis (2 ', 4'-dimethyloxyphenyl) -4- (4'-dimethylaminophenyl) -pyridine,
2,6-bis (2 ', 4'-diethyloxyphenyl) -4- (4'-dimethylaminophenyl) -pyridine,
2,6-bis (2 ', 4'-dipropyloxyphenyl) -4- (4'-dimethylaminophenyl) -pyridine,
2,6-bis (2 ', 4'-dibutyloxyphenyl) -4- (4'-dimethylaminophenyl) -pyridine,
2,6-bis (2 ', 4'-dipentyloxyphenyl) -4- (4'-dimethylaminophenyl) -pyridine,
2,6-bis (2 ', 4'-dihexyloxyphenyl) -4- (4'-dimethylaminophenyl) -pyridine,
2,6-bis (2 ', 4'-dimethyloxyphenyl) -4- (4'-diethylaminophenyl) -pyridine,
2,6-bis (2 ', 4'-diethyloxyphenyl) -4- (4'-diethylaminophenyl) -pyridine,
2,6-bis (2 ', 4'-dipropyloxyphenyl) -4- (4'-diethylaminophenyl) -pyridine,
2,6-bis (2 ', 4'-dibutyloxyphenyl) -4- (4'-diethylaminophenyl) -pyridine,
2,6-bis (2 ', 4'-dipentyloxyphenyl) -4- (4'-diethylaminophenyl) -pyridine,
2,6-bis (2 ', 4'-dihexyloxyphenyl) -4- (4'-diethylaminophenyl) -pyridine,
2,6-bis (2 ', 4'-dimethyloxyphenyl) -4- (4'-dipropylaminophenyl) -pyridine,
2,6-bis (2 ', 4'-diethyloxyphenyl) -4- (4'-dipropylaminophenyl) -pyridine,
2,6-bis (2 ', 4'-dipropyloxyphenyl) -4- (4'-dipropylaminophenyl) -pyridine,
2,6-bis (2 ', 4'-dibutyloxyphenyl) -4- (4'-dipropylaminophenyl) -pyridine,
2,6-bis (2 ', 4'-dipentyloxyphenyl) -4- (4'-dipropylaminophenyl) -pyridine,
2,6-bis (2 ', 4'-dihexyloxyphenyl) -4- (4'-dipropylaminophenyl) -pyridine,
2,6-bis (2 ', 4'-dimethyloxyphenyl) -4- (4'-dibutylaminophenyl) -pyridine,
2,6-bis (2 ', 4'-diethyloxyphenyl) -4- (4'-dibutylaminophenyl) -pyridine,
2,6-bis (2 ', 4'-dipropyloxyphenyl) -4- (4'-dibutylaminophenyl) -pyridine,
2,6-bis (2 ', 4'-dibutyloxyphenyl) -4- (4'-dibutylaminophenyl) -pyridine,
2,6-bis (2 ', 4'-dipentyloxyphenyl) -4- (4'-dibutylaminophenyl) -pyridine,
2,6-bis (2 ', 4'-dihexyloxyphenyl) -4- (4'-dibutylaminophenyl) -pyridine,
And the like.

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'-dimethylbenzomorpholin-7'-yl) -4-phenyloxy-quinazoline,
2- (4'-diethylaminophenyl) -4- (2 "-phenyloxyethyloxy) -quinazoline,
2- (4'-diethylaminophenyl) -4- (2 "-N-phenyl-N-ethylaminoethyloxy) -quinazoline,

2- (4'-dimethylaminophenyl) -4- (2 "-morpholinoethyloxy) -quinazoline,
2- (4'-dibenzylaminophenyl) -4- (2 "-phenyloxyethyloxy) -quinazoline,
2- (4'-diethylaminophenyl) -4- (2 "-phenyloxyethylthio) -quinazoline,
2- (4'-diethylaminophenyl) -4- [2 "-(1-naphthyloxy) ethyloxy] -quinazoline,
2- (3 ', 4'-dimethylbenzomorpholin-7'-yl)-(2 "-phenyloxyethyloxy) -quinazoline,
And the like.

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

As the diaza rhodamine lactone compound,
2- (dimethylamino) -8- (dimethylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran] -3 '-On,
2- (diethylamino) -8- (diethylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran] -3'- on,
2- (di-n-propylamino) -8- (di-n-propylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3' H) -Isobenzofuran] -3'-one,
2- (di-n-butylamino) -8- (di-n-butylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 ′ (3 ′ H) -Isobenzofuran] -3'-one,
2- (di-n-butylamino) -8- (dimethylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -iso Benzofuran] -3'-one,
2- (di-n-butylamino) -8- (diethylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 ′ (3′H) -isobenzofuran ] -3'-one,
2- (di-n-butylamino) -8- (N-ethyl-Ni-butylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran] -3'-one,
2- (di-n-butylamino) -8- (N-ethyl-Ni-amylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 ' (3′H) -isobenzofuran] -3′-one,
2- (di-n-butylamino) -8- (N-ethyl-N-n-hexylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran] -3'-one,
2- (di-n-butylamino) -8- (di-n-amylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 ′ (3′H ) -Isobenzofuran] -3'-one,
2- (di-n-butylamino) -8- (n-octylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -Isobenzofuran] -3'-one,
2- (dimethylamino) -8- (diethylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran] -3' -ON,
2- (diethylamino) -8- (dimethylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran] -3' -ON,
2- (morpholino) -8- (diethylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran] -3'- on,
2- (piperidino) -8- (diethylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran] -3'- on,
2- (N-methylpiperazino) -8- (diethylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran] -3 '-On,
2- (pyrrolidino) -8- (diethylamino) -4-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran] -3'- on,
2- (diethylamino) -8- (diethylamino) -4-methyl-4 ', 5', 6 ', 7'-tetrachloro-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5 1 '(3'H) -isobenzofuran] -3'-one,
2- (diethylamino) -8- (diethylamino) -spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 ′ (3′H) -isobenzofuran] -3′-one;
2- (di-n-butylamino) -8- (di-n-butylamino) -spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -iso Benzofuran] -3'-one,
2- (N-ethyl-Ni-amylamino) -8- (N-ethyl-Ni-amylamino) -spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '( 3'H) -isobenzofuran] -3'-one,
2- (di-n-butylamino) -8- (diethylamino) -spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran] -3' -ON,
2- (di-n-butylamino) -8- (N-ethyl-Ni-amylamino) -spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H ) -Isobenzofuran] -3'-one,
2- (piperidino) -8- (ethylamino) -4-methyl-7-methyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran ] -3'-one,
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'-one,
2- (di-n-butylamino) -8- (di-n-butylamino) -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3' H) -Isobenzofuran] -3'-one,
2- (di-n-butylamino) -8- (N-ethyl-Ni-amylamino) -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 ' (3′H) -isobenzofuran] -3′-one,
2- (piperidino) -8- (diethylamino) -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran] -3'- on,
2- (N-methyl-N-cyclohexylamino) -8- (diethylamino) -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H)- Isobenzofuran] -3′-one,
2- (dimethylamino) -8- (diethylamino) -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran] -3' -ON,
2- (i-amylamino) -8- (diethylamino) -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran] -3 '-On,
2- (pyrrolidino) -8- (diethylamino) -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran] -3'- on,
2- (N-methylpiperazino) -8- (diethylamino) -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran] -3 '-On,
2- (morpholino) -8- (diethylamino) -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran] -3'- on,
2- (N-methyl-N-benzylamino) -8- (diethylamino) -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H)- Isobenzofuran] -3′-one,
2- [di (2-methoxyethyl) amino] -8- (diethylamino) -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H)- Isobenzofuran] -3′-one,
2- (di-n-butylamino) -8- (diethylamino) -4- (4-methoxyphenyl) -spiro [5H- [1] benzopyrano (2,3-d) pyrimidine-5,1 ′ (3 ′ H) -Isobenzofuran] -3'-one,
2- (di-n-butylamino) -8- (diethylamino) -4- (4-chlorophenyl) -spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H ) -Isobenzofuran] -3'-one,
2- (di-n-butylamino) -8- (diethylamino) -4- (4-methylphenyl) -spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 ′ (3 ′ H) -Isobenzofuran] -3'-one,
2- [di (2-ethoxyethyl) amino] -8- (dimethylamino) -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 ′ (3′H) -Isobenzofuran] -3'-one,
2- (diethylamino) -8-[(2-methylphenyl) amino] -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 ′ (3′H) -iso Benzofuran] -3'-one,
2- (2,6-dimethylmorpholino) -8- (diethylamino) -4-phenyl-spiro [5H- [1] benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran ] -3'-one,
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,
And the like.

As the electron-accepting compound of the component (b), a group of compounds having an active proton, a group of pseudo-acidic compounds (not an acid, but a group of compounds which act as an acid in the composition to form a color of the component (a)), There is a group of compounds having electron vacancies.
As an example of a compound having an active proton, compounds having a phenolic hydroxyl group include monophenols to polyphenols, 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 phenol-aldehyde condensed resins such as bis- and tris-type phenols having an amide group, a halogen group and the like. Further, a metal salt of the compound having a phenolic hydroxyl group may be used.
Specific examples are described below.
Phenol, o-cresol, tert-butylcatechol, nonylphenol, n-octylphenol, n-dodecylphenol, n-stearylphenol, p-chlorophenol, p-bromophenol, o-phenylphenol, n-butyl p-hydroxybenzoate N-octyl p-hydroxybenzoate, resorcinol, dodecyl gallate, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfide, bis (3-allyl-4-hydroxyphenyl) sulfone, 4-hydroxy Phenyl-4-isopropoxyphenylsulfone, 4-benzyloxyphenyl-4-hydroxyphenylsulfone, 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. However, aromatic carboxylic acids and aliphatic carboxylic acids having 2 to 5 carbon atoms, carboxylic acid metal salts, acidic phosphoric acid esters and the like thereof It may be a compound selected from metal salts, 1,2,3-triazole and derivatives thereof, and the like.

The component (c) of the reaction medium that causes the electron transfer reaction by the components (a) and (b) to reversibly occur in a specific temperature range will be described.
Examples of the component (c) include alcohols, esters, ketones, ethers, and acid amides.
When applied to microencapsulation and secondary processing using the compound, since low-molecular-weight ones evaporate outside the capsule when subjected to high heat treatment, they have 10 or more carbon atoms to stably hold in the capsule. 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 Alcohol, heptadecyl alcohol, octadecyl alcohol, eicosyl alcohol, docosyl alcohol and the like.

  As the esters, esters having 10 or more carbon atoms are effective, and any combination of a monohydric carboxylic acid having an aliphatic and alicyclic or aromatic ring and a monohydric alcohol having an aliphatic and alicyclic or aromatic ring , Aliphatic and alicyclic esters obtained from any combination of polyhydric carboxylic acids having an aliphatic and alicyclic or aromatic ring and monohydric alcohols having an aliphatic and alicyclic or aromatic ring Alternatively, esters 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 are mentioned, and specifically, ethyl caprylate, octyl caprylate, caprylate Stearyl acid, myristyl caprate, docosyl caprate, 2-ethylhexyl laurate, n-decyl laurate, myris 3-methylbutyl phosphate, 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-butyl benzoate, 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-cyclohexanedioldidecyl, 1,4-cyclohexanedimethanol dimyristate, xylene glycol dicaprinate, xylene glycol distearate, etc. No.

Further, an ester of a saturated fatty acid and a branched aliphatic alcohol, an unsaturated fatty acid or a saturated or branched fatty acid having a branched or substituted ester of an aliphatic alcohol having 16 or more carbon atoms, cetyl butyrate, stearyl butyrate and Ester compounds selected from behenyl butyrate are also effective.
Specifically, 2-ethylhexyl butyrate, 2-ethylhexyl behenate, 2-ethylhexyl myristate, 2-ethylhexyl caprate, 3,5,5-trimethylhexyl laurate, 3,5,5-trimethylhexyl palmitate, 3,5,5-trimethylhexyl stearate, 2-methylbutyl caproate, 2-methylbutyl caprylate, 2-methylbutyl caprate, 1-ethylpropyl palmitate, 1-ethylpropyl stearate, 1-ethylpropyl behenate, 1-ethylhexyl laurate, 1-ethylhexyl myristate, 1-ethylhexyl palmitate, 2-methylpentyl caproate, 2-methylpentyl caprylate, 2-methylpentyl caprate, 2-methylpentyl laurate, 2-methylstearate Met 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, 3,3 stearic acid 7-Jim Octyl, 3,7-dimethyloctyl behenate, stearyl oleate, behenyl oleate, stearyl linoleate, behenyl linoleate, 3,7-dimethyloctyl erucate, stearyl erucate, isostearyl erucate, 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. Can be

  Further, in order to exhibit a large hysteresis characteristic with respect to the color density-temperature curve to change the color and to provide a color storage property depending on the temperature change, a temperature of 5 ° C. or more and less than 50 ° C. Carboxylic acid ester compounds exhibiting a ΔT value (melting point−cloud point), for example, a carboxylic acid ester containing a substituted aromatic ring in the molecule, an ester of a carboxylic acid containing an unsubstituted aromatic ring and an aliphatic alcohol having 10 or more carbon atoms A carboxylic acid ester containing a cyclohexyl group in the molecule, an ester of a fatty acid having 6 or more carbon atoms and an unsubstituted aromatic alcohol or phenol, a fatty acid having 8 or more carbon atoms and a branched aliphatic alcohol or ester, a dicarboxylic acid and an aromatic alcohol or Esters of branched aliphatic alcohols, dibenzyl cinnamate, heptyl stearate, didecyl adipate, adipine Dilauryl, dimyristyl adipate, dicetyl adipate, distearyl adipate, trilaurin, trimyristin, tristearin, dimyristin, distearate, and the like.

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

As ketones, aliphatic ketones having a total carbon number of 10 or more are effective, and 2-decanone, 3-decanone, 4-decanone, 2-undecanone, 3-undecanone, 4-undecanone, 5-undecanone, 5-undecanone, -Dodecanone, 3-dodecanone, 4-dodecanone, 5-dodecanone, 2-tridecanone, 3-tridecanone, 2-tetradecanone, 2-pentadecanone, 8-pentadecanone, 2-hexadecanone, 3-hexadecanone, 9-heptadecanone, 2-pentadecanone , 2-octadecanone, 2-nonadecanone, 10-nonadecanone, 2-eicosanone, 11-eicosanone, 2-heneicosanone, 2-docosanone, lauron, stearone, and the like.
Further, arylalkyl ketones having a total carbon number of 12 to 24, for example, n-octadecanophenone, n-heptadecanophenone, n-hexadecanophenone, n-pentadecanophenone, n-tetradecano Nophenone, 4-n-dodecaacetophenone, n-tridecanophenone, 4-n-undecanoacetophenone, n-laurophenone, 4-n-decanoacetophenone, n-undecanophenone, 4-n-nonylacetophenone, n-decanophenone, 4-n-octyl acetophenone, n-nonanophenone, 4-n-heptyl acetophenone, n-octanophenone, 4-n-hexyl acetophenone, 4-n-cyclohexyl acetophenone, 4-tert-butyl propiophenone , N-heptaphenone, 4-n-pentylacetop Non, cyclohexyl phenyl ketone, benzyl -n- butyl ketone, 4-n-butyl acetophenone, n- hexanophenone, 4-isobutyl acetophenone, 1-acetonaphthone, 2-acetonaphthone, cyclopentyl phenyl ketone.

  As the ethers, aliphatic ethers having a total carbon number of 10 or more are effective, and dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, dinonyl ether, didecyl ether, diundecyl ether, didodecyl ether, ditriethyl ether Decyl ether, ditetradecyl ether, dipentadecyl ether, dihexadecyl ether, dioctadecyl ether, decanediol dimethyl ether, undecanediol dimethyl ether, dodecanediol dimethyl ether, tridecanediol dimethyl ether, decanediol diethyl ether, undecanediol diethyl ether, etc. No.

  Examples of acid amides include acetamide, propionamide, butyric amide, caproic amide, caprylic amide, capric amide, lauric amide, myristic amide, palmitic amide, stearic amide, behenic amide, and oleic amide. , Erucamide, benzamide, caproic anilide, caprylic anilide, capric anilide, lauric anilide, myristic anilide, palmitic anilide, stearic anilide, behenic anilide, oleic anilide, erucic anilide, caproic acid N -Methylamide, caprylic acid N-methylamide, capric acid N-methylamide, lauric acid N-methylamide, myristic acid N-methylamide, palmitic acid N-methylamide, stearic acid N-methylamide , Behenic acid N-methylamide, oleic acid N-methylamide, erucic acid N-methylamide, lauric acid N-ethylamide, myristic acid N-ethylamide, palmitic acid N-ethylamide, stearic acid N-ethylamide, oleic acid N-ethylamide, laurin Acid N-butylamide, myristic acid N-butylamide, palmitic acid N-butylamide, stearic acid N-butylamide, oleic acid N-butylamide, lauric acid N-octylamide, myristic acid N-octylamide, palmitic acid N-octylamide, N-octylamide stearate, N-octylamide oleate, N-dodecylamide laurate, N-dodecylamide myristic, N-dodecylamide palmitate, N-dodecylamide stearate, Olay Acid N-dodecylamide, dilauric amide, dimyristic amide, dipalmitic amide, distearic amide, dioleic amide, trilauric amide, trimyristic amide, tripalmitic amide, tristearic amide, trioleic acid Amide, succinamide, adipic amide, glutaric amide, malonamide, azelaic amide, maleic amide, succinic N-methylamide, adipic N-methylamide, glutaric N-methylamide, malonic N-methylamide, Azelaic acid N-methylamide, succinic acid N-ethylamide, adipic acid N-ethylamide, glutaric acid N-ethylamide, malonic acid N-ethylamide, azelaic acid N-ethylamide, succinic N-butylamide, adipic acid N- Butylamide, glutaric acid N-butylamide, malonic acid N-butylamide, adipic acid N-octylamide, adipic acid N-dodecylamide and the like can be mentioned.

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

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

[Wherein, R ₁ represents a hydrogen atom or a methyl group, m represents an integer of 0 to 2, and _one of X ₁ and X ₂ represents — (CH ₂ ) _n OCOR ₂ or — (CH ₂ ) _n COOR ₂ , the other represents a hydrogen atom, n represents an integer of 0 to 2, R ₂ represents an alkyl group or an alkenyl group having 4 or more carbon atoms, Y ₁ and Y ₂ represent a hydrogen atom and 1 to 4 carbon atoms. Represents an alkyl group, a methoxy group, or a halogen, and r and p represent an integer of 1 to 3. ]
Among the compounds represented by the formula (1), when R ₁ is a hydrogen atom, a reversible thermochromic composition having a wider hysteresis width is preferably obtained, and further, R ₁ is a hydrogen atom; , M is more preferably 0.
In addition, among the compounds represented by the formula (1), a compound represented by the following general formula (2) is more preferably used.

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

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

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

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

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

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

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

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

[In the formula, X represents any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom, m represents an integer of 1 to 3, and n represents 1 to 20. Indicates an integer. ]
As the compound, diesters of succinic acid and 2-phenoxyethanol, diesters of suberic acid and 2-phenoxyethanol, diesters of sebacic acid and 2-phenoxyethanol, diesters of 1,10-decanedicarboxylic acid and 2-phenoxyethanol, A diester of 1,18-octadecanedicarboxylic acid and 2-phenoxyethanol can be exemplified.

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

[Wherein, R represents any one of an alkyl group having 4 to 22 carbon atoms, a cycloalkylalkyl group, a cycloalkyl group, and an alkenyl group having 4 to 22 carbon atoms, and X represents a hydrogen atom, an alkyl having 1 to 4 carbon atoms. Group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and n represents 0 or 1. ]
Examples of the compound include decyl 4-phenylbenzoate, lauryl 4-phenylbenzoate, myristyl 4-phenylbenzoate, cyclohexylethyl 4-phenylbenzoate, octyl 4-biphenylacetate, nonyl 4-biphenylacetate, and 4-biphenylacetic acid. Decyl, 4-biphenyl acetate lauryl, 4-biphenyl acetate myristyl, 4-biphenyl acetate tridecyl, 4-biphenyl acetate pentadecyl, 4-biphenyl acetate cetyl, 4-biphenyl acetate cyclopentyl, 4-biphenyl acetate cyclohexylmethyl, 4-biphenyl acetate hexyl And cyclohexylmethyl 4-biphenylacetate.

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

[In the formula, R represents any one of an alkyl group having 3 to 18 carbon atoms and an aliphatic acyl group having 3 to 18 carbon atoms, and X represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, 1 or 2 carbon atoms. Y represents a hydrogen atom or a methyl group, and Z represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 or 2 carbon atoms, or a halogen atom. Is shown. ]
Examples of the compound include phenoxyethyl 4-butoxybenzoate, phenoxyethyl 4-pentyloxybenzoate, phenoxyethyl 4-tetradecyloxybenzoate, esters of phenoxyethyl 4-hydroxybenzoate with dodecanoic acid, and phenoxyethyl vanillate. Can be exemplified.

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

[Wherein, R represents any one of an alkyl group having 4 to 22 carbon atoms, an alkenyl group having 4 to 22 carbon atoms, a cycloalkylalkyl group, and a cycloalkyl group, and X represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom. Y represents 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 benzoic acid ester of octyl p-hydroxybenzoate, benzoic acid ester of decyl p-hydroxybenzoate, p-methoxybenzoic acid ester of heptyl p-hydroxybenzoate, and o- Examples thereof include methoxy benzoate and benzoate of cyclohexylmethyl p-hydroxybenzoate.

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

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

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

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

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

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

Among the components (c), those having a melting point in the range of 80 ° C to 130 ° C are applied to the reversible thermochromic pigment (colorant A) of the present invention, and those having a lower melting point are two types. This is applied to a reversible thermochromic pigment (colorant B) used in combination with an ink exhibiting the above color change temperature range.
The high melting point having a melting point in the range of 80 ° C. to 130 ° C. is hardly eluted in the aqueous ink medium even with the elapse of time, so that it has particularly excellent stability and 60 to 60% of the total amount of the reversible thermochromic composition. By applying at 90% by mass, more preferably at 65 to 80% by mass, the mixture becomes a mixture of an appropriate ratio, and the reversible thermochromic pigment can constitute a decoloring temperature of 110 ° C. or less, which is a range in which the pigment can be decolorized by frictional heat. , And the color density is also satisfactory. If the content is less than 60% by mass, the temperature is lowered, and it is difficult to make the low melting point component (c) a decoloring temperature of 75 ° C. or higher, which is difficult to erase at ambient temperature. It is difficult to make the component (c) have a decoloring temperature of 110 ° C. or lower, and it is difficult to obtain a sufficient color density as a colorant.

  The reversible thermochromic composition is a compatibilizer containing the above-mentioned components (a), (b), and (c) as essential components, and the proportion of each component is determined by the concentration, the discoloration temperature, the discoloration form and the content of each component. Although it depends on the type, generally, the component ratio at which desired characteristics can be obtained is (B) component 0.1 to 100, preferably 0.1 to 50, and more preferably (B) component 1 to component 1. 0.5 to 20, (c) component 5 to 200, preferably 5 to 100, more preferably 10 to 100 (the ratios are all parts by mass).

It is preferable that the decolorizing temperature of the reversible thermochromic pigment be 75 ° C. or more and 110 ° C. or less by appropriately adjusting the above ratio using the above-mentioned component (c) having a high melting point.
By setting the decoloring temperature to the above range, it is possible to decolor the handwriting by frictional heat that can be generated by rubbing using a friction body, and even in a high temperature state at an environmental temperature, the handwriting is inadvertently generated. Decoloring is suppressed.

Further, various light stabilizers can be added as required.
The light stabilizer is contained to prevent light deterioration of the reversible thermochromic composition comprising the components (a), (b) and (c), and is contained in an amount of 0.3 to 1% by mass of the component (a). To 24% by mass, preferably 0.3 to 16% by mass. Among the light stabilizers, an ultraviolet absorber effectively blocks ultraviolet light contained in sunlight or the like and prevents light deterioration caused by an excited state due to a photoreaction of the component (a). In addition, antioxidants, singlet oxygen quenchers, superoxide anion quenchers, ozone quenchers, and the like suppress oxidation reactions due to light.
The light stabilizers may be used alone or in combination of two or more.

The reversible thermochromic composition is used as a reversible thermochromic pigment by being dispersed in a thermoplastic resin or a thermosetting resin, or by being encapsulated in microcapsules.
The microencapsulation is performed by a conventionally known interfacial polymerization method, in situ polymerization method, in-liquid curing coating method, phase separation method from an aqueous solution, phase separation method from an organic solvent, melting dispersion cooling method, air suspension. There are a coating method, a spray drying method, and the like, which are appropriately selected according to the application. Furthermore, a secondary resin film may be further provided on the surface of the microcapsules according to the purpose to impart durability, or the surface characteristics may be modified for practical use.
The microcapsule pigment preferably includes inclusions / wall film in a range of 7/1 to 1/1 (mass ratio). When the ratio of the wall film is within the above range, the color density and the color density at the time of color development are improved. It is possible to prevent a decrease in sharpness, and it is more preferable that the inclusion / wall film is 6/1 to 1/1 (mass ratio).
By being encapsulated in the microcapsules, a chemically and physically stable pigment can be constituted, and the particle diameter is practically in the range of 0.01 to 50 μm, preferably 0.1 to 30 μm, more preferably 0.5 to 20 μm. Satisfy the nature.
The average particle diameter is measured using the image analysis type particle size distribution measurement software "Macview" manufactured by Mountech Co., Ltd., and the area of the particle is determined from the area of the particle area to obtain a projected area circle equivalent diameter (Heywood diameter). This is a value calculated and measured as the average particle diameter of particles equivalent to an equal volume sphere based on the calculated value. When all or most of the particles have a particle size of more than 0.2 μm, an equal volume sphere is obtained by the Coulter method using a particle size distribution analyzer (manufactured by Beckman Coulter, Inc., product name: Multisizer 4e). It can also be measured as the average particle size of the corresponding particles.

  In the present invention, a reversible thermochromic pigment having a decoloring temperature of 40 ° C. or more and 70 ° C. or less is used as a colorant B together with the reversible thermochromic pigment (colorant A) using the above-described high melting point (c) component. By doing so, a thermochromic ink composition for a writing instrument that develops a multi-stage hue change depending on the heating temperature from coloring (1) to coloring (2) and further to decoloring is obtained. For this reason, a writing implement that is rich in interest and has a higher commercial value can be configured.

The discoloration of the reversible thermochromic pigment will be described.
When the reversible thermochromic pigment reaches a complete color development temperature (t ₁ ) by lowering the temperature from the decolored state, it completely changes to a color developing state, and when the temperature rises from the color developing state, it reaches a complete color erasing temperature (t ₄ ). It is a pigment that is completely decolored.
Specifically, the hysteresis characteristics in the color density-temperature curve of the reversible thermochromic pigment are shown in FIG. 2 in which 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, t ₄ is fully reached decolored state temperature (hereinafter, complete decoloring referred to as temperature) and a point showing the density at, t ₃ is the temperature begins to decoloring (hereinafter, referred to as decoloring starting temperature ) is a point showing the density at, t ₂ begins to color temperature (hereinafter, is a point showing the density at referred to as coloring initiation temperature), t ₁ is the temperature to reach completely colored state (hereinafter, complete coloring temperature )).
_Further, t 1 and the upper rectilinear between ~t _3, a measure of the lower straight line perpendicular distance discoloration contrast between t 2 ~t _4, a vertical line between t 1 ~t _2, t 3 ~t The distance between the median and the vertical line between the _four is the temperature width indicating the degree of hysteresis (hereinafter, referred to as hysteresis width ΔH), and the larger the ΔH value, the easier it is to maintain each state before and after discoloration. .
Here, the difference between t ₄ and t ₃ or the difference (Δt) between t ₂ and t ₁ is a measure of the sharpness of discoloration.

As an example, a visual change in the colorants A and B having different hues will be specifically described with reference to a color density-temperature curve in FIG. For convenience, the low-temperature decoloring side colorant B is referred to as a reversible thermochromic pigment B, and the high-temperature decoloring side colorant A is referred to as a reversible thermochromic pigment A.
Complete decolorization of the other reversible thermochromic pigment A (high-temperature decoloring side colorant A) to a higher temperature than the complete decoloring temperature (t ₄ ) of one reversible thermochromic pigment B (low-temperature decoloring side colorant B). In order to satisfy the color temperature (t ′ ₄ ) (hereinafter, the reversible thermochromic pigment A is described as (t ′) to distinguish it from the reversible thermochromic pigment B), both the reversible thermochromic pigments A and B are colored. The temperature is increased from the colored state (1), and when the temperature reaches the complete decoloring temperature (t ₄ ), the reversible thermochromic pigment B is decolorized to become colored (2), and the complete decolorizing temperature (t) When ' ₄ ) is reached, the reversible thermochromic pigment A decolorizes, so that a color change from coloring (2) to decoloring is visually recognized.
When the temperature reaches a complete color development temperature (t ₁ = t ′ ₁ ) due to the temperature drop, the reversible thermochromic pigment A and the reversible thermochromic pigment B develop color and return to coloring (1).
By adding a non-color-change coloring agent, the color changes of coloring (1), coloring (2), and coloring (3) are visually recognized, and three types of handwriting can be visually recognized.

Further, as another example, referring to FIG. 4 more specifically, the complete decoloring temperature (t ₄ ) of one reversible thermochromic pigment B is set higher than the complete decoloring temperature (t ₄ ) of the other reversible thermochromic pigment A. In order to satisfy t ' ₄ ), the temperature of the reversible thermochromic pigments A and B is increased from the state of coloring (1) in which both of the pigments have developed, and when the temperature reaches the complete decoloring temperature (t ₄ ), the reversible thermochromic pigment is When B loses color and becomes colored (2) and reaches the complete decoloring temperature (t ′ ₄ ), the reversible thermochromic pigment A loses color. It is visually recognized.
When the temperature reaches the complete color development temperature (t ′ ₁ ) due to the temperature decrease, the reversible thermochromic pigment A develops color and returns to coloring (2). When the temperature is further decreased to reach the complete color development temperature (t ₁ ), the reversible thermochromic pigment A reaches the complete color development temperature (t ₁ ). The discolorable pigment B develops color and returns to coloring (1).

Further, as another example, referring to FIG. 5, the complete decolorization temperature (t ₄ ) of one reversible thermochromic pigment B is set higher than the complete decolorization temperature (t ₄ ) of the other reversible thermochromic pigment A. In order to satisfy t ' ₄ ), the temperature of the reversible thermochromic pigments A and B is increased from the state of coloring (1) in which both of the pigments have developed, and when the temperature reaches the complete decoloring temperature (t ₄ ), the reversible thermochromic pigment is When B loses color and becomes colored (2) and reaches the complete decoloring temperature (t ′ ₄ ), the reversible thermochromic pigment A loses color. It is visually recognized.
When the temperature reaches the complete color development temperature (t ′ ₁ ) due to the temperature decrease, the reversible thermochromic pigment A develops color and returns to coloring (2). When the temperature is further decreased to reach the complete color development temperature (t ₁ ), the reversible thermochromic pigment A reaches the complete color development temperature (t ₁ ). The discolorable pigment B develops color and returns to coloring (1).

Further, as another example, referring to FIG. 6, the complete decolorization temperature (t ₄ ) of one reversible thermochromic pigment B is set higher than the complete decolorization temperature (t ₄ ) of the other reversible thermochromic pigment A. In order to satisfy t ' ₄ ), the temperature of the reversible thermochromic pigments A and B is increased from the state of coloring (1) in which both of the pigments have developed, and when the temperature reaches the complete decoloring temperature (t ₄ ), the reversible thermochromic pigment is When B loses color and becomes colored (2) and reaches the complete decoloring temperature (t ′ ₄ ), the reversible thermochromic pigment A loses color. It is visually recognized.
When the temperature reaches the complete color development temperature (t ₁ ) due to the temperature drop, the reversible thermochromic pigment B develops a color and becomes colored (3). When the temperature is further lowered to reach the complete color development temperature (t ′ ₁ ), the reversible thermochromic pigment B Pigment A develops color and returns to coloring (1).

In any of the above cases, the reversible thermochromic pigment A (colorant _A ) is placed at a temperature higher by 5 ° C. or more than the complete decoloring temperature (t ₄ ) (TA) of the reversible thermochromic pigment B (colorant B). Has a complete decoloring temperature (t ′ ₄ ) (T _B ), the color change can be clearly recognized, and it is preferably 10 ° C. or more, more preferably 15 ° C. or more.
Further, by having the complete decoloring temperature (t ′ ₄ ) of the reversible thermochromic pigment A higher by 5 to 70 ° C. than the complete decoloring temperature (t ₄ ) of the reversible thermochromic pigment B, Is easy to express, Preferably it is 10-60 degreeC, More preferably, it is 15-50 degreeC.
When the color is changed by frictional heat generated by a friction body described later, the reversible thermochromic pigment B is heated to a temperature higher by 15 to 40 ° C., preferably 20 to 35 ° C. than the complete decoloring temperature (t ₄ ). by having a complete decoloring temperature of discoloring pigment a (t _'4), which makes it easy to express the color change in friction heat.
Further, the complete color erasing temperature (t ₄ ) of the reversible thermochromic pigment B is 50 ° C. or higher, preferably 55 ° C. or higher, more preferably 60 ° C. or higher, and the complete color developing temperature (t ₁ ) is 0 ° C. or lower, preferably Is −5 ° C. or lower, more preferably −10 ° C. or lower, and the full color development temperature (t ′ ₁ ) of the reversible thermochromic pigment A is 0 ° C. or lower, preferably −5 ° C. or lower, more preferably −10 ° C. or lower. By this, it is easy to maintain the discolored state at normal temperature.

Next, an ink composition containing a colorant that is brought into a decolored state by the above-described heating will be described.
The coloring agent is dispersed in a vehicle for a writing implement containing water and / or an organic solvent and, if necessary, various additives, and can be used as an ink for a writing implement such as a marking pen, a ballpoint pen, a fountain pen, and a brush pen.
Examples of the various additives include a resin, a viscosity adjuster, a dispersant, an antisettling agent, an antifoaming agent, a penetrant, a pH adjuster, a humectant, a fungicide, a preservative, and a rust inhibitor.

Among them, examples of the vehicle for writing implement used in the ink for writing implement include an oil-based vehicle containing an organic solvent or an aqueous vehicle containing water and, if necessary, an organic solvent.
Examples of the organic solvent include ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, ethylene glycol monomethyl ether, and ethylene glycol. 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.

The ink composition of the present invention may contain a dye or a pigment, if necessary.
As the dye, acid dyes, basic dyes, and direct dyes that can be dissolved in an aqueous medium can all be used.
Pigments include inorganic pigments such as carbon black, ultramarine blue, and titanium dioxide pigments, azo pigments, phthalocyanine pigments, indigo pigments, thioindigo pigments, threne pigments, quinacridone pigments, anthraquinone pigments, sullon pigments, and diketopyrrolopyrrole pigments. Organic pigments such as pigments, dioxazine pigments, perylene pigments, perinone pigments, and isoindolinone pigments, and fluorescent pigments can be exemplified.
Further, a metal pigment obtained by treating an aluminum powder or a surface of an aluminum powder with a coloring resin, a metallic luster pigment having a metal deposited film formed on a transparent or colored transparent film, a luminous pigment, and a core substance of natural mica, synthetic mica, glass flakes, alumina A pearl pigment or the like in which the surface of a transparent film piece is coated with a metal oxide such as titanium oxide can also be used.

Examples of the writing implement ink include a shear-thinning ink containing a shear-thinning agent in a vehicle, a coagulable ink containing a water-soluble polymer coagulant in a vehicle, and suspending a pigment in a moderately coagulated 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 a good handwriting can be formed.
Further, when the writing implement to be filled with the ink is a ball-point pen, it is possible to prevent the ink from leaking from the gap between the ball and the tip when not in use, or to reverse the flow of the ink when the writing tip is left upward (upright state). Can be prevented.
Examples of the shear thinning agent include xanthan gum, welan gum, succinoglycan in which the constituent monosaccharide is an organic acid-modified heteropolysaccharide of glucose and galactose (average molecular weight of about 1,000,000 to 8,000,000), guar gum, locust bean gum and the like. Derivatives, hydroxyethylcellulose, alginic acid alkyl esters, polymers having a molecular weight of 100,000 to 150,000 having alkyl ester of methacrylic acid as a main component, glucomannan, thickener having gelling ability extracted from seaweeds such as agar and carrageenin Polysaccharides, benzylidene sorbitol and benzylidene xylitol or derivatives thereof, crosslinkable acrylic acid polymer, inorganic fine particles, polyglycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester, 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. Examples thereof include a mixture of N-alkyl-2-pyrrolidone and an anionic surfactant, and a mixture of polyvinyl alcohol and an acrylic resin.

Examples of the water-soluble polymer coagulant include polyvinyl pyrrolidone, polyethylene oxide, water-soluble polysaccharides, and the like.
Examples of the water-soluble polysaccharide include tragacanth gum, guar gum, pullulan, cyclodextrin, a water-soluble cellulose derivative, and the like. Specific examples of the water-soluble cellulose derivative include methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, and hydroxypropyl methyl cellulose. And the like.

By using a comb polymer dispersant having a carboxyl group in the side chain together with the polymer flocculant, the dispersibility of a loose aggregate of a colorant (reversible thermochromic pigment) by the polymer flocculant is improved. be able to.
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. Acrylic polymer compound having the following formula is preferable, and examples of the compound include Solsperse 43000 (trade name, manufactured by Lubrizol Japan Ltd.).

Further, by containing an organic nitrogen sulfur compound, when the ink composition is filled in a writing implement and put to practical use, the sedimentation of the colorant due to vibration can be further suppressed, so that the reversible thermochromic property in the form of microcapsules is obtained. This is advantageous when using pigments.
This further improves the dispersibility of dispersing a loose aggregate of the reversible thermochromic pigment with a comb-type polymer dispersant having a carboxyl group in a side chain.
As the organic nitrogen sulfur compound, a compound selected from a thiazole compound, an isothiazole compound, a benzothiazole compound, and a benzoisothiazole compound is used.
Specific examples of the organic nitrogen sulfur compound include 2- (4-thiazoyl) -benzimidazole (TBZ), 2- (thiocyanate methylthio) -1,3-benzothiazole (TCMTB), and 2-methyl-4-isothiazoline- One or more compounds selected from 3-one and 5-chloro-2-methyl-4-isothiazolin-3-one are used, preferably 2- (4-thiazoyl) -benzimidazole (TBZ), One 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 sulfur compound, manufactured by Permachem Asia Ltd., trade names: Topside 88, 133, 170, 220, 288, 300, 400, 500, 600, 700Z, 800, 950, manufactured by Hokuko Sangyo Co., Ltd., trade names: Hoxter HP, E50A, Hocside P200, 6500, 7400, MC, 369, and R-150.
The mass ratio of the comb-type polymer dispersant having a carboxyl group in the side chain and the organic nitrogen sulfur compound is 1: 1 to 1:10, preferably 1: 1 to 1: 5, and satisfies the above range. Thereby, the dispersibility of the loose aggregate of the reversible thermochromic pigment and the suppression of sedimentation of the microcapsule pigment due to vibration can be sufficiently exhibited.

Further, when a water-soluble resin applied for imparting stickiness or viscosity to the paper surface of the handwriting is added, the ink containing the comb-type polymer dispersant having a carboxyl group in the side chain and the organic nitrogen sulfur compound is used. As a result, the function of increasing the stability of the colorant is further improved.
Examples of the water-soluble resin include an alkyd resin, an acrylic resin, a styrene-maleic acid copolymer, a cellulose derivative, polyvinyl pyrrolidone, polyvinyl alcohol, dextrin, and the like. Preferably, polyvinyl alcohol is used.
Further, the polyvinyl alcohol is more preferably used because a partially saponified polyvinyl alcohol having a saponification degree of 70 to 89 mol% is rich in solubility even in an acidic region of the ink.
The water-soluble resin is added in an amount of 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 it into a ballpoint pen, a higher fatty acid such as oleic acid, a nonionic surfactant having a long-chain alkyl group, a polyether-modified silicone oil, thiophosphorous acid tri (alkoxycarbonylmethyl ester), Triesters of thiophosphorous acid such as tri (alkoxycarbonylethyl ester) thiophosphorous acid, phosphoric acid monoesters of polyoxyethylene alkyl ether or polyoxyethylene alkylaryl ether, phosphorus of polyoxyethylene alkyl ether or polyoxyethylene alkylaryl ether It is preferable to add a lubricant such as an acid diester or a metal salt, an ammonium salt, an amine salt or an alkanolamine salt thereof to prevent wear of the ball seat.

  In addition, if necessary, a resin such as an acrylic resin, a styrene-maleic acid copolymer, a cellulose derivative, polyvinylpyrrolidone, polyvinyl alcohol, or dextrin is added to impart sticking property or viscosity to paper, or sodium carbonate or sodium phosphate. , An inorganic salt such as sodium acetate, a pH adjuster such as an organic basic compound such as a water-soluble amine compound, a rust inhibitor such as benzotriazole, tolyltriazole, dicyclohexylammonium nitrite, diisopropylammonium nitrite, and saponin; Sodium salt of 1,2-benzthiazolin-3-one, sodium benzoate, sodium dehydroacetate, potassium sorbate, propyl paraoxybenzoate, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine Preservative or Are fungicides, ureas, nonionic surfactants, reduced or non-reduced starch hydrolysates, oligosaccharides such as trehalose, sucrose, cyclodextrin, glucose, dextrin, humectants such as sorbitol, mannitol, sodium pyrophosphate , A defoaming agent, a dispersant, and a fluorine-based surfactant or a nonionic surfactant for improving ink permeability.

  The ink may contain a reversible thermochromic pigment in an amount of preferably 10 to 40% by mass, more preferably 10 to 35% by mass, based on the total mass of the ink. When the content of the pigment is in the above range, a desired color density can be achieved, and further, a decrease in ink outflow property can be prevented.

In particular, it is preferable that the colorant B is 70% by mass or less based on the total amount of the colorant.
When the content of the colorant B is 70% by mass or less, preferably 60% by mass or less based on the total amount of the colorant, the color density of the colorant A in the entire ink can be easily increased. Even in the state of coloring (2), a handwriting with high visibility can be obtained with a clear hue.

The thermochromic ink composition for writing implements of the present invention, in an aqueous medium containing water and a water-soluble organic solvent, or in an oily medium, together with one or two or more decolorizable colorants, if necessary, various additives. It is prepared by charging and stirring.
For inks having a shear thinning property, two or more decolorizable colorants and various additives are added to an aqueous medium, stirred and dissolved, and further sheared in a solvent separately prepared. It is prepared by directly adding a dispersion in which a viscosity reducing agent is dispersed or a shear thinning agent, and stirring.

A writing instrument for storing the ink will be described.
When filling the ball-point pen, the structure and shape of the ball-point pen itself are not particularly limited. For example, the ball-point pen has an ink storage tube filled with shear-thinning ink in a shaft cylinder, and the ink storage tube has A ball-point pen which communicates with a ball-point pen tip mounted on the ink-jet head and further has a liquid stopper for preventing backflow close to the end face of the ink can be exemplified.
The ballpoint pen tip will be described in more detail. A tip formed by holding a ball in a ball holding portion formed by pressing and deforming the vicinity of the tip of a metal pipe inward from an outer surface, or cutting a metal material by a drill or the like A chip formed by holding a ball in a ball holding portion formed by the above, a chip provided with a resin ball receiving seat inside a metal or plastic chip, or a ball held by the chip is moved forward by a spring body. Energized ones can be applied.
Further, the ball is made of cemented carbide, stainless steel, ruby, ceramic, resin, rubber, or the like, having a thickness of 0.3 to 2.0 mm, preferably 0.3 to 1.5 mm, more preferably 0.3 to 1.0 mm. Those having a diameter of about the same can be applied.
As the ink storage tube for storing the ink, for example, a molded body made of a thermoplastic resin such as polyethylene, polypropylene, polyethylene terephthalate, or nylon, or a metal tubular body is used.
In addition to directly connecting the chip to the ink storage tube, the ink storage tube and the chip may be connected via a connecting member.
The ink storage tube may be a form of a refill, and the refill may be housed in a shaft cylinder made of resin, metal, or the like, or the shaft cylinder itself having a tip mounted on a tip may be used as an ink container. The shaft cylinder may be directly filled with ink.
When the ink composition is stored in a retractable ball-point pen, the structure and shape of the retractable ball-point pen are not particularly limited, and the writing tip provided on the ball-point pen refill is shafted in a state where it is exposed to the outside air. Any structure can be used as long as it is housed in a cylinder and the writing tip protrudes from the opening of the shaft cylinder by the operation of the retracting mechanism.
As a method of operating the retracting mechanism, for example, a knock type, a rotary type, a slide type, and the like can be given.
The knock type has a knock portion at a rear end portion or a side surface of the shaft tube, and a configuration in which a ballpoint pen tip is protruded and retracted from a front end opening portion of the shaft tube by pressing the knock portion, or a clip portion provided on the shaft tube. , The ball-point pen tip is made to protrude and retract from the front end opening of the barrel.
The rotary type has a configuration in which a rotating portion is provided at a rear portion of the barrel, and the ball-point pen tip is made to protrude and retract from a front end opening of the barrel by rotating the rotating portion.
The slide type has a slide portion on the side of the barrel, and a configuration in which the ballpoint pen tip is made to protrude and retract from the front end opening of the barrel by operating the slide, or by sliding a clip portion provided on the barrel, A configuration in which the ballpoint pen tip is made to protrude and retract from the front end opening of the barrel can be exemplified.
The retractable ballpoint pen is a composite type retractable ballpoint pen in which a plurality of ballpoint pen refills are accommodated in a barrel, and a writing tip of one of the ballpoint pen refills protrudes and retracts from a front end opening of the barrel by operating a retracting mechanism. You may.

The back end of the ink stored in the ink storage tube is filled with an ink backflow preventer.
The ink backflow preventive composition comprises a non-volatile liquid or a hardly volatile liquid.
Specifically, petrolatum, spindle oil, castor oil, olive oil, refined mineral oil, liquid paraffin, polybutene, α-olefin, α-olefin oligomer or cooligomer, dimethyl silicone oil, methylphenyl silicone oil, amino-modified silicone oil, Examples thereof include polyether-modified silicone oil and fatty acid-modified silicone oil, and one or two or more of them can be used in combination.
The non-volatile liquid and / or the non-volatile liquid are preferably thickened by adding a thickener to a suitable viscosity. As the thickener, silica whose surface is subjected to hydrophobic treatment, and whose surface is subjected to methylation treatment are used. Fine particle silica, aluminum silicate, swelling mica, clay-based thickeners such as bentonite and montmorillonite subjected to hydrophobic treatment, fatty acid metal soaps such as magnesium stearate, calcium stearate, aluminum stearate, zinc stearate, tribenzylidene sorbitol, Examples thereof include fatty acid amides, amide-modified polyethylene wax, hydrogenated castor oil, dextrin compounds such as fatty acid dextrin, and cellulose compounds.
Further, the liquid ink backflow preventive and the solid ink backflow preventive may be used in combination.

When filling the marking pen, the structure and shape of the marking pen itself is not particularly limited, for example, a fiber processed body in which an ink occluding body composed of a fiber bundle is built in a shaft cylinder and a capillary gap is formed A marking pen made by mounting a marking pen chip directly or via a relay member on a shaft cylinder, wherein the ink occluding body is impregnated with cohesive ink in the ink occluding body of the marking pen in which the ink occluding body and the chip are connected. For example, a marking pen or the like in which a chip and an ink storage tube are arranged via a valve body that is opened by pressing the chip and ink is directly stored in the ink storage tube can be exemplified.
The chip is a porous member having interconnected pores whose conventional porosity is generally selected from a range of 30 to 70%, such as a resin processed body of a fiber, a fusion processed body of a heat-fusible fiber, and a felt body, One end is processed into a shape suitable for the purpose, such as a shell shape, a rectangular shape, a chisel shape, or the like, and is provided for practical use.
The ink occluding body is formed by bundling crimped fibers in a longitudinal direction, and is provided inside a covering such as a plastic cylinder or a film, and is adjusted to have a porosity in a range of approximately 40 to 90%. Is done.
The valve body may be of a general-purpose pumping type, but is preferably set to a spring pressure which can be pressed and released by writing pressure.

  Further, the form of the ball-point pen and the marking pen is not limited to those described above, and may be a double-headed writing instrument on which a tip of a different form is mounted or a pen point for leading out ink of a different color is mounted.

In addition, the handwriting obtained by writing on a writing surface using the writing implement containing the ink composition for a writing implement can be discolored by a cooling tool or a heating tool.
Examples of the cooling device include a cooling and discoloring device using a Peltier element, a cooling and discoloring device filled with a coolant such as cold water and ice chips, a refrigerator and a freezer.
Examples of the heating tool include a heating color changing tool equipped with a resistance heating element, a heating color changing tool filled with hot water, and the like, and a hair dryer. Used.

As the friction member, an elastic body such as an elastomer or a plastic foam which is rich in elasticity and can generate appropriate friction when rubbing to generate frictional heat is suitable.
Note that the handwriting can be rubbed by using an eraser, but eraser scum is generated at the time of friction. Therefore, the above-described friction member which hardly generates eraser scum is preferably used.
As the material of the friction member, silicone resin, SEBS resin (styrene-ethylene-butadiene-styrene block copolymer), polyester-based resin, or the like is used.
As the friction member, a writing instrument set can be obtained by combining a writing instrument and a member having an arbitrary shape (friction body) separately. However, by providing the friction element in the writing instrument, portability is excellent.
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 by a friction member, the barrel is formed by 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 tip (top) of the cap or at the rear end of the barrel (portion where the writing tip is not provided).
In the case of a retractable writing instrument, the location where the friction member is provided is not particularly limited.For example, when the shaft cylinder itself is formed by a friction member, or when a clip is provided, the clip itself is formed by a friction member, A friction member can be provided in the vicinity of the opening of the barrel, at the rear end of the barrel (where the writing tip is not provided), or at the knocking part.

Incidentally, two or more kinds of the friction members may be provided. In that case, due to friction with the paper surface, that one emits a frictional heat in the range of T _B is a handwriting discoloration temperature T _A, the other is assumed to emit T _A more frictional heat is handwriting decoloring temperature preferable. By doing so, a desired discoloration step can be easily and reliably developed according to each friction member without worrying about the force applied during handwriting friction.

Examples will be described below. The parts in the examples are parts by mass, and the average particle diameter was measured by a Coulter method using a particle size distribution analyzer (manufactured by Beckman Coulter, product name: Multisizer 4e) by the Coulter method. Value.
The melting point is a value measured by FP81HT manufactured by METTLER TOLEDO.

Example 1
Preparation of reversible thermochromic pigment (1) 2,6-bis (2,4-diethyloxyphenyl) -4- (4-bis (4-methylphenyl) aminophenyl) pyridine as component (a), component (b) Reversible thermochromic composition comprising 5 parts of 2,2-bis (4'-hydroxyphenyl) hexafluoropropane as a component and 50 parts of 2- (4-benzyloxyphenyl) ethyl stearate [melting point 82 ° C.] as a component (c) The product was encapsulated in microcapsules to prepare a reversible thermochromic pigment.
The reversible thermochromic pigment has an average particle size of 2.0 μm, a complete color erasing temperature (t ′ ₄ ) of 80 ° C., and a complete color developing temperature (t ′ ₁ ) of 42 ° C., and changes color from orange to colorless with a change in temperature.

Preparation of thermochromic ink composition for writing implement (see Fig. 2)
20 parts of the reversible thermochromic pigment, 0.33 part of xanthan gum (shear-thinning agent), 10 parts of urea, 10 parts of glycerin, nonionic penetrating agent [San Nopco Co., Ltd., trade name: Nopco SW-WET] -366] 0.55 part, modified silicone antifoaming agent [manufactured by San Nopco Co., Ltd., trade name: Nopco 8034] 0.13 part, fungicide [Zeneca Co., Ltd., trade name: Proxel XL-2] A thermochromic ink composition for writing implements, consisting of 0.13 part and 58.86 parts of water, which changes color from orange to colorless with a change in temperature was prepared.

Preparation of Ballpoint Pen The ink composition was suction-filled into a polypropylene pipe, and connected to a ballpoint pen tip holding a 0.5 mm stainless steel ball at the tip via a resin holder. A ballpoint pen refill was obtained by filling a viscoelastic ink backflow preventer (liquid tap) having a main component, further fitting a tail plug at the rear end of the pipe, and performing deaeration by centrifugation.
Next, the ballpoint pen refill was assembled in a shaft barrel composed of a front barrel and a rear barrel, and a cap was fitted to obtain a thermochromic ballpoint pen. A friction member made of SEBS resin is attached to the rear end of the rear barrel.

Discoloration Behavior of Handwriting In the handwriting obtained by writing with the ballpoint pen, an orange handwriting is visually recognized at room temperature (25 ° C.), and when heated to 80 ° C., the reversible thermochromic pigment is decolorized (t ′ ₄ ). It becomes colorless.
When the temperature was cooled to 42 ° C. from this state, the pigment was completely colored (t ′ ₁ ) and a bright orange handwriting was visually recognized.

Examples 2-3, Comparative Examples 1-4
A thermochromic ink composition for a writing instrument was prepared in the same manner as in the thermochromic ink composition for a writing instrument of Example 1 except that the reversible thermochromic pigment was changed to obtain a thermochromic ballpoint pen. All of the obtained inks of Examples had no discoloration defect and retained the discoloration characteristics for a long period of time.
The following table shows the pigment compositions of the examples and comparative examples, and the results of the density retention test and handwriting erasure test of each ink.

The evaluations of the high-temperature holding test and the handwriting erasure test shown in Table 1 are as follows.
High-Temperature Retention Test After writing a continuous circle on JIS P3201 white writing paper A, the paper was left in an environment of 70 ° C. for 1 hour. Thereafter, the state of the handwriting was visually checked at room temperature.
Each symbol is as follows.
：: Vivid handwriting equivalent to that at the time of writing is visually recognized.
×: Handwriting disappeared and could not be visually recognized.

Handwriting erasure test After writing continuous circles on JIS P3201 white writing paper A, each handwriting when heated with an attached friction body was visually observed.
Each symbol is as follows.
A: Erasable easily.
：: Elimination was possible although it took time.
Δ: Handwriting was thin but could not be erased cleanly.
×: Handwriting remained without erasing.

Example 4
Preparation of reversible thermochromic pigment A (2) 2,6-bis (2,4-diethyloxyphenyl) -4- (4-bis (4-methylphenyl) aminophenyl) pyridine as component (b) Reversible thermochromic comprising 5 parts of 2,2-bis (4'-hydroxyphenyl) hexafluoropropane as a component and 50 parts of 2- (4-benzyloxyphenyl) ethyl stearate [melting point 82 ° C.] as a component (c). The composition a was encapsulated in microcapsules to prepare a reversible thermochromic pigment A.
The reversible thermochromic pigment A has an average particle diameter of 2.0 μm, a complete color erasing temperature (t ′ ₄ ) of 80 ° C., and a complete color developing temperature (t ′ ₁ ) of 42 ° C., and changes color from orange to colorless due to a temperature change. .

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

Preparation of thermochromic ink composition for writing implement (see FIG. 4)
10 parts of the reversible thermochromic pigment A, 10 parts of the reversible thermochromic pigment B, 0.33 part of xanthan gum (shear-thinning agent), 10 parts of urea, 10 parts of glycerin, nonionic penetrating agent [manufactured by San Nopco Co., Ltd.] (Trade name: Nopco SW-WET-366) 0.55 parts, modified silicone antifoaming agent (manufactured by San Nopco Co., Ltd., trade name: Nopco 8034) 0.13 parts, fungicide (Zeneca Co., Ltd.) Trade name: Proxel XL-2] A thermochromic ink composition for writing implements, consisting of 0.13 parts and 58.86 parts of water, was prepared which changes color from vermilion to orange, and further from orange to colorless in two steps according to temperature change.

Preparation of Ballpoint Pen The ink composition was suction-filled into a polypropylene pipe, and connected to a ballpoint pen tip holding a 0.5 mm stainless steel ball at the tip via a resin holder. A ballpoint pen refill was obtained by filling a viscoelastic ink backflow preventer (liquid tap) having a main component, further fitting a tail plug at the rear end of the pipe, and performing deaeration by centrifugation.
Next, the ballpoint pen refill was assembled in a shaft barrel composed of a front barrel and a rear barrel, and a cap was fitted to obtain a thermochromic ballpoint pen. A friction member made of SEBS resin is attached to the rear end of the rear barrel.

Discoloration behavior of handwriting The handwriting obtained by writing with the ballpoint pen has a bright vermilion color in which pigment A and pigment B are mixed at room temperature (25 ° C.), and is rubbed using a friction body attached to a cap. Then, at 64 ° C., the pigment B is decolorized (t ₄ ), and a bright orange handwriting by the pigment A is visually recognized. When the temperature is further raised to 80 ° C., the pigment A is decolorized (t ′ ₄ ). It becomes colorless.
The vivid vermilion, vivid orange, and colorless reversibly changing state were sequentially and appropriately visually discriminated by heating, and were rich in stepwise color change variations.

Examples 5 to 6
In the thermochromic ink composition for writing implements of Example 4, the thermochromic properties for writing implements were changed in the same manner except that the reversible thermochromic pigment A (pigment A) and the reversible thermochromic pigment B (pigment B) were changed. An ink composition was prepared to obtain a thermochromic ballpoint pen. All of the obtained inks maintained the discoloration characteristics for a long time without causing discoloration failure.
Further, when the handwriting formed on the paper surface was rubbed with the friction member, the rubbed portion changed color to a clear hue excellent in contrast with other portions. When the rubbing was further continued, the rubbed portion could be erased cleanly.
The following table shows the pigment composition of each example.

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

Claims (8)

  A reversible thermochromic composition comprising (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reaction medium for controlling the color reaction of (a) and (b). An aqueous ink composition using a reversible thermochromic pigment encapsulated in microcapsules as a colorant, wherein the component (c) has a melting point in the range of 80 ° C to 130 ° C, and the reversible thermochromic composition A thermochromic ink composition for writing implements in the range of 60 to 90% by mass of the total amount.   The thermochromic ink composition for a writing instrument according to claim 1, wherein the reversible thermochromic pigment has a color erasing temperature of 75C or more and 110C or less.   The heat for a writing instrument according to claim 2, wherein the reversible thermochromic pigment (colorant A) according to claim 2 and the reversible thermochromic pigment (colorant B) having a decoloring temperature of 40C or more and 70C or less are used in combination. Discolorable ink composition. The hue of the colorant B is different from the hue of the colorant _A , and a hue change occurs in two stages at two types of decolorization temperatures T _A and T _B (T _A > T _B ). Thermochromic ink composition for writing implements.   The thermochromic ink composition for a writing instrument according to any one of claims 1 to 4, wherein the colorant is added in a range of 10 to 40% by mass based on the total amount of the ink composition.   A writing implement incorporating the thermochromic ink composition for a writing implement according to any one of claims 1 to 5.   7. The writing implement according to claim 6, further comprising a friction member for discoloring the handwriting of the writing implement by frictional heat. It said friction member is made of two types, due to friction with the paper, one emits a frictional heat in the range of T _A from T _B, the writing instrument according to claim 7 wherein the other is one that emits T _A more frictional heat.

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