JP6216148B2 - Reversible thermochromic printed matter - Google Patents

Description

  The present invention relates to a reversible thermochromic printed matter. More specifically, the present invention relates to a reversible thermochromic printed matter capable of reproducing a natural color (natural color) reversible thermochromic image.

Conventionally, an electron-donating color-forming organic compound, an electron-accepting compound, and a reaction medium that reversibly causes an electron-donating reaction between the electron-donating color-forming organic compound and the electron-accepting compound in a specific temperature range. Several proposals have been disclosed regarding reversible thermochromic printed matter using as a coloring material a microcapsule pigment encapsulating each reversible thermochromic composition of yellow, cyan, and magenta as essential components (for example, Patent Document 1). To 3).
The reversible thermochromic printed matter is one in which a reversible thermochromic image of a natural color can be provided by creating a secondary color or a tertiary color by overlapping each color material.
However, the reversible thermochromic microcapsule pigment used as the coloring material tends to lose transparency because the wall film forming the capsule becomes thick as the particle size increases.
Therefore, the microcapsule pigment fixed on the upper layer of the color material greatly contributes to the hue, and the lower color material is shielded by the upper layer microcapsule pigment, and thus cannot contribute to the hue. For example, green is reproduced using yellow and cyan, but when the transparency of yellow decreases, cyan is shielded by yellow existing on cyan, so that the color becomes muddy and a clear green is reproduced. It becomes difficult to do.
Therefore, when a reversible thermochromic microcapsule pigment having poor transparency is used, it is difficult to form a reversible thermochromic image that faithfully reproduces a natural color.

Japanese Utility Model Publication No. 53-140506 JP 55-63293 A JP-A-8-11467

  The present inventor intends to provide a printed matter provided with a reversible thermochromic image of a natural color and provided with a reversible thermochromic image capable of faithfully reproducing the natural color.

The present invention, in supporting lifting member, the yellow, magenta, and each of the non-thermochromic coloring material for cyan, (b) an electron-donating coloring organic compound, (b) an electron-accepting compound, (c) the (B) Reversible color change from complementary colors of the non-thermochromic color materials of yellow, magenta, and cyan comprising a compound that is a reaction medium that reversibly causes an electron transfer reaction in the specific temperature range. A printed material provided with a reversible thermochromic natural color image by adhering a coloring material containing each of the reversible thermochromic microcapsule pigment encapsulating the thermochromic composition, wherein the microcapsule pigment has an average particle size A reversible thermochromic print having a diameter in the range of 0.1 to 10.0 μm and a particle size exceeding 15 μm is less than 20% by volume in the total microcapsule pigment is required.
Furthermore, it is required that the support is a puzzle piece, the puzzle piece is a jigsaw puzzle piece, and the like.

  The present invention provides a reversible thermochromic image of a natural color by creating a secondary color or a tertiary color by stacking and adhering a colorant having reversible thermochromic properties each having a hue of yellow, magenta, and cyan on a support. It is possible to provide a reversible thermochromic printed matter that is rich in practicality and capable of faithfully reproducing natural colors.

It is explanatory drawing which shows the discoloration behavior of the microcapsule pigment which included the heat decoloring type reversible thermochromic composition. It is explanatory drawing which shows the discoloration behavior of the microcapsule pigment which included the heat decoloring type reversible thermochromic composition which has color memory property. It is explanatory drawing which shows the discoloration behavior of the microcapsule pigment which included the heating coloring type reversible thermochromic composition.

The following (a) electron donating color-forming organic compound, (b) electron accepting compound, (c) a reaction medium in which the electron transfer reaction by the components (a) and (b) occurs reversibly in a specific temperature range. A reversible thermochromic composition that develops colors of yellow, magenta, and cyan, respectively, and a reversible thermochromic microcapsule pigment encapsulating the same will be described.
Examples of the reversible thermochromic microcapsule pigment include a predetermined temperature (discoloration point) described in JP-B-51-44706, JP-B-51-44707, JP-B-1-29398, and the like. Before and after the color change, the color disappears in the temperature range above the high temperature side discoloration point, and the color develops in the temperature range below the low temperature side discoloration point. The other state is maintained while the heat or cold required to develop the state is applied, but when the heat or cold is no longer applied, the hysteresis width returns to the state exhibited in the normal temperature range. Applying a reversible thermochromic microcapsule pigment containing a reversible thermochromic composition that has a relatively small characteristic (ΔH = 1 to 7 ° C.) (decolored by heating and develops color by cooling) (Fig. 1 Irradiation).

In addition, large hysteresis characteristics (ΔH _B = 8 to 50 ° C.) described in JP- _B -4-17154, JP-A-7-179777, JP-A-7-33997, JP-A-8-39936, and the like. ), That is, when the shape of the curve plotting the change in the color density due to the temperature change is lowering the temperature from the lower temperature side than the color changing temperature range, as opposed to increasing the temperature from the lower temperature side. In the specific temperature range, the color changes in a low temperature range below the complete color development temperature (t ₁ ) or the color erase state in the high temperature range above the complete color erase temperature (t ₄ ). Reversible thermal discoloration of a heat decoloring type (decolored by heating and developed by cooling) having a color memory property maintained in [temperature range between t _{2 and} t ₃ (substantially two-phase holding temperature range)] Reversible thermal discoloration encapsulating sexual composition Microencapsulated pigment can be applied (see FIG. 2).

The hysteresis characteristics in the color density-temperature curve of the microcapsule pigment encapsulating the reversible thermochromic composition will be described below with reference to the graph of FIG.
In FIG. 2, the vertical axis represents color density and the horizontal axis represents temperature. The change in color density due to the temperature change proceeds along the arrow. Here, A is a point indicating a density at a temperature t ₄ (hereinafter referred to as a complete decoloring temperature) reaching a completely decolored state, and B is a temperature t ₃ (hereinafter referred to as a decoloring start temperature) at which decoloring starts. C is a point indicating a density at a temperature t ₂ at which color development starts (hereinafter referred to as a color development start temperature), and D is a temperature t ₁ at which a fully colored state is reached (hereinafter referred to as a color development start temperature). , Referred to as a complete color development temperature).
Furthermore, a measure of the length of the line segment EF indicates the contrast of the color change, the line segment _{HG (t 3 + t 4/} 2-t 1 + t 2/2) of the length temperature width showing the degree of hysteresis (hereinafter, The greater the ΔH value, the easier it is to hold each state before and after the color change.
Here, the difference between t ₄ and t ₃ , or the difference between t ₂ and t ₁ (Δt) is a scale indicating the sensitivity of discoloration.

In order to present only the specific one of the states in the normal temperature range of the coloring and decoloring state of the reversible thermal discoloration microcapsule pigment (25 ° C. so) is complete decoloring temperature (t ₄₎ is located at 50 ° C. or higher In addition, the color development start temperature (t ₂ ) is preferably 5 ° C. or lower.
Here, the reason why the complete decoloring temperature (t ₄ ) is 50 ° C. or more and the color development start temperature (t ₂ ) is 5 ° C. or less in order to maintain the color development state in the normal temperature range. If the heating is stopped without reaching the complete decoloring temperature (t ₄ ) after the decoloring start temperature (t ₃ ), a phenomenon of returning to the first state occurs again, and color development starts from the decolored state Even if the cooling is stopped in a state where the temperature does not reach the complete color development temperature (t ₁ ) after passing through the temperature (t ₂ ), the color development state is maintained, so the complete color erasing temperature (t ₄ ) exceeds the normal temperature range. If it is 50 ° C. or higher, the color development state will be maintained in the normal use state, and if the color development start temperature (t ₂ ) is a temperature of 5 ° C. or less below the normal temperature range, the color disappearance state will be in normal use. Maintained.
In the temperature setting of the complete decoloring temperature (t ₄ ), a higher temperature is preferable in order to maintain the color development state in a normal use state, 55 ° C. or higher is preferable, and 60 ° C. or higher is preferable. More preferred.
Moreover, in the temperature setting of the color development start temperature (t ₂ ), it is preferably a lower temperature in order to maintain the decolored state in a normal use state, preferably 0 ° C. or less, and −5 ° C. or less. Is more preferred.
In order to make the microcapsule pigment encapsulating the reversible thermochromic composition into a colored state in advance, it is preferable to cool it in a general-purpose freezer as a cooling means, but considering the cooling capacity of the freezer, it is −50 ° C. The complete color development temperature (t ₁ ) is -50 ° C to 5 ° C, preferably -50 ° C to 0 ° C, more preferably -50 ° C to -5 ° C.
In the present invention, the hysteresis width (ΔH) is in the range of 40 ° C. to 100 ° C., preferably 50 to 100 ° C., more preferably 60 to 100 ° C.

Examples of the yellow (i) electron-donating color-forming organic compound include pyridine compounds, quinazoline compounds, and bisquinazoline compounds.
As the pyridine compound,
4- (4'-methylbenzylaminophenyl) -pyridine,
2,6-diphenyl-4- (4'-dimethylaminophenyl) -pyridine,
2,6-diphenyl-4- (4'-phenyl, 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-ethoxyethyl, N-methylaminophenyl) -pyridine,
2,6-bis (2'-ethyloxyphenyl) -4- (4'-N-ethoxyethyl, N-methylaminophenyl) -pyridine,
2,6-bis (2'-butyloxyphenyl) -4- (4'-N-ethoxyethyl, N-methylaminophenyl) -pyridine,
2,6-bis (2'-hexyloxyphenyl) -4- (4'-N-ethoxyethyl, N-methylaminophenyl) -pyridine,
2,6-bis (2'-octyloxyphenyl) -4- (4'-N-ethoxyethyl, 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'-methoxyphenyl) -4- (4'-dimethylaminophenyl) -pyridine,
2,6-dimethyl-3,5-biscarboethoxy-4- (4'-dimethylaminophenyl) -pyridine,
2- (2'-octoxyphenyl) -4- (4'-dimethylaminophenyl) -6-phenyl-pyridine,
2,6-diethoxy-4- (4'-diethylaminophenyl) -pyridine,
4- (4-methoxyphenyl) -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-methoxycarbonylphenyl) -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-methoxyphenyl) -2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (4-methoxyphenyl) -2,6-bis (4-morpholinophenyl) -pyridine,
4- (4-fluorophenyl) -2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (4-octoxyphenyl, methylamino) -2,6-diphenylpyridine,
4- (4-chlorophenyl) -2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (4-nitrophenyl) -2,6-bis (4-dimethylaminophenyl) -pyridine,
4- [4- (2-cyanoethyl), methylaminophenyl] -2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (2,5-dimethoxyphenyl) -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- (2-methyl-4-pyrrolidinylphenyl) -2,6-bis (4-dimethylaminophenyl) -pyridine,
4-phenyl-2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (4-methylphenyl) -2,6-bis (4-diethylaminophenyl) -pyridine,
4- (4-methoxyphenyl) -2,6-bis (4-diethylaminophenyl) -pyridine,
4- (4-methoxyphenyl) -2,6-bis (4-dibenzylaminophenyl) -pyridine,
4- (4-methoxyphenyl) -2,6-bis (4-piperidinylphenyl) -pyridine,
4- [2,4-bis (dimethylamino) phenyl] -2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (2-ethoxy-4-diethylaminophenyl) -2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (2-ethoxycarbonyl-4-diethylaminophenyl) -2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (4-benzyl, ethylaminophenyl) -2,6-bis (4-dimethylaminophenyl) -pyridine,
4- (4-dimethylaminophenyl) -2,6-diphenylpyridine,
4- [4- (2-cyanoethyl), benzylaminophenyl] -2,6-diphenylpyridine,
4- (4-dibenzylaminophenyl) -2,6-diphenylpyridine,
4- (4-dimethylaminophenyl) -2,6-bis (4-chlorophenyl) -pyridine,
4- (2-methyl-4-dimethylaminophenyl) -2,6-diphenylpyridine,
4- (2-ethyl-4-dimethylaminophenyl) -2,6-diphenylpyridine,
4- [4- (2-cyanoethyl), methylaminophenyl] -2,6-diphenylpyridine,
4- (4-methyl, phenylaminophenyl) -2,6-diphenylpyridine,
4- (4-chloroethyl, methylaminophenyl) -2,6-diphenylpyridine,
4- (4-Ethoxyethyl, methylaminophenyl) -2,6-diphenylpyridine and the like can be mentioned.

As the quinazoline compound,
2- (4'-dimethylaminophenyl) -4-methoxy-quinazoline,
2- (4′-dimethylaminophenyl) -4-phenoxy-quinazoline,
2- (4′-phenylmethylaminophenyl) -4-phenoxy-quinazoline,
2- (4'-piperidinophenyl) -4-phenoxy-quinazoline,
2- (4′-dimethylaminophenyl) -4- (4 ″ -chlorophenyloxy) -quinazoline,
2- (4′-dimethylaminophenyl) -4- (4 ″ -methoxyphenyloxy) -quinazoline,
2- (4'-dimethylaminophenyl) -4- (phenylmethylamino) -quinazoline,
2- (4'-dimethylaminophenyl) -4-morpholino-quinazoline,
2- (1'-ethyl-2 ', 2', 4'-trimethyl-tetrahydroquinolin-6'-yl) -4-phenoxy-quinazoline,
2- (1'-ethyl-2 ', 2', 4'-trimethyl-tetrahydroquinolin-6'-yl) -4-methoxy-quinazoline,
2- (1 ′, 2 ′, 2 ′, 4′-tetramethylhydroquinolin-6′-yl) -4-phenoxy-quinazoline,
2- (1'-ethyl-2'-methylhydroquinolin-6'-yl) -4-phenoxy-quinazoline,
2- (1 ′, 3′-dimethylindoline-5′-yl) -4-phenoxy-quinazoline,
2- (3 ′, 4′-dimethylbenzomorpholin-7′-yl) -4-phenoxy-quinazoline,
2- (4′-diethylaminophenyl) -4- (2 ″ -phenoxyethyloxy) -quinazoline,
2- (4'-diethylaminophenyl) -4- (2 "-phenylethylaminoethyloxy) -quinazoline,
2- (4'-dimethylaminophenyl) -4- (2 "-morpholinoethyloxy) -quinazoline,
2- (4'-dibenzylaminophenyl) -4- (2 "-phenoxyethyloxy) -quinazoline,
2- (4'-diethylaminophenyl) -4- (2 "-phenoxyethylthio) -quinazoline,
2- (4′-diethylaminophenyl) -4- [2 ″-(1-naphthoxy) ethyloxy] -quinazoline,
2- (3 ′, 4′-dimethylbenzomorpholin-7′-yl)-(2 ″ -phenoxyethyloxy) -quinazoline and the like.

As the bisquinazoline-based 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.

Examples of the magenta component (a) include benzofluorane compounds and indolylphthalide compounds.
As the benzofluorane compound,
6-dimethylamino-1,2-benzofluorane,
6-diethylamino-1,2-benzofluorane,
6-di-n-propylamino-1,2-benzofluorane,
6-di-n-butylamino-1,2-benzofluorane,
6-di-n-hexylamino-1,2-benzofluorane,
6-N-isobutyl-N-ethylamino-1,2-benzofluorane,
6-N-isoamyl-N-ethylamino-1,2-benzofluorane,
6-Nn-hexyl-N-ethylamino-1,2-benzofluorane,
6-dimethylamino-3,4-benzofluorane,
6-diethylamino-3,4-benzofluorane,
6-di-n-propylamino-3,4-benzofluorane,
6-di-n-butylamino-3,4-benzofluorane,
6-di-n-hexylamino-3,4-benzofluorane,
6-N-isobutyl-N-ethylamino-3,4-benzofluorane,
6-N-isoamyl-N-ethylamino-3,4-benzofluorane,
And 6-Nn-hexyl-N-ethylamino-3,4-benzofluorane.

As the indolylphthalide compound,
3,3-bis (1-ethyl-2-methylindol-3-yl) phthalide,
3,3-bis (1-propyl-2-methylindol-3-yl) phthalide,
3,3-bis (1-n-butyl-2-methylindol-3-yl) phthalide,
3,3-bis (1-isobutyl-2-methylindol-3-yl) phthalide,
3,3-bis (1-n-pentyl-2-methylindol-3-yl) phthalide,
3,3-bis (1-n-hexyl-2-methylindol-3-yl) phthalide,
3,3-bis (1-n-octyl-2-methylindol-3-yl) phthalide,
3,3-bis (1-ethyl-2-ethylindol-3-yl) phthalide,
3,3-bis (1-propyl-2-ethylindol-3-yl) phthalide,
3,3-bis (1-n-butyl-2-ethylindol-3-yl) phthalide,
3,3-bis (1-isobutyl-2-ethylindol-3-yl) phthalide,
3,3-bis (1-n-pentyl-2-ethylindol-3-yl) phthalide,
3,3-bis (1-n-hexyl-2-ethylindol-3-yl) phthalide,
3,3-bis (1-n-octyl-2-ethylindol-3-yl) phthalide,
3- (1-n-butyl-2-methylindole-3-yl) -3- (1-ethyl-2-methylindole) phthalide,
3- (1-n-octyl-2-methylindol-3-yl) -3- (1-n-butyl-2-methylindole) phthalide and the like can be mentioned.

Examples of the cyan (a) component include indolylphenyl phthalide compounds and indolylphenyl azaphthalide compounds.
As the indolylphenylphthalide compound,
3- (4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide,
3- (4-di-n-butylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide,
3- (4-N-phenyl-N-ethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide,
3- (4-diethylaminophenyl) -3- (1-n-butyl-2-methylindol-3-yl) phthalide,
3- (4-di-n-butylaminophenyl) -3- (1-n-butyl-2-methylindol-3-yl) phthalide,
3- (4-N-phenyl-N-ethylaminophenyl) -3- (1-n-butyl-2-methylindol-3-yl) phthalide,
1-methyl-2,3,4-trishydroquinolin-6-yl-3- (1-ethyl-2-methylindol-3-yl) phthalide,
Examples include 1-methyl-2,3,4-trishydroquinolin-6-yl-3- (1-n-butyl-2-methylindol-3-yl) phthalide.

As the indolylphenyl azaphthalide compound,
3- (4-diethylamino-2-methylphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide,
3- (4-diethylamino-2-ethylphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide,
3- (4-di-n-butylamino-2-methylphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide,
3- (4-di-n-butylamino-2-ethylphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide,
3- (4-diethylamino-2-methylphenyl) -3- (1-n-butyl-2-methylindol-3-yl) -4-azaphthalide,
3- (4-diethylamino-2-ethylphenyl) -3- (1-n-butyl-2-methylindol-3-yl) -4-azaphthalide,
3- (4-di-n-butylamino-2-methylphenyl) -3- (1-n-butyl-2-methylindol-3-yl) -4-azaphthalide,
3- (4-di-n-butylamino-2-ethylphenyl) -3- (1-n-butyl-2-methylindol-3-yl) -4-azaphthalide,
3- (4-diethylamino-2-methylphenyl) -3- (1-ethyl-2-methylindol-3-yl) -7-azaphthalide,
3- (4-diethylamino-2-ethylphenyl) -3- (1-ethyl-2-methylindol-3-yl) -7-azaphthalide,
3- (4-di-n-butylamino-2-methylphenyl) -3- (1-ethyl-2-methylindol-3-yl) -7-azaphthalide,
3- (4-di-n-butylamino-2-ethylphenyl) -3- (1-ethyl-2-methylindol-3-yl) -7-azaphthalide,
3- (4-diethylamino-2-methylphenyl) -3- (1-n-butyl-2-methylindol-3-yl) -7-azaphthalide,
3- (4-diethylamino-2-ethylphenyl) -3- (1-n-butyl-2-methylindol-3-yl) -7-azaphthalide,
3- (4-di-n-butylamino-2-methylphenyl) -3- (1-n-butyl-2-methylindol-3-yl) -7-azaphthalide,
3- (4-di-n-butylamino-2-ethylphenyl) -3- (1-n-butyl-2-methylindol-3-yl) -7-azaphthalide,
3- (4-N-phenyl-N-ethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide,
3- (4-N-phenyl-N-ethylamino-2-n-butoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide,
3- (4-Nn-butyl-phenyl-N-ethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide,
3- (4-Nn-butyl-phenyl-N-ethylamino-2-n-butoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide,
3- (4-N-phenyl-N-ethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-phenylindol-3-yl) -4-azaphthalide,
3- (4-N-phenyl-N-ethylamino-2-n-butoxyphenyl) -3- (1-ethyl-2-phenylindol-3-yl) -4-azaphthalide,
3- (4-Nn-butyl-phenyl-N-ethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-phenylindol-3-yl) -4-azaphthalide,
3- (4-Nn-butyl-phenyl-N-ethylamino-2-n-butoxyphenyl) -3- (1-ethyl-2-phenylindol-3-yl) -4-azaphthalide,
3- (4-diethylamino-2-methylphenyl) -3- (1-ethyl-2-phenylindol-3-yl) -4-azaphthalide,
3- (4-diethylamino-2-ethylphenyl) -3- (1-ethyl-2-phenylindol-3-yl) -4-azaphthalide,
3- (4-di-n-butylamino-2-methylphenyl) -3- (1-ethyl-2-phenylindol-3-yl) -4-azaphthalide,
3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-phenylindol-3-yl) -4-azaphthalide,
3- (4-N-phenyl-N-ethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -7-azaphthalide,
3- (4-N-phenyl-N-ethylamino-2-n-butoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -7-azaphthalide,
3- (4-Nn-butyl-phenyl-N-ethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -7-azaphthalide,
3- (4-Nn-butyl-phenyl-N-ethylamino-2-n-butoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -7-azaphthalide,
3- (4-N-phenyl-N-ethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-phenylindol-3-yl) -7-azaphthalide,
3- (4-N-phenyl-N-ethylamino-2-n-butoxyphenyl) -3- (1-ethyl-2-phenylindol-3-yl) -7-azaphthalide,
3- (4-Nn-butyl-phenyl-N-ethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-phenylindol-3-yl) -7-azaphthalide,
3- (4-Nn-butyl-phenyl-N-ethylamino-2-n-butoxyphenyl) -3- (1-ethyl-2-phenylindol-3-yl) -7-azaphthalide,
3- (4-diethylamino-2-methylphenyl) -3- (1-ethyl-2-phenylindol-3-yl) -7-azaphthalide,
3- (4-diethylamino-2-ethylphenyl) -3- (1-ethyl-2-phenylindol-3-yl) -7-azaphthalide,
3- (4-di-n-butylamino-2-methylphenyl) -3- (1-ethyl-2-phenylindol-3-yl) -7-azaphthalide,
And 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-phenylindol-3-yl) -7-azaphthalide.

If necessary, a reversible thermochromic microcapsule pigment encapsulating a reversible thermochromic composition that develops a black color can be used in combination.
Examples of the black (I) component include fluoran compounds,
2-anilino-3-methyl-6-dimethylamino-fluorane,
2-anilino-3-methyl-6-diethylamino-fluorane,
2-anilino-3-methyl-6-di-n-butylamino-fluorane,
2-anilino-3-methyl-6-N-ethyl-N-propylamino-fluorane,
2-anilino-3-methyl-6-N-ethyl-N-isobutylamino-fluorane,
2-anilino-3-methyl-6-N-ethyl-N-isoamylamino-fluorane,
2-anilino-3-methyl-6-N-ethyl-N-isoamylamino-fluorane,
2-anilino-3-methyl-6-N-ethyl-N-cyclohexylamino-fluorane,
2-anilino-3-methyl-6-N-ethyl-N-4'-methylphenylamino-fluorane,
2-anilino-3-methyl-6-N-ethyl-N-tetrahydrofurfurylamino-fluorane,
2-2'-chloroanilino-6-diethylamino-fluorane,
2-2'-chloroanilino-6-di-n-butylamino-fluorane,
2-2'-chloroanilino-6-N-ethyl-N-isobutylamino-fluorane,
2-2'-chloroanilino-6-N-ethyl-N-isoamylamino-fluorane,
2-2'-chloroanilino-6-N-ethyl-N-cyclohexylamino-fluorane,
2-2'-chloroanilino-6-N-ethyl-N-4'-methylphenylamino-fluorane,
2-2'-chloroanilino-6-N-ethyl-N-tetrahydrofurfurylamino-fluorane,
2-2 ', 4'-dimethylanilino-3-methyl-6-diethylamino-fluorane,
2-2 ', 4'-dimethylanilino-3-methyl-6-di-n-butylamino-fluorane,
2-2 ', 4'-dimethylanilino-3-methyl-6-N-ethyl-N-isobutylamino-fluorane,
2-2 ', 4'-dimethylanilino-3-methyl-6-N-ethyl-N-isoamylamino-fluorane,
2-2 ', 4'-dimethylanilino-3-methyl-6-N-ethyl-N-cyclohexylamino-fluorane,
2-2 ', 4'-dimethylanilino-3-methyl-6-N-ethyl-N-4'-methylphenylamino-fluorane,
2-2 ', 4'-dimethylanilino-3-methyl-6-N-ethyl-N-tetrahydrofurfurylamino-fluorane,
2-4'-methylanilino-3-methyl-6-diethylamino-fluorane,
2-4'-methylanilino-3-methyl-6-di-n-butylamino-fluorane,
2-4'-methylanilino-3-methyl-6-N-ethyl-N-isobutylamino-fluorane,
2-4'-methylanilino-3-methyl-6-N-ethyl-N-isoamylamino-fluorane,
2-4'-methylanilino-3-methyl-6-N-ethyl-N-cyclohexylamino-fluorane;
2-4'-methylanilino-3-methyl-6-N-ethyl-N-4'-methylphenylamino-fluorane,
2-4'-methylanilino-3-methyl-6-N-ethyl-N-tetrahydrofurfurylamino-fluorane,
2-4'-n-butylanilino-3-methyl-6-diethylamino-fluorane,
2-4'-n-butylanilino-3-methyl-6-N-ethyl-N-isobutylamino-fluorane,
2-4'-n-butylanilino-3-methyl-6-N-ethyl-N-isoamylamino-fluorane,
2-4'-n-butylanilino-3-methyl-6-N-ethyl-N-cyclohexylamino-fluorane,
2-3'-trifluoromethylanilino-6-diethylamino-fluorane,
2-3'-trifluoromethylanilino-6-di-n-butylamino-fluorane,
2-3′-trifluoromethylanilino-6-N-ethyl-N-isobutylamino-fluorane,
2-3'-trifluoromethylanilino-6-N-ethyl-N-isoamylamino-fluorane and the like.

As the electron-accepting compound of the component (b), a compound group having active protons, a pseudo-acidic compound group (a compound group that is not an acid but acts as an acid in the composition to cause the component (I) to develop color), There is a group of compounds having electron vacancies.
Examples of compounds having active protons include monophenols to polyphenols as compounds having phenolic hydroxyl groups, and alkyl groups, aryl groups, acyl groups, alkoxycarbonyl groups, carboxy groups and esters thereof as substituents. Alternatively, those having an amide group, a halogen group, etc., and bis-type and tris-type phenols, phenol-aldehyde condensation resins and the like can be mentioned. Moreover, the metal salt of the compound which has the said phenolic hydroxyl group may be sufficient.

Specific examples are given below.
Phenol, o-cresol, tertiary butylcatechol, nonylphenol, n-octylphenol, n-dodecylphenol, n-stearylphenol, p-chlorophenol, p-bromophenol, o-phenylphenol, n-butyl p-hydroxybenzoate N-octyl p-hydroxybenzoate, resorcin, dodecyl gallate, 2,2-bis (4-hydroxyphenyl) propane, 4,4-dihydroxydiphenylsulfone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) sulfide, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4 -Hydroxyphenyl) -3-methylbu 1,1-bis (4-hydroxyphenyl) -2-methylpropane, 1,1-bis (4-hydroxyphenyl) n-hexane, 1,1-bis (4-hydroxyphenyl) n-heptane, , 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-ethylhexane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) ethyl Propionate, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,2 Bis (4-hydroxyphenyl) n- heptane, there is 2,2-bis (4-hydroxyphenyl) n- nonane.
The compound having a phenolic hydroxyl group can develop the most effective thermochromic property, but aromatic carboxylic acids and aliphatic carboxylic acids having 2 to 5 carbon atoms, carboxylic acid metal salts, acidic phosphate esters and their It may be a compound selected from metal salts, 1,2,3-triazole and derivatives thereof.

The (c) component of the reaction medium that causes the electron transfer reaction by the (a) and (b) components to occur reversibly in a specific temperature range includes alcohols, esters, ketones, ethers, acid amides, and the like. Can be mentioned.
Among the components (c), those having a low molecular weight evaporate out of the capsule when subjected to a high heat treatment. Therefore, a compound having 10 or more carbon atoms is preferably used in order to stably hold the component in the capsule.
As the alcohols, aliphatic monovalent saturated alcohols having 10 or more carbon atoms are effective. Specifically, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl Alcohol, heptadecyl alcohol, octadecyl alcohol, eicosyl alcohol, docosyl alcohol, etc. are mentioned.
As the esters, esters having 10 or more carbon atoms are effective, and any combination of a monovalent carboxylic acid having an aliphatic and alicyclic or aromatic ring and a monohydric alcohol having an aliphatic and alicyclic or aromatic ring. Esters, aliphatic and alicyclic rings obtained from any combination of esters, aliphatic and alicyclic or aromatic polyvalent carboxylic acids obtained from the above and monohydric alcohols having aliphatic and alicyclic or aromatic rings Or esters obtained from any combination of monovalent carboxylic acid having an aromatic ring and aliphatic and alicyclic or polyhydric alcohol having an aromatic ring, specifically, ethyl caprylate, octyl caprylate, capryl Stearyl acid, myristyl caprate, docosyl caprate, 2-ethylhexyl laurate, n-decyl laurate, myris 3-methylbutyl acid, cetyl myristate, isopropyl palmitate, neopentyl palmitate, nonyl palmitate, cyclohexyl palmitate, n-butyl stearate, 2-methylbutyl stearate, 3,5,5-trimethylhexyl stearate, stearin N-undecyl acid, pentadecyl stearate, stearyl stearate, cyclohexylmethyl stearate, isopropyl behenate, hexyl behenate, lauryl behenate, behenyl behenate, cetyl benzoate, stearyl p-tert-butylbenzoate, dimyristyl phthalate , Distearyl phthalate, dimyristyl oxalate, dicetyl oxalate, dicetyl malonate, dilauryl succinate, dilauryl glutarate, diundecyl adipate, azelaic acid Lauryl, di- (n-nonyl) sebacate, dineopentyl 1,18-octadecylmethylenedicarboxylate, ethylene glycol dimyristate, propylene glycol dilaurate, propylene glycol distearate, hexylene glycol dipalmitate, 1,5-pentane Diol distearate, 1,2,6-hexanetriol trimyristate, 1,4-cyclohexanediol didecyl, 1,4-cyclohexanedimethanol dimyristate, xylene glycol dicaprate, xylene glycol distearate, etc. Can be mentioned.
In addition, esters of saturated fatty acids and branched fatty alcohols, unsaturated fatty acids or branched or substituted saturated fatty acids and esters of fatty alcohols having 16 or more carbon atoms, cetyl butyrate, stearyl butyrate and Ester compounds selected from behenyl butyrate are also effective.
Specifically, 2-ethylhexyl butyrate, 2-ethylhexyl behenate, 2-ethylhexyl myristate, 2-ethylhexyl caprate, 3,5,5-trimethylhexyl laurate, 3,5,5-trimethylhexyl palmitate, 3,5,5-trimethylhexyl stearate, 2-methylbutyl caproate, 2-methylbutyl caprylate, 2-methylbutyl caprate, 1-ethylpropyl palmitate, 1-ethylpropyl stearate, 1-ethylpropyl behenate, 1-ethylhexyl laurate, 1-ethylhexyl myristate, 1-ethylhexyl palmitate, 2-methylpentyl caproate, 2-methylpentyl caprylate, 2-methylpentyl caprate, 2-methylpentyl laurate, 2-stearate Mechi 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, stearate 7-Jime Luoctyl, 3,7-dimethyloctyl behenate, stearyl oleate, behenyl oleate, stearyl linoleate, behenyl linoleate, 3,7-dimethyloctyl erucate, stearyl erucate, isostearyl erucate, cetyl isostearate, isostearate Examples include stearyl acid, 2-methylpentyl 12-hydroxystearate, 2-ethylhexyl 18-bromostearate, isostearyl 2-ketomyristate, 2-ethylhexyl 2-fluoromyristate, cetyl butyrate, stearyl butyrate, and behenyl butyrate. It is done.

  In addition, as the component (c) for obtaining a reversible thermochromic composition having color memory, a carboxylic acid ester compound exhibiting a ΔT value (melting point-cloud point) of 5 ° C. or more and less than 50 ° C., for example, in a molecule A carboxylic acid ester having a substituted aromatic ring, an ester of a carboxylic acid having an unsubstituted aromatic ring and an aliphatic alcohol having 10 or more carbon atoms, a carboxylic acid ester having a cyclohexyl group in the molecule, a fatty acid having 6 or more carbon atoms, and Unsubstituted aromatic alcohol or ester of phenol, fatty acid having 8 or more carbon atoms and branched aliphatic alcohol or ester, dicarboxylic acid and ester of aromatic alcohol or branched aliphatic alcohol, dibenzyl cinnamate, heptyl stearate, didecyl adipate , Dilauryl adipate, dimyristyl adipate, dicetyl adipate, distearate adipate , Trilaurin, trimyristin, tristearin, Dimyristate, distearate and the like are used.

Also, fatty acid ester compounds obtained from an odd aliphatic monohydric alcohol having 9 or more carbon atoms and an aliphatic carboxylic acid having an even number of carbon atoms, n-pentyl alcohol or n-heptyl alcohol and an even fat having 10 to 16 carbon atoms. A fatty acid ester compound having a total carbon number of 17 to 23 obtained from a group carboxylic acid is also effective.
Specifically, n-pentadecyl acetate, n-tridecyl butyrate, n-pentadecyl butyrate, n-undecyl caproate, n-tridecyl caproate, n-pentadecyl caproate, n-nonyl caprylate, n-undecyl caprylate, N-tridecyl caprylate, n-pentadecyl caprylate, n-heptyl caprate, n-nonyl caprate, n-undecyl caprate, n-tridecyl caprate, n-pentadecyl caprate, n-pentyl laurate, lauric acid n-heptyl, n-nonyl laurate, n-undecyl laurate, n-tridecyl laurate, n-pentadecyl laurate, n-pentyl myristate, n-heptyl myristate, n-nonyl myristate, n-myristate Undecyl, n-tridecyl myristate, N-pentadecyl ristinate, 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-undecyl eicosanoate, n-tridecyl eicosanoate, n-pentadecyl eicosanoate, n-nonyl behenate, n-behenate Examples include undecyl, n-tridecyl behenate, and n-pentadecyl behenate.

As the ketones, aliphatic ketones having a total carbon number of 10 or more are effective, and 2-decanone, 3-decanone, 4-decanone, 2-undecanone, 3-undecanone, 4-undecanone, and 5-undecanone. 2-dodecanone, 3-dodecanone, 4-dodecanone, 5-dodecanone, 2-tridecanone, 3-tridecanone, 2-tetradecanone, 2-pentadecanone, 8-pentadecanone, 2-hexadecanone, 3-hexadecanone, 9-heptadecanone, 2 -Pentadecanone, 2-octadecanone, 2-nonadecanone, 10-nonadecanone, 2-eicosanone, 11-eicosanone, 2-heneicosanone, 2-docosanone, laurone, stearone and the like.
Further, arylalkyl ketones having 12 to 24 carbon atoms in total, such as n-octadecanophenone, n-heptadecanophenone, n-hexadecanophenone, n-pentadecanophenone, n-tetradecano Phenone, 4-n-dodecanacetophenone, n-tridecanophenone, 4-n-undecanoacetophenone, n-laurophenone, 4-n-decanoacetophenone, n-undecanophenone, 4-n-nonylacetophenone, n -Decanophenone, 4-n-octylacetophenone, n-nonanophenone, 4-n-heptylacetophenone, n-octanophenone, 4-n-hexylacetophenone, 4-n-cyclohexylacetophenone, 4-tert-butylpropiophenone, n-heptaphenone, 4-n-pentylacetophene Emissions, cyclohexyl phenyl ketone, benzyl -n- butyl ketone, 4-n-butyl acetophenone, n- hexanophenone, 4-isobutyl acetophenone, 1-acetonaphthone, 2-acetonaphthone, may be mentioned cyclopentyl phenyl ketone.

  As ethers, aliphatic ethers having a total carbon number of 10 or more are effective, and dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, dinonyl ether, didecyl ether, diundecyl ether, didodecyl ether. , Ditridecyl ether, ditetradecyl ether, dipentadecyl ether, dihexadecyl ether, dioctadecyl ether, decane diol dimethyl ether, undecane diol dimethyl ether, dodecane diol dimethyl ether, tridecane diol dimethyl ether, decane diol diethyl ether, undecane diol diethyl ether Etc.

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

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

[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 or alkenyl group having 4 or more carbon atoms, Y ₁ and Y ₂ represent a hydrogen atom, 1 to 4 carbon atoms An alkyl group, a methoxy group, or halogen, and r and p each represent an integer of 1 to 3. ]
Among the compounds represented by the formula (1), when R ₁ is a hydrogen atom, it is preferable because a reversible thermochromic composition having a wider hysteresis width can be obtained, and R ₁ is a hydrogen atom, and , M is more preferably 0.
Of 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 alkenyl group having 8 or more carbon atoms, preferably an alkyl group having 10 to 24 carbon atoms, more preferably an alkyl group having 12 to 22 carbon atoms.
Specific examples of the compound include octanoic acid-4-benzyloxyphenylethyl, nonanoic acid-4-benzyloxyphenylethyl, decanoic acid-4-benzyloxyphenylethyl, undecanoic acid-4-benzyloxyphenylethyl, and dodecanoic acid. -4-benzyloxyphenylethyl, tridecanoic acid-4-benzyloxyphenylethyl, tetradecanoic acid-4-benzyloxyphenylethyl, pentadecanoic acid-4-benzyloxyphenylethyl, hexadecanoic acid-4-benzyloxyphenylethyl, heptadecanoic acid Examples thereof include -4-benzyloxyphenylethyl and octadecanoic acid-4-benzyloxyphenylethyl.

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

(In the formula, R represents an alkyl group or alkenyl group having 8 or more carbon atoms, m and n each represents an integer of 1 to 3, X and Y represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, carbon, respectively. (The alkoxy group of Formula 1-4 is shown, and a halogen.)
Specific examples of the compound include 1,1-diphenylmethyl octanoate, 1,1-diphenylmethyl nonanoate, 1,1-diphenylmethyl decanoate, 1,1-diphenylmethyl undecanoate, 1,1-dodecanoic acid 1,1- Diphenylmethyl, tridecanoic acid 1,1-diphenylmethyl, tetradecanoic acid 1,1-diphenylmethyl, pentadecanoic acid 1,1-diphenylmethyl, hexadecanoic acid 1,1-diphenylmethyl, heptadecanoic acid 1,1-diphenylmethyl, octadecanoic acid An example is 1,1-diphenylmethyl.

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

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

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

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

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

  Further, (b) a specific alkoxyphenol compound having a linear or side chain alkyl group having 3 to 18 carbon atoms as an electron-accepting compound (Japanese Patent Laid-Open No. 11-129623), a specific hydroxybenzoic acid ester (Japanese Patent Laid-Open No. 2001) No. -105732), reversible thermochromic microcapsule pigments containing a heat-colorable reversible thermochromic composition using gallic acid ester (Japanese Patent Laid-Open No. 2003-253149) or the like can also be applied (FIG. 3).

  The blending ratio of the components (A), (B), and (C) depends on the concentration, the color change temperature, and the type of each component. With respect to Component 1, (b) Component 0.1-50, preferably 0.5-20, (C) Component 1-800, preferably 5-200 (all the proportions are in parts by mass). is there). Moreover, you may use each component in mixture of 2 or more types, respectively.

The reversible thermochromic composition is used as a reversible thermochromic microcapsule pigment encapsulated in microcapsules. This is because the reversible thermochromic composition can be kept in the same composition under the various use conditions and can exhibit the same effects.
Methods for microencapsulating the reversible thermochromic composition include interfacial polymerization, interfacial polycondensation, in situ polymerization, in-liquid curing coating, phase separation from aqueous solution, and phase separation from organic solvent. There are a melt dispersion cooling method, an air suspension coating method, a spray drying method, and the like, which are appropriately selected according to use. Further, a secondary resin film may be provided on the surface of the microcapsule according to the purpose to impart durability, or the surface characteristics may be modified for practical use.
The microcapsule pigment may have a circular cross section or a non-circular cross section.
Here, the mass ratio of the reversible thermochromic composition to the microcapsule wall membrane satisfies the range of 7: 1 to 1: 1, preferably 6: 1 to 1: 1.
When the ratio of the reversible thermochromic composition to the wall film is larger than the above range, the thickness of the wall film becomes too thin, and the resistance to pressure and heat tends to decrease, and the ratio of the wall film to the reversible thermochromic composition When the value is larger than the above range, color density and sharpness during color development tend to be reduced.

The microcapsule pigment has an average particle diameter of 0.1 to 10 μm, preferably 0.1 to 8 μm, more preferably 0.5 to 6 μm, satisfying practicality.
When the average particle diameter exceeds 10 μm, the microcapsules may lack dispersion stability, and when the average particle diameter is less than 0.1 μm, it is difficult to exhibit high density color development.
The particle size is measured using a laser diffraction / scattering particle size distribution measuring device (manufactured by Horiba, Ltd .; LA-300), and the average particle size (median diameter) is calculated on the basis of the numerical value. To do.
Further, the microcapsule pigment has particles exceeding 15 μm in less than 20% by volume in the total microcapsule pigment, preferably less than 15% by volume, more preferably less than 10% by volume. Particles exceeding 15 μm exceed 20% by volume. Since the ratio of the presence of microcapsule pigments with poor transparency increases, the color due to the lower colorant in the area where the colorant overlaps tends to be shielded by the upper capsule pigment, giving the desired hue. It becomes difficult.

The reversible thermochromic microcapsule pigments that develop colors of yellow, magenta, and cyan, respectively, are used as coloring materials and are contained in the coloring material.
Examples of the colorant include gravure printing ink, offset printing ink, process printing ink, ink jet ink, or toner dispersed in a vehicle containing additives as necessary. Paper, synthetic paper, yarn, fabric, A reversible thermochromic print can be obtained by forming a reversible thermochromic natural color image on a support such as flocked or brushed fabric, non-woven fabric, synthetic leather, leather, plastic, glass, ceramics, wood, stone, metal, etc. .
The reversible thermochromic natural color image of the reversible thermochromic print formed using each of the colorants reversibly changes from a state in which no image is formed to a natural color image due to temperature change.
In addition, on the surface of the printed matter, one or two or more kinds selected from an ultraviolet absorber, an antioxidant, a singlet oxygen quencher, a superoxide anion quencher, an ozone quencher, a visible light absorber, and an infrared absorber. It is also possible to provide a light stabilizer layer in which an appropriate amount of a drug is dispersed in a binder resin.
By using a puzzle piece as the support, it is possible to obtain a puzzle that reversibly changes its color from a state in which no image is formed due to a temperature change to a natural color image, thereby improving the commercial value.
The puzzle pieces are puzzle pieces having the same shape or different shapes, and may be a three-dimensional fitting puzzle having irregularities on the puzzle piece in addition to the two-dimensional fitting puzzle.
Moreover, a jigsaw puzzle can also be obtained by using a jigsaw puzzle piece as the puzzle piece.

Next, each of yellow, magenta, and cyan non-thermochromic coloring materials, (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, (c) the above-mentioned (a) and (b) Includes a reversible thermochromic composition that changes from a complementary color of the non-thermochromic colorant of yellow, magenta, and cyan to a colorless color, which is a reaction medium that reversibly causes an electron transfer reaction in a specific temperature range. A coloring material containing each of the reversible thermochromic microcapsule pigments will be described.
Each colorant includes a cyan non-thermochromic colorant and a reversible thermothermochromic microcapsule pigment that reversibly changes from orange to colorless according to temperature change, magenta non-thermochromic colorant and green A colorant comprising a reversible thermothermochromic microcapsule pigment that reversibly changes from colorless to colorless, a non-thermochromic colorant of yellow, and a reversible thermothermochromic microcapsule pigment that reversibly changes from purple to colorless Including coloring material.
The non-thermochromic color material may be encapsulated in the microcapsule pigment together with the reversible thermochromic composition or may not be encapsulated in the microcapsule pigment.
As the non-thermochromic color material, a general pigment or dye is used.
Both the non-thermochromic colorant and the reversible thermochromic microcapsule pigment are used as a colorant and contained in the colorant.
Examples of the colorant include gravure printing ink, offset printing ink, process printing ink, inkjet ink, or toner dispersed in a vehicle containing additives as necessary, and reversible on the same support as described above. A reversible thermochromic print can be obtained by forming a thermochromic natural color image.
The reversible thermochromic natural color image of the reversible thermochromic print formed using each of the colorants reversibly changes from a black and white image to a natural color image due to temperature change.
In addition, by using a puzzle piece as the support, a puzzle that reversibly changes color from a black and white image to a natural color image due to a temperature change can be obtained, and the merchantability can be improved.
The puzzle pieces are puzzle pieces having the same shape or different shapes, and may be a three-dimensional fitting puzzle having irregularities on the puzzle piece in addition to the two-dimensional fitting puzzle.
Moreover, a jigsaw puzzle can also be obtained by using a jigsaw puzzle piece as the puzzle piece.

Among the color materials having reversible thermochromic properties exhibiting the yellow, magenta, and cyan hues, in a system in which the color change temperature of at least one color is configured differently from the other colors, a unique aspect is visually recognized according to the temperature change. be able to.
Further, the reversible thermochromic printed matter can be written using a writing instrument containing a writing instrument ink using a reversible thermochromic microcapsule pigment as a color material, or a reversible thermochromic microcapsule pigment can be used as a color material. It is also possible to print using the stamp ink.

Example 1
Preparation of reversible thermochromic microcapsule pigment (a): Heat consisting of 1.5 parts of 6-bismethoxyfluorane, 6 parts of 2,2-bis (4'-hydroxyphenyl) hexafluoropropane and 50 parts of cyclohexylmethyl stearate The reversible thermochromic composition was encapsulated in microcapsules of an epoxy resin film obtained by an epoxy prepolymer / amine compound interfacial polymerization method to obtain a reversible thermochromic microcapsule pigment.
The reversible thermal discoloration microcapsule pigment has an average particle size of 8.5 .mu.m, a capsule pigment exceeding 15μm is 7% by volume of the total, yellow at 13 ° C. or less, the pigment that changes color to colorless at 41 ° C. or higher (t ₁ : 13 ° C., t ₂ : 16 ° C., t ₃ : 38 ° C., t ₄ : 41 ° C.).

Preparation of reversible thermochromic microcapsule pigment (b) 3-diethylamino-5,6-benzofluorane 1.5 parts, 2,2-bis (4'-hydroxyphenyl) hexafluoropropane 10 parts, cyclohexylmethyl stearate The reversible thermochromic composition comprising 50 parts of heat decoloring type was encapsulated in microcapsules of an epoxy resin film obtained by an epoxy prepolymer / amine compound interfacial polymerization method to obtain a reversible thermochromic microcapsule pigment.
The reversible thermochromic microcapsule pigment has an average particle size of 9.5 μm, and the capsule pigment exceeding 15 μm is 15% by volume of the total, and is a pigment that changes its color to magenta at 13 ° C. or lower and colorless at 41 ° C. or higher (t ₁ : 13 ° C., t ₂ : 16 ° C., t ₃ : 38 ° C., t ₄ : 41 ° C.).

Preparation of reversible thermochromic microcapsule pigment (c) 3- (4'-diethylaminophenyl) -3- (1'-ethyl-2'-methylindol-3'-yl) phthalide 1.5 parts, 2,2 -Epoxy resin obtained by interfacial polymerization of epoxy prepolymer / amine compound with a heat decolorable reversible thermochromic composition comprising 10 parts of bis (4'-hydroxyphenyl) hexafluoropropane and 50 parts of cyclohexylmethyl stearate The film was encapsulated in a microcapsule to obtain a reversible thermochromic microcapsule pigment.
The reversible thermochromic microcapsule pigment has an average particle diameter of 9.5 μm, and capsule pigments exceeding 15 μm are 15% by volume of the total, and are pigments that change color to cyan at 13 ° C. or lower and colorless at 41 ° C. or higher (t ₁ : 13 ° C., t ₂ : 16 ° C., t ₃ : 38 ° C., t ₄ : 41 ° C.).

Preparation of Colorant A 10 parts of the microcapsule pigment (b), 10 parts of the microcapsule pigment (c), 3 parts of the yellow pigment, and 77 parts of alkyd resin-based gel varnish were uniformly stirred to give Colorant A (reversible thermochromic property). Offset ink) was obtained.

Preparation of Colorant B 10 parts of the microcapsule pigment (a), 10 parts of the microcapsule pigment (c), 3 parts of magenta pigment, and 77 parts of alkyd resin-based gel varnish are uniformly stirred to give Colorant B (reversible thermochromic property). Offset ink) was obtained.

Preparation of Coloring Material C 10 parts of the microcapsule pigment (a), 10 parts of the microcapsule pigment (b), 3 parts of the cyan pigment, and 77 parts of alkyd resin gel varnish are uniformly stirred to form the coloring material C (reversible thermochromic property). Offset ink) was obtained.

Using the colorants A, B, and C, reversible thermal discoloration by offset printing on white art paper with a thickness of 40 μm using an offset plate with 50 lines / inch of separation lines in which flower pictures are photo-separated into three colors. A printed material was obtained.
In the printed material, a reversible thermochromic image of a black and white flower was visually observed at 13 ° C. or lower, and this state was maintained at 16 to 38 ° C. Next, when the temperature was raised to 41 ° C. or higher, the reversible thermochromic image of color black changed to a reversible thermochromic natural color image that faithfully reproduced the natural color, and this state was maintained at 16 to 38 ° C. When the printed material was cooled again to 13 ° C. or less, a black and white image was obtained, and this change in appearance could be reproduced repeatedly.

Example 2
Preparation of reversible thermochromic microcapsule pigment (a) comprising 1.5 parts of 6-bismethoxyfluorane, 6 parts of 2,2-bis (4'-hydroxyphenyl) hexafluoropropane, and 50 parts of n-nonyl palmitate A reversible thermochromic pigment was obtained by encapsulating a heat decolorable reversible thermochromic composition in microcapsules of an epoxy resin film obtained by an epoxy prepolymer / amine compound interfacial polymerization method.
The reversible thermochromic microcapsule pigment has an average particle diameter of 1.0 μm, and capsule pigments exceeding 15 μm are 0% by volume of the total, and the pigment discolors yellow at 13 ° C. or lower and colorless at 33 ° C. or higher (t ₁ : 13 ° C., t ₂ : 18 ° C., t ₃ : 28 ° C., t ₄ : 33 ° C.).

Preparation of reversible thermochromic microcapsule pigment (b) 1.5 parts of 3-diethylamino-5,6-benzofluorane, 10 parts of 2,2-bis (4'-hydroxyphenyl) hexafluoropropane, n-palmitate A reversible thermochromic microcapsule pigment was obtained by encapsulating a heat decolorable reversible thermochromic composition comprising 50 parts of nonyl in an epoxy resin film microcapsule obtained by an epoxy prepolymer / amine compound interfacial polymerization method. .
The reversible thermochromic microcapsule pigment has an average particle diameter of 0.80 μm, and capsule pigments exceeding 15 μm are 0% by volume of the total, and pigments that change magenta at 13 ° C. or lower and colorless at 33 ° C. or higher (t ₁ : 13 ° C., t ₂ : 18 ° C., t ₃ : 28 ° C., t ₄ : 33 ° C.).

Preparation of reversible thermochromic microcapsule pigment (c) 3- (4'-diethylaminophenyl) -3- (1'-ethyl-2'-methylindol-3'-yl) phthalide 1.5 parts, 2,2 An epoxy obtained by interfacial polymerization of epoxy prepolymer / amine compound with a heat-erasable reversible thermochromic composition comprising 10 parts of bis (4'-hydroxyphenyl) hexafluoropropane and 50 parts of n-nonyl palmitate A reversible thermochromic microcapsule pigment was obtained by encapsulating in a resin film microcapsule.
The reversible thermochromic microcapsule pigment has an average particle diameter of 1.0 μm, and capsule pigments exceeding 15 μm are 0% by volume of the total, and pigments that change to cyan at 13 ° C. or lower and colorless at 33 ° C. or higher (t ₁ : 13 ° C., t ₂ : 18 ° C., t ₃ : 28 ° C., t ₄ : 33 ° C.).

Preparation of Colorant A 10 parts of the microcapsule pigment (b), 10 parts of the microcapsule pigment (c), 3 parts of a yellow pigment, styrene acrylic copolymer resin emulsion (trade name: NeoCryl A-1052, solid content 49%, 5 parts of Zeneca Co., Ltd.), 10 parts of ethylene glycol, 0.2 part of the antifungal agent, 0.1 part of the antifoaming agent, and 61.7 parts of water are uniformly mixed, and coloring material A (reversible thermochromic inkjet) Ink) was prepared.

Production of Colorant B 10 parts of the above microcapsule pigment (a), 10 parts of microcapsule pigment (c), 3 parts of magenta pigment, styrene acrylic copolymer resin emulsion (trade name: NeoCryl A-1052, solid content 49%, 5 parts of Zeneca Co., Ltd.), 10 parts of ethylene glycol, 0.2 part of antifungal agent, 0.1 part of antifoaming agent, and 61.7 parts of water are uniformly mixed, and coloring material B (reversible thermochromic inkjet) Ink) was prepared.

Preparation of Colorant C 10 parts of the above microcapsule pigment (a), 10 parts of microcapsule pigment (b), 3 parts of cyan pigment, styrene acrylic copolymer resin emulsion (trade name: NeoCryl A-1052, solid content 49%, 5 parts of Zeneca Co., Ltd.), 10 parts of ethylene glycol, 0.2 part of the antifungal agent, 0.1 part of the antifoaming agent, and 61.7 parts of water are uniformly mixed, and the coloring material C (reversible thermochromic inkjet) Ink) was prepared.

The coloring material was accommodated in an ink cartridge.
The ink cartridge was set in an ink jet recording apparatus, and a photographic image of an automobile was printed on recording paper to obtain a reversible thermochromic printed matter.
When the printed material was 13 ° C. or lower, a reversible thermochromic image of a black and white automobile was visually recognized, and this state was maintained at 18 to 28 ° C. Next, when heated to 33 ° C. or higher, the reversible thermochromic image of color black changed to a reversible thermochromic image faithfully reproducing the natural color, and this state was maintained at 18 to 28 ° C. When the printed material was cooled again to 13 ° C. or less, a black and white image was obtained, and this change in appearance could be reproduced repeatedly.

Example 3
Preparation of reversible thermochromic microcapsule pigment (a) 1.5 parts of 6-bismethoxyfluorane, 6 parts of 2,2-bis (4'-hydroxyphenyl) hexafluoropropane, 4-benzyloxyphenylethyl caprate 50 The reversible thermochromic composition of the heat decoloring type comprising a part was encapsulated in microcapsules of an epoxy resin film obtained by an epoxy prepolymer / amine compound interfacial polymerization method to obtain a reversible thermochromic microcapsule pigment.
The reversible thermochromic microcapsule pigment has an average particle diameter of 2.0 μm, and capsule pigments exceeding 15 μm are 0% by volume of the total, and are pigments that change color to yellow at −20 ° C. or lower and colorless at 57 ° C. or higher (t _{1: -20 ℃, t 2:} -9 ℃, t 3: 40 ℃, t 4: was 57 ° C.).

Preparation of reversible thermochromic microcapsule pigment (b) 3-diethylamino-5,6-benzofluorane 1.5 parts, 2,2-bis (4'-hydroxyphenyl) hexafluoropropane 10 parts, capric acid 4- A reversible thermochromic microcapsule pigment comprising 50 parts of benzyloxyphenylethyl in a heat decolorable reversible thermochromic composition encapsulated in an epoxy resin film microcapsule obtained by an epoxy prepolymer / amine compound interfacial polymerization method Got.
The reversible thermochromic microcapsule pigment has an average particle diameter of 1.8 μm, and capsule pigments exceeding 15 μm are 0% by volume of the total, and the pigment (t ₁ : −20 ° C., t ₂ : −9 ° C., t ₃ : 40 ° C., t ₄ : 57 ° C.).

Preparation of reversible thermochromic microcapsule pigment (c) 3- (4'-diethylaminophenyl) -3- (1'-ethyl-2'-methylindol-3'-yl) phthalide 1.5 parts, 2,2 -Heat-decolorable reversible thermochromic composition comprising 10 parts of bis (4'-hydroxyphenyl) hexafluoropropane and 50 parts of 4-benzyloxyphenylethyl caprate by an epoxy prepolymer / amine compound interfacial polymerization method. The resultant epoxy resin film was encapsulated in microcapsules to obtain reversible thermochromic microcapsule pigments.
The reversible thermochromic microcapsule pigment has an average particle diameter of 1.8 μm, and capsule pigments exceeding 15 μm are 0% by volume of the total, and pigments that change to cyan at −20 ° C. or lower and colorless at 57 ° C. or higher (t ₁ : −20 ° C., t ₂ : −9 ° C., t ₃ : 40 ° C., t ₄ : 57 ° C.).

Preparation of Colorant A 10 parts of the microcapsule pigment (b), 10 parts of the microcapsule pigment (c), 3 parts of a yellow pigment, 74 parts of a polyester resin having a softening point of 70 ° C. as a binder resin, and a low molecular weight as a release agent After mixing 3 parts of polyethylene, the mixture was melt-kneaded with a biaxial extruder at a kneading temperature of 90 ° C., cooled and solidified, and pulverized and classified to obtain Colorant A (reversible thermochromic toner) having a particle size of 11 μm.

Preparation of Colorant B 10 parts of the microcapsule pigment (a), 10 parts of the microcapsule pigment (c), 3 parts of magenta pigment, 74 parts of a polyester resin having a softening point of 70 ° C. as a binder resin, and a low molecular weight as a release agent After mixing 3 parts of polyethylene, the mixture was melt-kneaded by a biaxial extruder at a kneading temperature of 90 ° C., cooled and solidified, and pulverized and classified to obtain a coloring material B (reversible thermochromic toner) having a particle size of 11 μm.

Preparation of coloring material C 10 parts of the above microcapsule pigment (a), 10 parts of microcapsule pigment (b), 3 parts of cyan pigment, 74 parts of a polyester resin having a softening point of 70 ° C. as a binder resin, and a low molecular weight as a release agent After mixing 3 parts of polyethylene, the mixture was melt-kneaded with a biaxial extruder at a kneading temperature of 90 ° C., cooled and solidified, and pulverized and classified to obtain a coloring material C (reversible thermochromic toner) having a particle size of 11 μm.

The coloring material was accommodated in a cartridge.
The cartridge was set in a laser printer, and a photographic image of a building was printed on a recording sheet to obtain a reversible thermochromic printed matter.
When the printed matter was set to −20 ° C. or lower, a reversible thermochromic image of a black and white building was visually recognized, and this state was maintained at −9 to 40 ° C. Next, when the temperature was increased to 57 ° C. or higher, the reversible thermochromic image of color black changed to a reversible thermochromic natural color image that faithfully reproduced the natural color, and this state was maintained at −9 to 40 ° C. When the printed material was again cooled to −20 ° C. or lower, a black and white image was obtained, and this change in appearance could be reproduced repeatedly.

Example 4
Using the coloring materials A, B, and C obtained in Example 1 , offset printing is performed on white paper with a thickness of 4 mm using an offset plate with a separation line number of 50 lines / inch obtained by photo-decomposing the landscape into three colors. A thermochromic print was obtained.
The reversible thermochromic printed matter was cut into a plurality of puzzle pieces to obtain a reversible thermochromic puzzle.
Each of the puzzles was cut into a jigsaw puzzle having the same shape.
In the puzzle, a reversible thermochromic image of a monochrome scene was visually recognized at 13 ° C. or lower, and this state was maintained at 16 to 38 ° C. Next, when the temperature was raised to 41 ° C. or higher, the reversible thermochromic image of color black changed to a reversible thermochromic natural color image that faithfully reproduced the natural color, and this state was maintained at 16 to 38 ° C. When the printed material was cooled again to 13 ° C. or less, a black and white image was obtained, and this change in appearance could be reproduced repeatedly.

Comparative Example 1
Preparation of reversible thermochromic microcapsule pigment (a): Heat consisting of 1.5 parts of 6-bismethoxyfluorane, 6 parts of 2,2-bis (4'-hydroxyphenyl) hexafluoropropane and 50 parts of cyclohexylmethyl stearate The reversible thermochromic composition was encapsulated in microcapsules of an epoxy resin film obtained by an epoxy prepolymer / amine compound interfacial polymerization method to obtain a reversible thermochromic microcapsule pigment.
The reversible thermochromic microcapsule pigment has an average particle diameter of 11.0 μm, and capsule pigments exceeding 15 μm account for 23% by volume of the total, and the pigment discolors yellow at 13 ° C. or lower and colorless at 41 ° C. or higher (t ₁ : 13 ° C., t ₂ : 16 ° C., t ₃ : 38 ° C., t ₄ : 41 ° C.).

Preparation of reversible thermochromic microcapsule pigment (b) 3-diethylamino-5,6-benzofluorane 1.5 parts, 2,2-bis (4'-hydroxyphenyl) hexafluoropropane 10 parts, cyclohexylmethyl stearate The reversible thermochromic composition comprising 50 parts of heat decoloring type was encapsulated in microcapsules of an epoxy resin film obtained by an epoxy prepolymer / amine compound interfacial polymerization method to obtain a reversible thermochromic microcapsule pigment.
The reversible thermal discoloration microcapsule pigment has an average particle diameter of 11.0 .mu.m, capsule pigments exceeding 15μm is 23% by volume of the total, magenta at 13 ° C. or less, the pigment that changes color to colorless at 41 ° C. or higher (t ₁ : 13 ° C., t ₂ : 16 ° C., t ₃ : 38 ° C., t ₄ : 41 ° C.).

Preparation of reversible thermochromic microcapsule pigment (c) 3- (4'-diethylaminophenyl) -3- (1'-ethyl-2'-methylindol-3'-yl) phthalide 1.5 parts, 2,2 -Epoxy resin obtained by interfacial polymerization of epoxy prepolymer / amine compound with a heat decolorable reversible thermochromic composition comprising 10 parts of bis (4'-hydroxyphenyl) hexafluoropropane and 50 parts of cyclohexylmethyl stearate The film was encapsulated in a microcapsule to obtain a reversible thermochromic microcapsule pigment.
The reversible thermochromic microcapsule pigment has an average particle size of 11.0 μm, and capsule pigments exceeding 15 μm account for 23% by volume of the pigment, and the pigment (t ₁ : 13 ° C., t ₂ : 16 ° C., t ₃ : 38 ° C., t ₄ : 41 ° C.).

Preparation of Colorant A 10 parts of the microcapsule pigment (b), 10 parts of the microcapsule pigment (c), 3 parts of the yellow pigment, and 77 parts of alkyd resin-based gel varnish were uniformly stirred to give Colorant A (reversible thermochromic property). Offset ink) was obtained.

Preparation of Colorant B 10 parts of the microcapsule pigment (a), 10 parts of the microcapsule pigment (c), 3 parts of magenta pigment, and 77 parts of alkyd resin-based gel varnish are uniformly stirred to give Colorant B (reversible thermochromic property). Offset ink) was obtained.

Preparation of Coloring Material C 10 parts of the microcapsule pigment (a), 10 parts of the microcapsule pigment (b), 3 parts of the cyan pigment, and 77 parts of alkyd resin gel varnish are uniformly stirred to form the coloring material C (reversible thermochromic property). Offset ink) was obtained.

Using the colorants A, B, and C, the flower is reversibly printed on white art paper with a thickness of 40 μm using an offset plate with a resolution of 50 lines / inch. A thermochromic print was obtained.
In the printed matter, although a reversible thermochromic image of a flower is visually recognized at 41 ° C. or higher, the color is different from a natural color, and the original hue cannot be faithfully reproduced.

t ₁ Full color development temperature of microcapsule pigment encapsulating reversible thermochromic composition of heat decoloring type t ₂ Color development start temperature of microcapsule pigment encapsulating reversible thermochromic composition of heat decoloring type t ₃ Heat decoloration Decoloration start temperature of microcapsule pigment encapsulating reversible thermochromic composition of color type t ₄ Complete decolorization temperature of microcapsule pigment encapsulating reversible thermochromic composition of heat decoloring type T ₁ complete decoloring temperature T ₂ heat-coloring type of decoloring starting temperature T ₃ heating color development type reversible thermal discoloration microcapsule pigment enclosing a reversible thermochromic composition of the microcapsule pigment enclosing a reversible thermochromic composition Color development start temperature of the microcapsule pigment encapsulating the composition T ₄ Complete color development temperature of the microcapsule pigment encapsulating the reversible thermochromic composition of the ₄ heating color development type ΔH Hysteresis width

Claims (3)

On the support, each of yellow, magenta, and cyan non-thermochromic colorants, (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, (c) the above-mentioned (a), ( (B) A reversible thermochromic composition that changes from a complementary color of the non-thermochromic colorant of yellow, magenta, and cyan to a colorless color, comprising a compound that is a reaction medium that reversibly causes an electron transfer reaction in a specific temperature range. A reversible thermochromic microcapsule pigment encapsulating each of the reversible thermochromic microcapsule pigments to provide a reversible thermochromic natural color image, wherein the microcapsule pigment has an average particle size of 0.1. A reversible thermochromic print characterized in that particles in the range of ~ 10.0 μm and greater than 15 μm are less than 20% by volume in the total microcapsule pigment. The reversible thermochromic printed matter according to claim 1, wherein the support is a puzzle piece. The reversible thermochromic printed matter according to claim 2, wherein the puzzle piece is a jigsaw puzzle piece.

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