JP2016121344A - Solid writing body and solid writing body set using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance decorative effect of handwriting by useful solid writing body using a thermochromic microcapsule pigment as a coloring agent and provide a solid writing body having decorative effect and capable of adding brightness to handwriting and surely deleting handwriting without remaining brightness during heating discharging.SOLUTION: There is provided a solid writing body containing a reversible thermochromic microcapsule pigment including a temperature-sensitive color-memory composition consisting of (a) an electron donative coloration organic compound, (b) an electron receptive compound and (c) a reactive medium generating an electron donating and receiving reaction by the (a) and (b) components in a specific temperature range reversibly, a transparent metallic sheen pigment, an excipient, a filler and a binder resin. There is also provided a solid writing body set consisting of the solid writing body and a friction body.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a solid cursive body. Furthermore, the present invention relates to a solid cursive body capable of forming a handwriting having reversible thermochromic property and a solid cursive set using the same.

  Conventionally, solid cursives using a reversible thermochromic composition capable of storing and holding the state before and after the color change in a constant temperature range such as a normal temperature range have been proposed (see, for example, Patent Documents 1 to 3). .

  The solid cursive forms a handwriting that changes color due to temperature change by using a reversible thermochromic composition alone or a microcapsule encapsulant as a colorant to be added to a wax as a shaping material. In particular, when a microcapsule pigment encapsulating a heat decoloring type reversible thermochromic composition is used, the handwriting can be easily erased by frictional heat, making it possible to correct misprints and form highlights for coloring, etc. For example, it can be applied to writing or drawing on a notebook or notebook.

Japanese Utility Model Publication No. 7-6248 JP 2008-291048 A JP 2009-166310 A

Kondo Yasuo and Koishi Masumi, “Microcapsules: Its Production, Properties, and Applications”, Sankyo Publishing Co., Ltd., 1977

The present invention enhances the effect of handwriting decoration by the above-described highly convenient solid cursive material, and can impart glitter to the handwriting, and at the same time, reliably write without leaving a glittering feeling at the time of heat decoloring. It is intended to provide a solid cursive body with a high decorative effect that can erase the effect.
Furthermore, the present invention provides a technique that can suppress discoloration characteristic defects that are likely to occur in the solid cursive material having the glitter.

The solid cursive according to the present invention comprises at least (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) an electron-receiving reaction by the components (a) and (b) in a specific temperature range. A reversible thermochromic microcapsule pigment containing a thermochromic color memory composition comprising a reversibly occurring reaction medium, a transparent metallic luster pigment, a shaping material, a filler, and a binder resin. It is a requirement that
Further, the transparent metallic luster pigment is a pigment in which a material selected from natural mica, synthetic mica, glass, aluminum oxide, and talc is used as a core substance, and the core substance is coated with a metal oxide, the transparent metal The gloss pigment has a particle size in the range of 10 to 500 μm, the addition amount of the transparent metallic luster pigment is 5 to 50% by mass, the transparent metallic luster pigment and the reversible thermochromic microcapsule pigment. It is a requirement that the blending ratio of is 1: 1 to 5: 1.
Further, a styrene resin is added separately from the binder resin, the styrene resin is a styrene acrylic resin, and the addition amount of the styrene resin is 0.1 to 10% by mass. Is a requirement.
Furthermore, it is a requirement that the solid cursive material according to any one of the above is used as an inner core, and an outer shell that covers the outer peripheral surface of the inner core is provided.
Furthermore, a solid cursive set consisting of any of the solid cursives described above and a frictional body is a requirement.

According to the present invention, the handwriting that can be easily erased by frictional heat can be imparted with metallic luster-like glitter, and the convenience and decoration that can reliably erase the handwriting without leaving a glittering feeling at the time of heating and erasing. It becomes a solid cursive with high effect.
Also, by adding a styrenic resin together with the binder resin, poor discoloration characteristics at low temperatures that are likely to occur in glittering solid cursive materials (suppressing the recoloration of the erased handwriting in a temperature range higher than the set temperature) Therefore, it is possible to store a drawn object with a rich radiance without worrying about the temperature range.

It is explanatory drawing which shows the discoloration behavior of the handwriting of the solid cursive body by this invention.

  The solid cursive according to the present invention comprises a reversible thermochromic microcapsule pigment encapsulating a thermochromic color memory composition comprising at least components (a), (b), and (c), a binding material, In addition to the core component containing the agent and the binder resin, a transparent metallic luster pigment is used.

  The solid cursive according to the present invention can alternately exhibit the first coloring state and the second coloring state. According to the present invention, the first color development state and the second color development state are expressed in a two-colored state, that is, two color development states of colored (1) and colored (2), a colored state and a decolored state, or a decolored state. This means that the state and the coloring state are interchangeably exhibited. That is, when the temperature rises from the first color development state and changes to the second color development state, the color (1) changes to the color (2), the color development state changes to the color erasure state, that is, the heat disappears. Includes color type changes.

The discoloration behavior of handwriting when writing with a solid cursive according to the present invention will be described with reference to FIG. In FIG. 1, 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, also referred to as a complete decoloring temperature) that reaches a completely decolored state, and B is a temperature t ₃ (hereinafter, decolorized) at which decolorization is started. C is a point indicating a density at a temperature t _{2 at} which color development is started (hereinafter sometimes referred to as a color development start temperature), and D is a complete color development state. temperature t ₁ to reach a point showing the density at _{(hereinafter,} sometimes referred to complete coloring temperature). Discoloration temperature region is a temperature range between the t ₁ and t _4, both states of the colored state and the decolored state can coexist, a complete decolored state and a fully-colored state at a temperature range of between t ₂ and t ₃ The temperature range can be selectively exhibited. The length of the line segment EF is a scale indicating the rate of discoloration, and the length of the line segment HG passing through the midpoint of the line segment EF indicates the degree of hysteresis (hereinafter sometimes referred to as ΔH). It is. In the present invention, by having this ΔH value, a hysteresis characteristic in which the first color development state and the second color development state are selectively maintained in a certain temperature range is exhibited.

  As the component (A) included in the microcapsule pigment used in the solid writing material according to the present invention, a so-called leuco dye that is usually used in a heat-sensitive material such as heat-sensitive paper can be used. Specific examples include diphenylmethane phthalides, indolyl phthalides, diphenyl methane azaphthalides, phenyl indolyl azaphthalides, fluorans, styrinoquinolines, diazarhodamine lactones, and the like.

  More specifically, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3- (4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) ) Phthalide, 3,3-bis (1-n-butyl-2-methylindol-3-yl) phthalide, 3,3-bis (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- [2 -Ethoxy-4- (N-ethylanilino) phenyl] -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 3,6-diphenylaminofluorane, 3,6-dimethoxyfluorane 3,6-di-n-butoxyfluorane, 2-methyl-6- (N-ethyl-Np-tolylamino) fluorane, 3-chloro-6-cyclohexylaminofluor Lan, 2-methyl-6-cyclohexylaminofluorane, 2- (2-chloroanilino) -6-di-n-butylaminofluorane, 2- (3-trifluoromethylanilino) -6-diethylaminofluorane, 2- (N-methylanilino) -6- (N-ethyl-Np-tolylamino) fluorane, 1,3-dimethyl-6-diethylaminofluorane, 2-chloro-3-methyl-6-diethylaminofluorane, 2 -Anilino-3-methyl-6-diethylaminofluorane, 2-anilino-3-methyl-6-di-n-butylaminofluorane, 2-xylidino-3-methyl-6-diethylaminofluorane, 1,2- Benz-6-diethylaminofluorane, 1,2-benz-6- (N-ethyl-N-isobutylamino) fluorane, 1, -Benz-6- (N-ethyl-N-isoamylamino) fluorane, 2- (3-methoxy-4-dodecoxystyryl) quinoline, spiro [5H- (1) benzopyrano (2,3-d) pyrimidine- 5,1 ′ (3′H) isobenzofuran] -3′-one, 2- (diethylamino) -8- (diethylamino) -4-methyl-spiro [5H- (1) benzopyrano (2,3-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- (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-amylamino) -4-methyl-spiro [5H- (1) benzopyrano (2,3-g) pyrimidin-5,1 '(3'H) isobenzofuran] -3-one, 3- (2-methoxy-4-dimethylamino Phenyl) -3- (1-butyl-2-methylindol-3-yl) -4,5,6,7-tetrachlorophthalide, 3- (2-ethoxy-4-diethylaminophenyl) -3- (1 -Ethyl-2-methylindol-3-yl) -4,5,6,7-tetrachlorophthalide, 3- (2-ethoxy-4-diethylaminophenyl) -3- (1-pentyl-2-methylindole -3-yl) -4,5,6,7-te Lachlorophthalide, 3 ', 6'-bis [phenyl (2-methylphenyl) amino] -spiro [isobenzofuran-1 (3H), 9'-[9H] xanthen] -3-one, 3 ', 6'-bis [Phenyl (3-methylphenyl) amino] -spiro [isobenzofuran-1 (3H), 9 '-[9H] xanthen] -3-one, 3', 6'-bis [phenyl (3-ethylphenyl) amino ] -Spiro [isobenzofuran-1 (3H), 9 '-[9H] xanthen] -3-one.

  Furthermore, there can be mentioned pyridine-based, quinazoline-based, bisquinazoline-based compounds and the like that are effective in developing fluorescent yellow to red color development.

  (B) Component electron-accepting compounds include active proton-containing compounds, pseudo-acidic compounds (compounds that are not acids but act as acids in the composition to cause component (I) to develop color), electrons There is a group of compounds having pores. 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. Or what has an amide group, a halogen group, etc., a phenol-aldehyde condensation resin etc., such as a bis type and a tris type phenol, are mentioned. Moreover, the metal salt of the compound which has the said phenolic hydroxyl group can also be used.

More specifically, phenol, o-cresol, tertiary butylcatechol, nonylphenol, n-octylphenol, n-dodecylphenol, n-stearylphenol, p-chlorophenol, p-bromophenol, o-phenylphenol, p- N-butyl 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-Bis (4-hydroxyphenyl) -3-methylbutane, 1,1-bis (4-hydroxyphenyl) -2-methylpropane, 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, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) ethylpropionate, 2,2-bis (4-hydroxy) Phenyl) -4-methylpentane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-hydroxyphenyl) n-hepta , 2,2-bis (4-hydroxyphenyl) such as n- nonane, and the like.

  In addition, the compound having a phenolic hydroxyl group can exhibit the most effective thermochromic property, but aromatic carboxylic acid and aliphatic carboxylic acid having 2 to 5 carbon atoms, carboxylic acid metal salt, acidic phosphate ester and A compound selected from those metal salts, 1,2,3-triazole and derivatives thereof can also be used.

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

  Specific examples of the component (c), which is a reaction medium that causes the electron transfer reaction by the component (a) and component (b) to occur reversibly in a specific temperature range, include alcohols, esters, ketones, or Mention may be made of ethers.

  The component (c) is preferably a large hysteresis characteristic regarding the color density-temperature curve (a curve plotting a change in color density due to a temperature change changes the temperature from the low temperature side to the high temperature side and the high temperature side to the low temperature side). A carboxylic acid ester compound that exhibits a ΔT value (melting point-cloud point) of 5 ° C. or higher and lower than 50 ° C., which can form a reversible thermochromic composition that exhibits color memory, and changes color when changing to the side) For example, a carboxylic acid ester having a substituted aromatic ring in the molecule, 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, 6 carbon atoms Fatty acid and unsubstituted aromatic alcohol or phenol ester, fatty acid having 8 or more carbon atoms and branched aliphatic alcohol or ester, dicarboxylic acid And esters of aromatic alcohols or branched aliphatic alcohols, dibenzyl cinnamate, heptyl stearate, didecyl adipate, dilauryl adipate, dimyristyl adipate, dicetyl adipate, distearyl adipate, trilaurin, trimyristin, tristearin, Dimyristin, distearin and the like can be 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 number of fats 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 may be used.

  Specifically, as esters, n-pentadecyl acetate, n-tridecyl butyrate, n-pentadecyl butyrate, n-undecyl caproate, n-tridecyl caproate, n-pentadecyl caproate, n-nonyl caprylate, capryl N-undecyl acid, n-tridecyl caprylate, n-pentadecyl caprylate, n-heptyl caprate, n-nonyl caprate, n-undecyl caprate, n-tridecyl caprate, n-pentadecyl caprate, n-laurate -Pentyl, n-heptyl laurate, n-nonyl laurate, n-undecyl laurate, n-tridecyl laurate, n-pentadecyl laurate, n-pentyl myristate, n-heptyl myristate, n-nonyl myristate , N-undecyl myristate, myristic N-tridecyl acid, n-pentadecyl myristate, n-pentyl palmitate, n-heptyl palmitate, n-nonyl palmitate, n-undecyl palmitate, n-tridecyl palmitate, n-pentadecyl palmitate, n stearate Nonyl, n-undecyl stearate, n-tridecyl stearate, n-pentadecyl stearate, n-nonyl eicosanoate, n-undecyl eicosanoate, n-tridecyl eicosanoate, n-pentadecyl eicosanoate, n-nonyl behenate , N-undecyl behenate, n-tridecyl behenate, n-pentadecyl behenate and the like.

  As the ketones, aliphatic ketones having a total carbon number of 10 or more are effective, and 2-decanone, 3-decanone, 4-decanone, 2-undecanone, 3-undecanone, 4-undecanone, 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.

  Furthermore, as arylalkyl ketones having 12 to 24 carbon atoms, for example, n-octadecanophenone, n-heptadecanophenone, n-hexadecanophenone, n-pentadecanophenone, n-tetra Decanophenone, 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-butylpropio Phenone, n-heptaphenone, 4-n-pentylace Phenone, phenyl ketone, benzyl -n- butyl ketone, 4-n-butyl acetophenone, n- hexanophenone, 4-isobutyl acetophenone, 1-acetonaphthone, 2-acetonaphthone, like 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、ａは０〜２の整数を示し、Ｘ_１のいずれか一方は−（ＣＨ_２）_ｎＯＣＯＲ’又は−（ＣＨ_２）_ｎＣＯＯＲ’、他方は水素原子を示し、ｂは０〜２の整数を示し、Ｒ’は炭素数４以上のアルキル基又はアルケニル基を示し、Ｙ１はそれぞれ独立に水素原子、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、ｂはそれぞれ独立に１〜３の整数を示す。） Furthermore, a compound represented by the following general formula (1) is preferably used as the component (c).

(In the formula, R ₁ represents a hydrogen atom or a methyl group, a represents an integer of 0 to 2, and _one of X ₁ represents — (CH ₂ ) _n OCOR ′ or — (CH ₂ ) _n COOR ′, The other represents a hydrogen atom, b represents an integer of 0 to 2, R ′ represents an alkyl group or alkenyl group having 4 or more carbon atoms, Y1 is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, A methoxy group or a halogen, and b independently represents an integer of 1 to 3)

Among the compounds represented by the above (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 further R ₁ is a hydrogen atom, and The case where a is 0 is more preferable.

（式中のＲ_２は、炭素数８以上のアルキル基又はアルケニル基、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。） Of the compounds represented by (1), compounds represented by the following general formula (2) are more preferably used.

(R ₂ in the formula is 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、ｃはそれぞれ独立に１〜３の整数を示し、Ｘ_３はそれぞれ独立に水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、又はハロゲンを示す。） 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, c represents an integer of 1 to 3 each independently, X ₃ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, (A C1-C4 alkoxy group or a halogen is shown.)

  Specific examples of the compound include 1,1-diphenylmethyl octanoate, 1,1-diphenylmethyl nonanoate, 1,1-diphenylmethyl decanoate, 1,1-diphenylmethyl undecanoate, 1,1-dodecanoic acid 1,1- Diphenylmethyl, 1,1-diphenylmethyl tridecanoate, 1,1-diphenylmethyl tetradecanoate, 1,1-diphenylmethyl pentadecanoate, 1,1-diphenylmethyl hexadecanoate, 1,1-diphenylmethyl heptadecanoate, octadecanoic acid Examples include 1,1-diphenylmethyl.

（式中、Ｘ_４はそれぞれ独立に水素原子、炭素数１〜４のアルキル基、メトキシ基、又はハロゲン原子のいずれかを示し、ｅはそれぞれ独立に１〜３の整数を示し、ｄは１〜２０の整数を示す。） Furthermore, a compound represented by the following general formula (4) can also be used as the component (c).

(In the formula, each X ₄ independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, or a halogen atom, e represents each independently an integer of 1 to 3, and d represents 1; Represents an integer of ~ 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 Etc. can be exemplified ether.

（式中、Ｒ_５は炭素数１〜２１のアルキル基又はアルケニル基を示し、ｆはそれぞれ独立に１〜３の整数を示す。） Furthermore, a compound represented by the following general formula (5) can also be used as the component (c).

(In the formula, R ₅ represents an alkyl group or alkenyl group having 1 to 21 carbon atoms, and f independently 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 a diester of 1,4-bis (2-hydroxyethoxy) benzene and lauric acid, a diester of 1,4-bis (2-hydroxyethoxy) benzene and myristic acid, and the like.

（式中、Ｘ_６はそれぞれ独立に水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、又はハロゲン原子のいずれかを示し、ｈは１〜３の整数を示し、ｇは１〜２０の整数を示す。） Furthermore, a compound represented by the following general formula (6) can also be used as the component (c).

(In the formula, each of X ₆ independently 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, h represents an integer of 1 to 3, g represents an integer of 1 to 20.)

  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, Examples include a diester of 1,18-octadecanedicarboxylic acid and 2-phenoxyethanol.

  The mixing ratio of the three components (A), (B), and (C) included in the microcapsule pigment used in the solid cursive according to the present invention is determined by the concentration, the color change temperature, the color change form, and the type of each component. The blending ratio at which desired characteristics are obtained is, in mass ratio, (A) component: (B) component: (C) component = 1: 0.1-50: 1-800, ) Component: (B) Component: (C) Component = 1: 0.5-20: 5-200. Each of these components may be used in combination of two or more.

The microcapsule pigment used in the solid cursive according to the present invention has various additives such as an antioxidant, an ultraviolet absorber, an infrared absorber, a solubilizing agent, an antiseptic / antifungal agent, etc., as long as the function is not affected. Can be added.
When the first coloring state and the second coloring state change between colored (1) and colored (2), the solid cursive according to the present invention contains a non-thermochromic colorant such as a dye or pigment. This can be achieved.

  In the microcapsule pigment used in the present invention, the mass ratio between the inclusion and the wall membrane is preferably inclusion: wall membrane = 1: 1 to 7: 1. If the ratio of inclusions is larger than this range, the thickness of the wall film becomes thinner and weakens against pressure and heat, and the microcapsules tend to be destroyed. Tend to decrease. More preferably, the inclusion: wall membrane = 1: 1 to 6: 1. If it is within this range, the density and visibility in the colored state are high, and the microcapsules are not destroyed.

  The microcapsule pigment used in the solid cursive according to the present invention is not particularly limited, but preferably has an average particle size of 0.1 to 50 μm. If it is smaller than this range, the color density tends to be lowered. If it is larger than this range, the dispersion stability and processability tend to be inferior when used in a solid cursive. More preferably, it is 0.3-30 micrometers. Within this range, the color development state is good, and the dispersion stability and processability are improved.

  The average particle diameter of the microcapsule pigment referred to in the present invention is represented by the value of D50 expressed on a volume basis when the particle diameter is measured. As an example of the measurement, a value obtained by measuring using a laser diffraction / scattering particle size distribution measuring apparatus (manufactured by Horiba, Ltd .; LA-300) and calculating an average particle diameter (median diameter) based on the numerical value. Is used.

  The mixing ratio of the microcapsule pigment used in the solid cursive according to the present invention is preferably 1 to 70% by mass with respect to the total mass of the inner core of the solid cursive. If it is smaller than this range, the color density tends to decrease, and if it is larger than this range, the strength of the inner core of the solid cursive tends to decrease. Preferably, it is 5-50 mass%, More preferably, it is 10-40 mass%. If it exists in this range, the intensity | strength and handwriting density | concentration of a solid cursive body can be made compatible.

  For the microcapsule pigment, a generally known method as described in Non-Patent Document 1, for example, can be used as a production method. Specifically, coacervate method, interfacial polymerization method, interfacial polycondensation method, in-situ polymerization method, submerged drying method, submerged curing method, suspension polymerization method, emulsion polymerization method, air suspension coating method, spray The dry method etc. are mentioned and it selects suitably.

The transparent metallic luster pigment used in the solid cursive according to the present invention is a glittering pigment having a light transmitting property. Therefore, when the microcapsule pigment is in a colored state, it exhibits a glittering property due to reflected light, and in a decolored state, it is light. Transparency due to transmission is visible. In ordinary solid cursives (those that are not thermally decolored), metal powder such as aluminum is used as a glittering material, but since it does not have transparency (light transmission), it can be erased by handwriting (microcapsule pigment) In the discolored state), the color of the metal powder such as aluminum remains and remains. Therefore, the transparent metallic luster pigment of the present invention is applied.
Any material can be used as the transparent metallic luster pigment as long as it exhibits the above-mentioned effects. Preferably, a material selected from natural mica, synthetic mica, flat glass pieces, flaky aluminum oxide, and talc is used. As the core material, a core material coated with a metal oxide or a cholesteric liquid crystal type is used.

Transparent metallic luster pigments with natural mica as the core material are effective when the surface of natural mica particles is coated with titanium oxide, and the top layer of titanium oxide is coated with iron oxide or non-thermochromic dyes. is there.
Specific examples of pigments obtained by coating the surface of the natural mica with a metal oxide such as titanium oxide include 100 series, 200 series, 300 series, and 500 series of trade names “Iriodin” manufactured by Merck & Co., for example. Product No .: 100 (particle size distribution: 10 to 60 μm: silver pearl), 153 (particle size distribution: 20 to 100 μm: flash pearl), 163 (particle size distribution: 20 to 160 μm: shimmer pearl), 183 (particle size distribution: 45 to 500 μm: supernova white) 201 (particle size distribution 5-25 μm: rutile fine gold), 205 (particle size distribution 10-60 μm: rutile platinum gold), 225 (particle size distribution 10-60 μm: rutile blue pearl), 235 (particle size distribution 10-60 μm: rutile green) Pearl), 249 (particle size distribution: 10 to 125 μm: hula Shugold), 300 (particle size distribution 10-60 μm: Gold Pearl), 530 (particle size distribution 10-125 μm: glitter bronze), trade name “Lumina Colors” manufactured by Engelhard, Inc. Product number: Lumina Gold (particle size distribution 10-48 μm: Gold), Lumina Red (particle size distribution 10-48 μm: metallic red), Lumina Red Blue (particle size distribution 10-48 μm: metallic blue), Lumina Aqua Blue (particle size distribution 10-48 μm: metallic blue), Lumina Green (particle size distribution 10 -48 [mu] m: metallic green), lumina turquoise (particle size distribution 10-48 [mu] m: metallic green), trade name "Pearl Glaze" manufactured by Nippon Koken Kogyo Co., Ltd. Product number: MS-100R (20-100 [mu] m: silver), ML-100R (20 ~ 200μm: Silver), MXL Examples thereof include −100R (45 to 500 μm: silver), MC-355R (30 to 100 μm: gold), MC-383R (45 to 500 μm: gold), and the like.

Transparent metallic luster pigments with synthetic mica as the core material and coated with a metal oxide such as titanium oxide are metal ions that cause coloring factors such as impurities and iron compared to systems using natural mica as the core material. In addition to being excellent in glitter, it has a glittering appearance and excellent transparency.
The pigment exhibits a metallic luster of gold, silver, or metallic color depending on the coverage of the metal oxide covering the surface of the synthetic mica.
As the synthetic mica, KMg ₃ (AlSi ₃ O ₁₀ ) F ₂ may be mentioned.
Although the shape of the mica is not specified, a flat shape or a scale shape can be exemplified. Examples of the metal oxide that covers the surface of the synthetic mica include metal oxides such as titanium, zirconium, chromium, vanadium, and iron. Preferred examples include metal oxides mainly composed of titanium oxide.
Specific examples of pigments in which the surface of the synthetic mica is coated with a metal oxide are trade names “ultimica” manufactured by Nippon Koken Kogyo Co., Ltd., product number: SB-100 (5 to 30 μm: silver), SD-100 ( 10-100 μm: silver), SE-100 (15-100 μm: silver), SF-100 (44-150 μm: silver), SH-100 (150-600 μm: silver), YB-100 (5-30 μm: gold) YD-100 (10-60 μm: gold), YE-100 (15-100 μm: gold), YF-100 (44-150 μm: gold), RB-100 (5-300 μm: metallic red), RD-100 ( 10-60 μm: metallic red), RE-100 (15-100 μm: metallic red), RF-100 (44-150 μm: metallic red), RBB- 00 (5-30 μm: metallic purple), RBD-100 (10-60 μm: metallic purple), RBE-100 (15-100 μm: metallic purple), RBF-100 (44-150 μm: metallic purple), VB-100 ( 5-30 μm: metallic violet), VD-100 (10-60 μm: metallic violet), VE-100 (15-100 μm: metallic violet), VF-100 (44-150 μm: metallic violet), BB-100 (5- 30 μm: metallic blue), BD-100 (10-60 μm: metallic blue), BE-100 (15-100 μm: metallic blue), BF-100 (44-150 μm: metallic blue), GB-100 (5-30 μm: metallic Lean), GD-100 (10~60μm: metallic green), GE-100 (15~100μm: metallic green), GF-100 (44~150μm: metallic green) and the like can be exemplified.

A transparent metallic luster pigment having a flat glass piece or talc as a core substance, and the surface thereof being coated with a metal oxide such as titanium oxide, exhibits a metallic luster of gold, silver or metallic color depending on the coverage of the metal oxide.
Specifically, as a pigment in which the surface of the flat glass piece is coated with a metal oxide, a trade name “META SHINE” MC5090RS (90 μm: silver) manufactured by Nippon Sheet Glass Co., Ltd., in which a scaly glass piece is coated with titanium oxide. MC5090RY (90 μm: gold), MC5090RR (90 μm: red), MC5090RV (90 μm: purple), MC5090RB (90 μm: blue), MC5090RG (90 μm: green), MC1080RS (80 μm: silver), MC1080RY (80 μm: gold), MC1080RR (80 μm: red), MC1080RB (80 μm: blue), MC1080RG (80 μm: green), MC1040RS (40 μm: silver), MC1040RY (40 μm: gold), MC1040RR (40 μm: red), MC1040RB (40 μm) Blue), MC1040RG (40 μm: Green), MC1020RS (20 μm: Silver), MC1020RY (20 μm: Gold), MC1020RR (20 μm: Red), MC1020RB (20 μm: Blue), MC1020RG (20 μm: Green), MC1080RSS1 (80 μm: Silver) ), MC1080RYS1 (80 μm: gold), and the like.
Specific examples of the pigment in which the surface of the talc is coated with a metal oxide are trade names “Silseem” manufactured by Nippon Koken Kogyo Co., Ltd .: Misty Pearl Silver (10 μm: silver), Misty Pearl Yellow (10 μm: yellow) ), Misty Pearl Red (11 μm: red), Misty Pearl Blue (11 μm: blue), and the like.

The transparent metallic luster pigment with flaky aluminum oxide as the core material and the surface coated with a metal oxide such as titanium oxide has less impurity content than the system of natural mica, making it brilliant. Are better.
Examples of the metal oxide covering the surface of the aluminum oxide include metal oxides such as titanium, zirconium, chromium, vanadium, iron, etc., preferably a metal oxide mainly composed of titanium oxide is applied, Depending on the coverage of the metal oxide, it exhibits a metallic color such as gold, silver or metallic.
Specific examples of pigments obtained by coating the surface of the flaky aluminum oxide with a metal oxide include trade names “Silary” manufactured by Merck Co., Ltd .: T50-10 (10-30 μm: silver), T60-10 WNT (10-30 μm). : Silver), T60-20WNT (10-30 μm: Gold), T60-24WNT (10-30 μm: Metallic Green), T60-23WNT (10-30 μm: Metallic Blue), and the like.

The liquid crystal polymer used as the cholesteric liquid crystal type metallic luster pigment has a property that only a part of the light incident in a wide spectral region is reflected by the interference effect of light, and the light is transmitted through all other regions. The region of the reflection spectrum is determined by the pitch width of the helical polymer and the refractive index of the material, and the reflection spectral region is divided into light components polarized in the left and right helices, with the direction of rotation of the helix. Accordingly, one can be reflected and the other can be transmitted. As a result, the cholesteric liquid crystal type metallic luster pigment has the property of transmitting and reflecting over the entire spectral region, that is, the color flop property in which the color tone changes depending on the excellent metallic luster and the viewpoint.
The cholesteric liquid crystal type metallic luster pigment has transparency as well as glitter.
Specific examples of the cholesteric liquid crystal type metallic luster pigment include materials based on a siloxane skeleton having a mesogen in the side chain.
Specific examples of the cholesteric liquid crystal type metallic luster pigment include trade name “Helicone HC” manufactured by Wacker Chemie, product number: Sapphire (SLM90020) [blue → dark], Scarabeus (SLM90120) [green → blue], Jade (SLM90220). ) [Gold color → green blue], Maple (SLM90320) [red copper color → green] and the like.

The transparent metallic luster pigment exhibits a luster equivalent to or higher than that obtained when a metallic luster pigment that does not have transparency, such as a metallic luster pigment or a metallic luster pigment in which a core material is coated with a metal, and has a reversible heat. When the discolorable microcapsule pigment is decolored, it cannot be visually recognized without causing a residual color.
In addition, a plurality of pigments having different hues and particle sizes (particle size distributions) can be used in combination as a transparent metallic luster pigment, or non-thermochromic general dyes and pigments can be used in combination to make the color change more diverse.

The particle size of the transparent metallic luster pigment is preferably in the range of 10 to 500 μm. Since the handwriting of the solid cursive material is in a laminated state without penetrating into the paper surface as compared with the handwriting of the ink, if it is smaller than 10 μm, it is buried in the handwriting and it is difficult to obtain the desired glitter. Moreover, when larger than 500 micrometers, it will become easy to produce malfunctions, such as grind | pulverizing by kneading | mixing etc. at the time of solid cursive manufacture.
The particle diameter is measured by appropriately using a laser diffraction / scattering particle size measuring device, a dynamic light scattering particle size distribution measuring device, a Coulter counter, or the like according to the shape and size of the particles.

The addition amount of the transparent metallic luster pigment is preferably 5 to 50% by mass, more preferably 5 to 35% by mass. In the above range, desired glitter can be obtained, and stability over time after production is particularly excellent.
In particular, by blending the transparent metallic luster pigment and the reversible thermochromic microcapsule pigment so that the blending ratio is 1: 1 to 5: 1, it is located in the lower layer or gap of the microcapsule pigment in a handwritten state. Since the reflective surface is visible without being concealed, it can exhibit excellent glitter with high reflectivity, especially 1: 1 to 3: 1 (ie equivalent to 3 times the transparent metallic luster pigment) In the range of (used in an amount), it is particularly preferable since high stability over a long period of time can be easily obtained in addition to the above-described excellent glitter.

  As a shaping material used for the solid cursive of the present invention, for example, a wax, a gelling agent, clay and the like can be used. Any wax may be used as long as it is conventionally known. Specifically, carnauba wax, wax, beeswax, microcrystalline wax, montan wax, candelilla wax, sucrose fatty acid ester, dextrin fatty acid ester. , Polyolefin wax, styrene-modified polyolefin wax, paraffin wax and the like. As the gelling agent, conventionally known ones can be used, and examples thereof include 12 hydroxystearic acid, dibenzylidene sorbitols, tribenzylidene sorbitols, amino acid oils, and higher fatty acid alkali metal salts. Examples of clay minerals include kaolin, bentonite, and montmorillonite. The shaping material preferably contains at least one of polyolefin wax, sucrose fatty acid ester or dextrin fatty acid ester. Specific examples include waxes such as polyethylene, polypropylene, polybutylene, α-olefin polymer, ethylene-propylene copolymer, and ethylene-butene copolymer.

  In particular, among the polyolefin waxes, those having a softening point in the range of 100 ° C. to 130 ° C. and a penetration of 10 or less are preferably used because of high writing feeling. If the penetration exceeds 10, the solid cursive will tend to be too soft and difficult to write, and the handwriting will be stretched on the paper surface during rubbing and erasing (wax will be thinned). This will contaminate the blank area of the surface and cause color transfer and smudge to other paper.

  In addition, the measuring method of the softening point and the penetration of the polyolefin wax is standardized in JIS K2207, and the penetration value represents 0.1 mm as penetration. Therefore, it is a solid cursive letter that is harder as the number is smaller and softer as the number is larger.

  Specifically, Neo Wax Series (polyethylene manufactured by Yashara Chemical Co., Ltd.), Sun Wax Series (polyethylene manufactured by Sanyo Chemical Industries, Ltd.), High Wax Series (polyolefin manufactured by Mitsui Chemicals, Inc.), AC polyethylene (Honeywell) Polyethylene).

  When the solid currant according to the present invention contains at least one of sucrose fatty acid ester, dextrin fatty acid ester, and side chain crystalline polyolefin, it can be preferably used because the handwriting concentration can be improved.

  As the sucrose fatty acid ester, an ester having a C12 to C22 fatty acid as a constituent fatty acid is particularly preferable, and palmitic acid and stearic acid are more preferable. Specifically, Mitsubishi Chemical Foods Co., Ltd .: Ryoto Sugar Ester Series, Daiichi Kogyo Seiyaku Co., Ltd .: Sugar Wax Series and the like can be mentioned.

  The dextrin fatty acid ester used in the solid cursive according to the present invention is particularly preferably an ester having a C14 to C18 fatty acid as a constituent fatty acid, more preferably palmitic acid, myristic acid, or stearic acid. Specifically, Chiba Flour Milling Co., Ltd .: Leopard series, etc. are mentioned.

As the side chain crystalline polyolefin, those having a long alkyl group in the side chain are applied, and specifically, those having a long chain alkyl group of C12 to C28 are preferable. Further, the long-chain alkyl group in the side chain is not particularly limited to a straight-chain type or a branched type, but a straight-chain type is more preferable from the viewpoint of crystallinity. Further, as one of the side chain crystalline polyolefins, there can be mentioned a polyolefin having a highly branched structure (referred to as a highly branched polyolefin).
In addition, from the viewpoint of the mechanical strength and discoloration characteristics of the solid cursive material, and the handleability during production, the side chain crystalline polyolefin preferably has a weight average molecular weight Mw of 2,000 to 50,000, preferably 10,000 to 10,000. 30,000 is preferred. The number average molecular weight Mn of the side chain crystalline polyolefin is preferably 1,000 to 10,000. Here, the weight average molecular weight and the number average molecular weight are measured by gel permeation chromatography based on polystyrene.
Specifically, Toyokuni Oil Co., Ltd. product: HS crystal 4100, HS crystal 6100, Idemitsu Kosan Co., Ltd .: El crystal 4100, El crystal 6100 etc. are mentioned, As a hyperbranched polyolefin, Baker Hughes make: VYBAR103, VYBAR260, VYBAR343, VYBAR852, etc. are mentioned.

  As a mixture ratio of the shaping material used for the solid cursive according to the present invention, 0.2 to 70% by mass is preferable based on the total mass. If it is smaller than this range, it tends to be difficult to obtain a shape as a writable inner core of the solid cursive body, and if it is larger than this range, it tends to be difficult to obtain a sufficient writing density. Preferably, it is 0.5 to 40% by mass, and when it is in this range, the shape of the solid cursive body and the handwriting concentration can be compatible.

  The filler used in the solid cursive according to the present invention is blended for the purpose of improving the strength of the solid cursive and adjusting the writing quality. Examples of the filler that can be used in the present invention include talc, clay, silica, calcium carbonate, barium sulfate, alumina, mica, boron nitride, potassium titanate, and glass flake. Talc and calcium carbonate are preferred from the viewpoint of the effect on the discoloration performance.

  The blending ratio of the filler is preferably 10 to 55% by mass with respect to the total mass. If it is smaller than this range, the strength tends to decrease, and if it is larger than this range, the color developability tends to decrease or the writing quality tends to be poor.

  The compounding ratio of the filler, the shaping material, and the microcapsule is not particularly limited, but the shaping material is generally 0.1 to 5 and preferably 0.5 to the microcapsule 1 on a mass basis. And the filler is 0.1 to 5, preferably 0.5 to 2.

The binder resin used in the solid cursive according to the present invention is blended for the purpose of improving the strength of the solid cursive, but natural resins and synthetic resins can be used. Specific examples include olefin resins, cellulose resins, vinyl alcohol resins, pyrrolidone resins, acrylic resins, styrene resins, amide resins, and basic group-containing resins. In particular, ethylene vinyl acetate copolymer resin, ethylene vinyl alcohol copolymer resin, and polyvinyl alcohol resin are suitable because molding stability is improved by the combined use with polyester polyol resin.
As addition amount of the said binder resin, it is preferable that it is the range of 0.5-5 mass% in the whole quantity.

  Further, a hindered amine compound can be added to the solid cursive according to the present invention. By adding the hindered amine compound, there is a feature that the afterimage of the portion where the handwriting is erased becomes more difficult to be visually recognized. For this reason, it is preferable because the re-writing property can be satisfied and the merchantability can be improved without impairing the appearance of the writing surface.

When the molecular weight of the hindered amine compound is 1000 or less, the hindered amine compound is highly compatible with the shaping material and hardly bleeds out, so that clear handwriting can be formed even after aging.
The hindered amine compound having a melting point of 120 ° C. or lower can produce a solid writing material without applying excessive heat during production, so that the reversible thermochromic microcapsule pigment and various additives deteriorate. Can be prevented.
The addition amount of the hindered amine compound is preferably 0.1 to 5% by mass in the total amount. By adding within the above range, it is possible to effectively neutralize the bleed-out component from the microcapsule pigment, and the afterimage of the place where the handwriting is erased becomes more difficult to be visually recognized, so that the appearance of the writing surface is not impaired. Moreover, the re-writing property can be satisfied, and the merchantability can be improved.

  Furthermore, various additives can be added as needed. Examples of the additives include viscosity modifiers, fungicides, antiseptics, antibacterial agents, ultraviolet light inhibitors, and fragrances.

The thermochromic solid writing material having the glitter having the above composition tends to cause a poor color change characteristic in a low temperature state as compared with the conventional thermochromic solid writing material having no glittering property. This is a phenomenon that occurs when the transparent metallic luster pigment acts on the reversible thermochromic microcapsule pigment when the composition is formed into a solid state. This is a problem that occurred in finding a thermochromic solid cursive material excellent in properties. As a result of further studies to solve the above problems, it has been found that the use of a styrenic resin for the composition solves the problem.
Thereby, since composition deformation of the microcapsule pigment can be reliably suppressed over a long period of time, the erased handwriting will not be recolored again in a low temperature region that is less than the set temperature (higher than the set temperature). .

  Examples of the styrenic resin include polystyrene, styrene acrylic resin, acrylonitrile butadiene styrene resin, styrene acrylonitrile resin, styrene butadiene resin, and styrene ethylene butadiene styrene resin.

In particular, among the styrenic resins, a styrene acrylic resin is preferable because a high effect can be exhibited with a small amount of addition.
Specific examples include Hymer SB305, Hymer SBM73F, and Himer SB317 manufactured by Sanyo Chemical Industries.

  The addition amount of the styrenic resin is 0.1 to 10% by mass, preferably 0.5% to 5% by mass, based on the total mass of the solid cursive body. If the amount is less than 0.1% by mass, the discoloration characteristics may be inferior. If the amount exceeds 10% by mass, the above-mentioned effect is not improved, so that no more addition is required.

  The solid cursive body according to the present invention can be used alone as a cursive body, or can have a core-sheath structure (double core) provided with an outer shell that covers the outer peripheral surface by using it as an inner core. Such an outer shell can prevent the solid cursive inside from being damaged by physical contact, and can also contribute to the improvement of the mechanical strength of the entire solid cursive. Such an outer shell may or may not contain a colorant that contributes to handwriting formation, but generally the tip of a solid cursive is often cut into a cone, so the outer shell is not included in the handwriting. Often has no effect. For this reason, it is common not to add a colorant to the outer shell.

The outer shell can be formed of a general-purpose resin or the like, but it is preferable to use a shaping material from the viewpoint that a stable covering state can be maintained.
For example, a wax or a gelling agent can be used as the shaping material. Any wax may be used as long as it is conventionally known. Specifically, carnauba wax, wax, beeswax, microcrystalline wax, montan wax, candelilla wax, sucrose fatty acid ester, dextrin fatty acid ester. , Polyolefin wax, styrene-modified polyolefin wax, paraffin wax, stearic acid and the like. As the gelling agent, conventionally known ones can be used, and examples thereof include 12 hydroxystearic acid, dibenzylidene sorbitols, tribenzylidene sorbitols, amino acid oils, and higher fatty acid alkali metal salts. The shaping material preferably contains at least one of polyolefin wax, sucrose fatty acid ester or dextrin fatty acid ester. Specific examples include waxes such as polyethylene, polypropylene, polybutylene, α-olefin polymer, ethylene-propylene copolymer, and ethylene-butene copolymer, and the use of a shaping material that can be used for the inner core. Can do. Furthermore, it is preferable to use the same material as the shaping material used for the inner core because the interface between the inner core and the outer shell is appropriately fused and unnecessary interface peeling does not occur. The blending ratio of the shaping material used for the outer shell is preferably 10% by mass to 90% by mass with respect to the total mass of the outer shell. Within this range, the moldability is improved, which is preferable. The blending amount of the shaping material is more preferably 10% by mass to 90% by mass, and further preferably 20% by mass to 70% by mass. If it is within this range, the moldability of the solid cursive body, the solid cursive body The light resistance is further improved.

  A filler can be mix | blended with the shaping | molding material with the outer shell of the solid cursive body by this invention. Fillers include calcium carbonate, clay, kaolin, bentonite, montmorillonite, talc, titanium dioxide, barium sulfate, zinc oxide, mica, potassium titanate whisker, magnesium oxysulfate whisker, aluminum borate whisker, wax Lastite, attapulgite, sepiolite, silica, etc., ceramics such as silicon nitride, boron nitride, aluminum nitride, boron oxide, alumina, zirconia, natural graphite, artificial graphite, graphite such as expanded graphite, expanded graphite, Examples thereof include carbon blacks such as oil furnace black, gas furnace black, channel black, thermal black, acetylene black and lamp black.

  The blending ratio of the filler is preferably 10% by mass or more, and preferably 90% by mass or less, based on the total mass of the outer shell. From the viewpoint of improving the light resistance and moldability of the solid cursive and the strength of the solid cursive, it is preferable that the blending ratio of the filler is large. On the other hand, from the viewpoint of improving the moldability of the outer core, it is preferable that the amount of the filler is small. More preferably, the blending ratio of the filler is 10% by mass to 80% by mass, and further preferably 30% by mass to 80% by mass. Within this range, all of the light resistance, formability, and strength of the solid cursive body are more preferable.

Further, an elastic resin can be blended in the outer shell. When an elastic resin is used for the outer shell, the affinity between the inner core and the outer shell of the solid cursive body is improved, defects formed during the production are reduced, and the strength such as impact resistance can be improved. . Moreover, the moldability at the time of manufacture is also improved.
Here, the elastic resin refers to a resin having elasticity when in a solid state.
In order to obtain the effect as described above, the blending ratio of the elastic resin is preferably 1% by mass or more, and more preferably 3% by mass or more with respect to the total mass of the outer shell. On the other hand, in order to keep moldability etc. favorable, it is preferable that it is 15 mass% or less, and it is more preferable that it is 10 mass% or less.

The outer shell used for the solid cursive according to the present invention can be added with various additives as necessary for the purpose of imparting various functions. Examples of the additive include the aforementioned hindered amine compounds, colorants, antifungal agents, antiseptics, antibacterial agents, ultraviolet absorbers, lubricants, and fragrances. Any of these additives can be used. A single additive may have a plurality of functions. For example, some stearic acid functions as a shaping agent as well as a slip agent. Thus, when the additive which has a function of a lubricant is added, the further effect, such as a moldability improving, is acquired. In addition, ultraviolet absorbers not only absorb ultraviolet rays but also prevent various materials contained in the outer shell from fading due to ultraviolet rays, and thus may have a function of improving light stability and storage stability.
Furthermore, it is also possible to add the above-mentioned reversible thermochromic microcapsule pigment as necessary. In that case, it is preferable to use a pigment having the same hue as the microcapsule pigment used in the inner core, but a microcapsule pigment having a different hue can also be used.

As a manufacturing method of the solid cursive body by this invention, it can manufacture using extrusion molding or compression molding. To give a specific example of the core-sheath structure, the outer shell is disposed on the outer peripheral surface of the inner core lump, and the outer shell covering the outer peripheral surface of the inner core is provided by compression molding with a press. A cursive script can be obtained.
When the molding is performed at a high temperature, the solid cursive is manufactured by cooling at a low temperature for the purpose of coloring the reversible thermochromic microcapsule pigment.

The thickness and length of the solid cursive according to the present invention can be arbitrarily selected according to the purpose. For example, when considering the case where the solid cursive according to the present invention is used as a pencil core, the thickness is generally 2.0 to 5.0 mm, preferably 2.5 to 4.0 mm, and long The thickness is generally 60 to 300 mm, preferably 80 to 200 mm.
In the case of a core-sheath structure, the thickness of the inner core and the thickness of the outer shell can be arbitrarily selected, but if the outer shell is thick, the impact resistance tends to be excellent, When the thickness of the outer shell is thin, the amount of exposure of the inner core increases, so that it tends to be easy to use. The thickness of the outer shell with respect to the radial length of the inner core is preferably 10 to 100%, and more preferably 20 to 50%. The solid cursive according to the present invention can also be used for applications other than pencils, such as a mechanical pencil lead and crayon, and the thickness and length can be appropriately adjusted according to the application.

  The solid cursive according to the present invention can be written on various writing surfaces. Furthermore, the handwriting can be discolored by rubbing with a finger or application of a heating or cooling tool.

  Examples of the heating tool include an energization heating color changing tool equipped with a resistance heating element, a heating color changing tool filled with hot water, and a hair dryer. Preferably, a friction member is used as a means capable of changing color by a simple method. Used.

  The friction member is preferably an elastic body such as an elastomer or a plastic foam which is rich in elasticity and can generate an appropriate friction during friction to generate frictional heat. As the material of the friction member, silicone resin, SEBS resin (styrene ethylene butylene styrene block copolymer), polyester resin, or the like can be used. The friction member can be obtained by combining a solid cursive body and a friction body, which is a separate member of arbitrary shape, to obtain a solid cursive set, but the solid cursive body or a solid curly body containing the solid cursive body in an exterior container By providing the friction member on the exterior of the writing instrument, it becomes excellent in portability. Specifically, a form in which the exterior is provided with a friction member in the shape of a pencil, such as wood or paper, or a crayon.

  Examples of the cooling / heating tool include a cooling / heating discoloration tool using a Peltier element, a cooling / heating discoloration tool filled with a refrigerant such as cold water and ice pieces, a cold insulation agent, and application of a refrigerator and a freezer.

  Examples will be described below, but the present invention is not limited to these examples.

(Production of microcapsule pigment A)
(Ii) 5 parts by mass of 2- (2-chloroanilino) -6-di-n-butylaminofluorane as component (5) 2,5 parts of 2,2-bis (4′-hydroxyphenyl) hexafluoropropane as component (b) 4,4 ′-(2-methylpropylidene) bisphenol 3.0 parts by weight, and (c) a reversible thermochromic composition consisting of 50 parts by weight of 4-benzyloxyphenylethyl laurate as component (C) Then, a wall mixture material was mixed with 30.0 parts by mass of an aromatic isocyanate prepolymer and 40.0 parts by mass of a co-solvent, emulsified and dispersed in an 8% aqueous polyvinyl alcohol solution, and stirred while heating. Then, 2.5 parts by mass of a water-soluble aliphatic modified amine was added, and stirring was continued to obtain a reversible thermochromic microcapsule suspension. The suspension was centrifuged to isolate reversible thermochromic microcapsules. In addition, the average particle diameter of the microcapsule is 2.3 μm, and exhibits a behavior having hysteresis characteristics of t ₁ : −8 ° C., t ₂ : −1 ° C., t ₃ : 52 ° C., t ₄ : 65 ° C., The color changed reversibly from black to colorless and from colorless to black.

(Production of microcapsule pigment B)
(Ii) 5.0 parts by mass of 9-ethyl (3-methylbutyl) amino-spiro [12H-benzo (α) xanthen-12,1 ′ (3′H) -isobenzofuran] -3′-one as component ( B) 3.04 parts by mass of 4,4 '-(2-ethylhexane-1,1-diyl) diphenol as component, 5.0 parts of 2,2-bis (4'-hydroxyphenyl) -hexafluoropropane, (C) Heat-dissolving a temperature-sensitive color-changing color memory composition consisting of 50.0 parts by mass of capric acid-4-benzyloxyphenylethyl as a component, and 30.0 parts by mass of an aromatic isocyanate prepolymer as a wall film material; A solution in which 40.0 parts by mass of the co-solvent was mixed was emulsified and dispersed in an 8% aqueous polyvinyl alcohol solution, and stirring was continued while heating. Then, 2.5 parts by mass of a water-soluble aliphatic modified amine was added and further stirred. To obtain a thermochromic microcapsule suspension continues. The suspension was centrifuged to isolate thermochromic microcapsules.
In addition, the average particle diameter of the microcapsule is 2.3 μm, and exhibits a behavior having hysteresis characteristics of t ₁ : −20 ° C., t ₂ : −10 ° C., t ₃ : 48 ° C., t ₄ : 58 ° C., The color changed reversibly from pink to colorless and from colorless to pink.

(Production of microcapsule pigment C)
(I) As component (3- (4-diethylamino-2-hexyloxyphenyl) -3- (1) -ethyl-2-methylindol-3-yl) -4-azaphthalide (2.0 parts by mass), (b) component 1,1-bis (4′-hydroxyphenyl) hexafluoropropane 4.0 parts by mass, 1,1-bis (4′-hydroxyphenyl) n-decane 4.0 parts by mass, (ha) caprylic acid as component A microcapsule pigment was obtained in the same manner as the microcapsule pigment A, except that the thermosensitive color-changing color memory composition was composed of 50.0 parts by mass of -4-benzyloxyphenylethyl (melting point 57 ° C.). The microcapsule pigment has an average particle size of 3.0 μm and exhibits a behavior having hysteresis characteristics of t ₁ : −24 ° C., t ₂ : −10 ° C., t ₃ : 42 ° C., t ₄ : 55 ° C. The color changed reversibly from blue to colorless and from colorless to blue.

  The composition of the solid cursives of the examples and comparative examples is shown in the following table. In addition, the numerical value of the composition in a table | surface shows a mass part.

The contents of the raw materials in the table will be described along the note numbers.
(1) MERCK, trade name: Iriodin 6103 (synthetic mica-coated type, particle size 5 to 40 μm)
(2) Product made by MERCK, trade name: Iriodin 163 (natural mica-coated type, particle size 20 to 180 μm)
(3) Product name: Miraval 5411 (flat glass coating type, particle size 20 to 200 μm), manufactured by MERCK
(4) Product name: Iriodin100 (natural mica-coated type, particle size 10 to 60 μm), manufactured by MERCK
(5) Nippon Koken Kogyo Co., Ltd., trade name: Pearl Glaze MC-383R (natural mica coated type, 45-500 μm)
(6) Nippon Koken Kogyo Co., Ltd., trade name: Twinkle Pearl MS (synthetic mica coating type, 10-100 μm)
(7) Sanyo Chemical Industries, Ltd., trade name: Sun Wax 171-P
(8) Daiichi Kogyo Seiyaku Co., Ltd., trade name: Sugar Wax F-10
(9) Product name: High Wax 2203A, manufactured by Mitsui Chemicals, Inc.
(10) Product name: Ryoto Sugar Ester P-170, manufactured by Mitsubishi Chemical Foods Corporation
(11) manufactured by Toyokuni Oil Co., Ltd., trade name: HS Crysta 4100 (Mw: 16,000)
(12) Product name: FH105, manufactured by Fuji Talc Industry Co., Ltd.
(13) Product name: TINUVIN770DF, manufactured by BASF
(14) Sanyo Chemical Industries, Ltd., trade name: Heimer ST95 polystyrene (styrene resin)
(15) Sanyo Chemical Industries, Ltd., trade name: Hymer SB305 (styrene acrylic resin)
(16) Sanyo Chemical Industries, Ltd., trade name: Hymer SBM73F (styrene acrylic resin)

(Manufacture of solid cursive A)
The above blends were kneaded with a kneader, and the resulting kneaded product was compression molded with a press set to an outer diameter of 3 mm and a length of 60 mm, cooled to −20 ° C., and returned to room temperature for solid writing. A body (single core) was obtained.

(Manufacture of solid cursive B)
The above blends were kneaded with a kneader, and 69 parts by mass of talc, 10 parts by mass of a sucrose fatty acid ester, 10 parts by mass of a polyolefin wax, ethylene acetic acid were provided on the outer peripheral surface so that the obtained kneaded product became an inner core. A kneaded product consisting of 10 parts by mass of a vinyl copolymer (elastic resin) is wound to form an outer shell, and compression-molded by a press. The outer diameter is 3 mm, the length is 60 mm (the inner core is 2 mm, and the outer shell. To obtain a solid cursive with a core-sheath structure. In addition, the said dimension is a setting value, The solid cursive is manufactured by cooling to -20 degreeC after compression molding and returning to normal temperature.

Handwriting erasure test Using each of the solid writing bodies A and B obtained in the examples and comparative examples, the JIS P3201 writing paper A was hand-painted into a circular shape at room temperature. Thereafter, half of the circle was rubbed off using a friction body made of SEBS resin. The handwriting state at that time was confirmed visually. Note that Comparative Example 4 was excluded from this test because it had no glitter.
Discoloration characteristic test The test paper in the friction erase state used in the handwriting erase test (with half of the circle erased) was allowed to stand at 5 ° C. for 24 hours, and then the state of the erased portion was visually confirmed at room temperature. In addition, since Comparative Examples 1-3 was not able to be erase | eliminated by the previous test, it excluded from this test.
The results of the test are shown in the following table.

The evaluation of the test results is as follows.
Handwriting erasure test ○: The handwriting that was not erased had glitter, and the erased portion disappeared cleanly without a residual color.
X: The glitter of the handwriting which was not erased was dull, and the metallic luster remained in the erased part.
Discoloration characteristic test A: Recurrent color of the erased portion was not observed, and good discoloration characteristics were obtained.
A: Almost no recurrence color at the erased portion, and good discoloration characteristics were maintained.
Δ: Partially reappearing color at the erased portion and deterioration in the discoloration characteristic was observed, but at a level causing no practical problem.
X: Recurrent color of the erased portion was confirmed, and the erasing performance was deteriorated.

Preparation of Pencils 22 pencils were obtained by storing and molding in a circular outer shaft (wood shaft) using the solid cursive bodies A and B obtained using Examples 1 to 11.
When writing on the paper using the pencil, a black, pink or blue handwriting could be formed.
The handwriting formed by the pencil was decolored (erased) by rubbing with a friction body made of SEBS resin.

Preparation of pencil with friction body A cylindrical friction body made of SEBS resin was fixed to the rear end of the pencil via a metal connecting member to obtain a pencil with friction body.
The handwriting formed on the paper surface using the pencil with a friction body is erased by rubbing with a friction body provided at the rear end to obtain a pencil with a friction body excellent in portability and high convenience. I was able to.

Production of Solid Cursive Set A solid cursive set was obtained by combining 11 pencils using the solid cursive B and a rectangular parallelepiped friction body made of SEBS resin.
The handwriting formed on the paper surface using the pencil was erased by rubbing using a friction body, and a more convenient set that could be easily written and erased was obtained.

t ₁ Complete coloring temperature of the handwriting of the heat decoloring type solid cursive according to the present invention t ₂ Color development start temperature of the handwriting of the heat decoloring type solid cursive according to the present invention t ₃ Heat decoloring type solid writing of the present invention Decolorization start temperature t of body handwriting t ₄ Complete decolorization temperature of handwriting of heat decoloring type solid cursive according to the present invention ΔH Temperature range indicating the degree of hysteresis

Claims (10)

  At least (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, (c) a reaction medium for reversibly causing an electron transfer reaction by the components (a) and (b) in a specific temperature range; A solid writing material comprising a reversible thermochromic microcapsule pigment encapsulating a thermochromic color memory composition comprising: a transparent metallic luster pigment, a shaping material, a filler, and a binder resin.   2. The solid cursive according to claim 1, wherein the transparent metallic luster pigment is a pigment in which a material selected from natural mica, synthetic mica, glass, aluminum oxide, and talc is used as a core substance, and the core substance is coated with a metal oxide. .   The solid cursive according to claim 1 or 2, wherein a particle diameter of the transparent metallic luster pigment is in the range of 10 to 500 µm.   The addition amount of the said transparent metallic luster pigment is 5-50 mass%, The solid cursive body as described in any one of Claims 1-3.   The solid cursive according to any one of claims 1 to 4, wherein a blending ratio of the transparent metallic luster pigment and the reversible thermochromic microcapsule pigment is 1: 1 to 5: 1.   Solid writing material as described in any one of Claims 1-5 formed by adding a styrene resin separately from the said binder resin. The solid writing material according to claim 6, wherein the styrenic resin is a styrene acrylic resin.   The solid cursive according to claim 6 or 7, wherein the addition amount of the styrenic resin is 0.1 to 10% by mass.   A solid cursive body comprising the solid cursive body according to any one of claims 1 to 8 as an inner core and an outer shell covering an outer peripheral surface of the inner core.   A solid cursive set comprising the solid cursive according to claim 1 and a friction body.

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