JP2016011390A - Solid writing material and solid writing material set using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solid writing material having excellent shape stability capable of maintaining desired dimensions during molding without causing the contraction fluctuations of a core diameter during freezing in the production process even when a thermochromic microcapsule pigment is used as a coloring agent.SOLUTION: There is provided a solid writing material which comprises: a reversible thermochromic microcapsule pigment including a temperature-sensitive color-changeable color-memorizing composition comprising at least (A) an electron-donating color-developing organic compound, (B) an electron-accepting compound and (C) a reaction medium which reversibly induces an electron donating and accepting reaction by the components (A) and (B) in a specific temperature range; an excipient; a binder; a binder resin; and a polyester polyol resin. There is provided a solid writing material set which is composed of the solid writing material and a friction body.

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 reversibly storing and maintaining 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-decolorable reversible thermochromic composition is used, the handwriting can be easily erased by frictional heat, making it a highly convenient handwriting that can be corrected in error. For example, the present invention can be applied to writing on a notebook or notebook, drawing, and the like.

  The solid cursive material using the microcapsule pigment is generally manufactured in a core shape by extruding and molding the composition under high temperature and then cooling at low temperature to develop the color of the microcapsule pigment. It is. At this time, when the microcapsule pigment is cooled until it freezes, the microcapsule pigment may change in volume, and the outer diameter of the molded core may shrink. For this reason, the desired core diameter cannot be obtained and cannot be accommodated in the wooden shaft in the form of a pencil, or when the core-sheath structure is provided with an outer shell, there are problems such as cracks occurring in the outer shell. It occurred.

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

  In view of the above-described problems, the present invention does not cause shrinkage fluctuations in the core diameter during freezing in the manufacturing process, even when a thermochromic microcapsule pigment is used as a colorant. It is to provide a solid cursive body excellent in shape stability capable of maintaining the desired dimensions.

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 reversibly thermochromic microcapsule pigment containing a thermochromic color memory composition comprising a reversibly occurring reaction medium, a shaping material, a binder, a binder resin, and a polyester polyol resin. It is necessary to become.
Furthermore, the addition amount of the polyester polyol resin is 0.3 to 5% by mass in the total amount, and the addition amount of the reversible thermochromic microcapsule pigment is 10% by mass or more.
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, even when a thermochromic microcapsule pigment that needs to be cooled at a low temperature in the production process is used as a colorant, the shrinkage fluctuation of the core diameter during freezing cooling can be achieved by adding a polyester polyol resin. Thus, a solid cursive body excellent in shape stability capable of maintaining a desired dimension during molding can be obtained.

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, A polyester polyol resin is used in addition to a core material component containing an agent and a binder resin.

  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 alcohol or branched aliphatic alcohol, dibenzyl cinnamate, heptyl stearate, didecyl adipate, dilauryl adipate, dimyristyl adipate, dicetyl adipate, distearyl adipate, trilaurin, trimyristin, tristearin, Dimyristin, distearin and the like can be arranged.

  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 a total carbon number of 12 to 24, 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, decanediol 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.
In addition, when adding 10 mass% or more, since the volume change rate in a frozen state becomes large, the structure of this invention becomes especially useful.

  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, the 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 polyester polyol resin used in the solid writing material according to the present invention is a polymer compound composed of an alcohol having at least an ester bond (—CO—O—) and two or more hydroxyl groups in the main chain as one kind of alkylene resin. . Since the (CH) group of —CH ₂ (CH) _n —CH ₂ — in the molecule is about 50%, it does not react with moisture in the atmosphere, and moisture is not lost even when the temperature is raised from a cooled state to room temperature. It is a substance that is difficult to absorb.

Examples of the polyester polyol resin include “Paogen” manufactured by Daiichi Kogyo Seiyaku Co., Ltd. and “Byron 300” manufactured by Toyobo Co., Ltd.
The blending amount is 0.3 to 5% by mass in the total amount, preferably 0.5 to 3% by mass, and if it is within this range, the action for reducing the diameter reduction of the solid cursive when freeze-cooling is particularly effective. Highly demonstrated.

  As the shaping material used for the solid cursive according to the present invention, for example, wax, gelling agent, clay and the like can be used. As the wax, any conventionally known wax may be used. 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 a sucrose fatty acid ester or a dextrin fatty acid ester, it is 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 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 with respect to 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.
If the melting point of the hindered amine compound is 120 ° C. or lower, a solid cursive material can be produced without excessive heating during production, thereby preventing the reversible thermochromic microcapsule pigment and various additives from deteriorating. it can.
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.

  Various additives can be added to the solid cursive according to the present invention as necessary. Examples of the additives include viscosity modifiers, fungicides, antiseptics, antibacterial agents, ultraviolet light inhibitors, and fragrances.

  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, so that they 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.

  After 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. Conventionally, when the microcapsule pigment is cooled until it freezes and then returned to room temperature, the microcapsule pigment undergoes a volume change, the outer diameter of the molded core shrinks, and the desired core diameter cannot be obtained. there were. In the present invention, since a skeleton that does not react with moisture can be formed in the solid writing body by blending a polyester polyol resin that hardly absorbs moisture, it can be used in the atmosphere even during cooling or when the temperature is raised from the cooled state to room temperature. It is possible to suppress swelling of the outer diameter of the core without absorbing moisture. For this reason, it is possible to manufacture products with stable quality without causing problems such as cracks in the outer shell when it becomes a core-sheath structure with an outer shell that can no longer be accommodated on the wooden shaft in the form of a pencil. Is possible.

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) Sanyo Chemical Industries, Ltd., trade name: Sun Wax 171-P
(2) Product name: High Wax 2203A, manufactured by Mitsui Chemicals, Inc.
(3) Yashara Chemical Co., Ltd., trade name: Neowax LA-05
(4) Product name: Ryoto Sugar Ester P-170, manufactured by Mitsubishi Chemical Foods Corporation
(5) Product name: LMS-200, manufactured by Fuji Talc Industry Co., Ltd.
(6) Product name: Paogen PP-15, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
(7) Product name: TINUVIN770DF, manufactured by BASF

(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.

The actual size of the core diameter (outer diameter) of each solid cursive A obtained in the examples and comparative examples was measured, and the dimensional difference from that before freezing (cooled at room temperature without cooling to −20 ° C.). (Μm) was measured. In addition, for the actual size measurement, 10 samples each were measured using a laser type outer diameter measuring instrument [manufactured by Keyence Corporation, LS-3001], and an average value was obtained.
Moreover, the external appearance state of each solid cursive B after coloring was confirmed by visual observation.
The results of the test are shown below.

In addition, the evaluation regarding the symbol in the said table | surface is as follows.
State of outer shell ○: A uniform covering state is formed without cracking or bending.
X: Generation | occurrence | production of a crack is seen or the shape is curving.

Preparation of Pencils Ten pencils were obtained by storage molding in a round outer shaft (wood shaft) using the solid cursive bodies A and B obtained using Examples 1-5.
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 five 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.

  The solid cursive according to the present invention can be used for various writing tools such as marking pens, pencils, and colored pencils, drawing materials for coloring and drawing, temperature indicating materials such as temperature indicators, and the like.

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 (5)

  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 cursive material comprising a reversible thermochromic microcapsule pigment encapsulating a temperature-sensitive color-changing color memory composition comprising, a shaping material, a filler, a binder resin, and a polyester polyol resin.   The solid cursive according to claim 1, wherein the amount of the polyester polyol resin added is 0.3 to 5% by mass in the total amount.   The solid cursive according to claim 1 or 2, wherein an addition amount of the reversible thermochromic microcapsule pigment is 10% by mass or more.   A solid cursive body comprising the solid cursive body according to any one of claims 1 to 3 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 body according to claim 1 and a friction body.

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