JP2014080453A - Solid writing body and solid writing body setting using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solid writing body in which discoloration of calligraphy is favorable, and temporal stability after color change is excellent.SOLUTION: A solid writing body includes: (1) a reversible thermochromic microcapsule pigment that includes a reversible thermochromic composition that includes: at least (a) an electron donative coloration organic compound, (b) an electron-accepting compound, (c) a reaction medium that reversibly generates an electron giving and receiving reaction by the (a) component and (b) component in a specific temperature zone; (2) a vehicle; and (3) a basicity group-containing resin.

Description

  The present invention relates to a solid cursive body and a solid cursive set using the same. More specifically, the present invention relates to a solid cursive body capable of forming a handwriting having reversible thermochromic properties and a solid cursive body set including a solid cursive body and a friction body.

  Conventionally, solid cursives using reversible thermochromic compositions capable of reversibly 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.

  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, resulting in a highly convenient handwriting that can be corrected in error. For example, it can be used for writing in a notebook or notebook, drawing, or the like. However, in the solid cursive material, depending on the material used for the shaping material, the discoloration or decoloring is not sufficient, or the discolored or decolored handwriting that has been discolored or decolored after being discolored or decolored is used. There was room for improvement as a solid cursive script, such as poor stability.

  There have already been several examples of studying how to obtain a solid writing material in which a microcapsule pigment in which a reversible thermochromic composition is encapsulated in a microcapsule is uniformly dispersed in a shaping material.

  Patent Document 1 describes that various waxes can be used as a microcapsule encapsulating a reversible thermosensitive dye and a shaping material. In the example of this document, paraffin wax is used as a shaping material. Patent Documents 2 and 3 also disclose a solid writing material including a microcapsule pigment in which a reversible thermochromic composition is encapsulated in a microcapsule and a shaping material. In these documents, it is disclosed that various materials such as paraffin wax, animal and plant waxes, higher alcohols, ketones, fat fatty acids, liquid hydrocarbons, and the like can be used as excipients. .

  However, solid writing instruments including these reversible thermochromic microcapsules have not necessarily had sufficient physical properties. That is, when general paraffin is used as the shaping material, the rigidity as a solid writing instrument may be insufficient, or the formability of the writing material may be insufficient. For this reason, in order to improve such a physical characteristic and to make a solid cursive tough, combining various resins with a shaping material is examined. However, according to the study by the present inventors, for example, when general dextrin or polyacrylate is combined with a solid cursive character as described above, the physical properties are improved, but the characteristics as a cursive character are improved. It was found that there were points to be improved. Specifically, it has been found that the writability, discoloration or erasability, or the aging stability of the handwriting after discoloration or decoloration changes, and in particular, the discoloration or decolorization is often insufficient.

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

  In view of the above-described problems, the present invention aims to provide a solid cursive material with good discoloration or decoloring property of handwriting and excellent temporal stability after discoloration or decoloration. is there.

The solid cursive according to the present invention is:
(1) 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 component (a) and the component (b) in a specific temperature range;
It comprises a reversible thermochromic microcapsule pigment encapsulating a reversible thermochromic composition containing, (2) a shaping material, and (3) a basic group-containing resin.

  Also. The solid cursive set according to the present invention comprises the solid cursive and the friction body.

  ADVANTAGE OF THE INVENTION According to this invention, the discoloration and erasing of a handwriting are favorable, and the solid cursive body with the temporal stability of the discolored and erasing handwriting is also provided.

It is a graph explaining the hysteresis characteristic in the color density-temperature curve of the heat decoloring type reversible thermochromic composition used in the present invention. It is a graph explaining the hysteresis characteristic in the color density-temperature curve of the heat decoloring type reversible thermochromic composition having color memory used in the present invention. It is a graph explaining the hysteresis characteristic in the color density-temperature curve of the heat coloring type reversible thermochromic composition used in the present invention.

  The embodiment of the present invention will be described in detail as follows.

  The solid cursive of the present invention comprises (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) an electron-donating reaction by the components (a) and (b) in a specific temperature range. A reversible thermochromic composition in a colored state comprising at least a reaction medium that is generated, or a reversible thermochromic microcapsule pigment in which the reversible thermochromic composition is encapsulated in microcapsules in a shapeable wax. Widely used waxes are effective as they are dispersed and hardened.

  Specific examples of the excipient include petroleum waxes such as paraffin wax, microcrystalline wax, petrolactam, oxidized paraffin wax and oxidized petrolactam having a melting point of 40 to 120 ° C., oxidized polyethylene wax, montanic acid wax, and ethylene vinyl acetate. Synthetic waxes such as copolymer wax, ethylene acrylic copolymer wax, vinyl ether wax, shellac, carnauba wax, castor wax, animal and plant waxes such as beef tallow oil, behenyl behenate, stearyl bebenate, stearyl palmitate, stearyl myristate , Stearyl laurate, stearyl stearate, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, stearone, behenic acid, Fatty fatty acids, liquids such as esters, higher alcohols, ketones, fatty acids, palm oil, liquid paraffin, polybutene, polybutadiene, styrene oligomers, etc., such as esters of arylic acid, palmitic acid, myristic acid, lauric acid, lignomorinic acid, and serotic acid And hydrocarbons.

  The solid cursive according to the present invention includes a basic group-containing resin. Here, the basic group means a group capable of reacting with an acid group. For example, not only a terminal group such as a primary amino group, a secondary amino group, a maternity amino group, and an amide group, but also an amide bond and an imide group. Includes binding and the like. The main chain structure of the resin is not particularly limited, and may be either a saturated hydrocarbon chain or an unsaturated hydrocarbon chain, and may contain an aromatic group. Yes. Further, it may be a linear or branched structure, and may have a cyclic structure. Furthermore, an ether bond or a carbonyl bond may be included as necessary. Further, it may be a homopolymer, a copolymer, or a graft polymer. Furthermore, when it is a copolymer, it may be a random copolymer or a block copolymer. Furthermore, it may be a synthetic resin or a natural resin.

  The basic group-containing resin may have a substituent other than the basic group as long as the effects of the present invention are not impaired. Such substituents include hydroxyl groups, cyano groups, nitro groups, nitroso groups and halogens. Moreover, although acid groups, such as a carboxyl group and a sulfo group, may be included, care should be taken because the effects of the present invention may not be sufficiently exerted if included in excess of the basic group. In such a case, the entire basic group-containing resin is preferably basic.

  Various kinds of such basic group-containing resins are known, and can be arbitrarily selected as necessary. Specific examples include polyamide resins, polyamine resins, polyacrylamide resins, polyurethane resins, urea resins, polyimide resins, polyalkyleneimine resins, polyamideimide resins, polyethyleneimine resins, gelatin, or aminated natural resins. Of these, polyamide resins, polyalkyleneimine resins, polyacrylamide resins, gelatin, and aminated natural resins are preferable, and nylon, polyethyleneimine, polyacrylamide, gelatin, and aminated starch are particularly preferable. Most preferred are nylon, polyethyleneimine, and aminated starch. Since these resins do not contain acid groups and residual acids in the molecule, they are considered to work suitably. Various types of such basic group-containing resins are commercially available, and they can also be used.

  In the present invention, the reason why the use of a basic group-containing resin improves the stability over time after discoloration or decoloration of the handwriting has not been fully elucidated, but is presumed to be due to the following reasons. ing. Since the basic group-containing resin is a polymer compound, it is difficult to penetrate into the wall film of the microcapsule, and it is difficult to cause an interaction that affects the discoloration and decoloring of the inclusion, and a reversible thermochromic composition. It is thought that it is difficult to impair the original function of things. In addition, when the electron-accepting compound and the electron-donating compound are leached out of the microcapsule, the electron-donating compound becomes an electron-accepting material such as a shaping material, filler, and various additives existing outside the electron-accepting compound and the microcapsule. May react and discolor, but the reaction is also inhibited by preferential coordination of the basic groups contained in the resin to the electron-accepting compound that has been leached out of the microcapsule. . Since the basic group is a powerful electron donating group, it is considered that the handwriting is favorably discolored and decolored, and the discolored and decolored handwriting has good stability over time.

  The solid cursive according to the present invention can be written on a medium such as paper, and the handwriting can be discolored by applying heat to the handwriting. This discoloration of the handwriting is realized by the reversible thermochromic composition constituting the handwriting. In the present invention, “discoloration” includes not only color change but also “color development” or “decoloration”.

  In the present invention, any reversible thermochromic composition can be used. Such a reversible thermochromic composition changes color before and after a predetermined temperature (color change point), decolored in a temperature range above the high temperature side color change point, and develops color in a temperature range below the low temperature side color change point. Presents a state, and only one of the two states is present in the normal temperature range, and the other state is maintained while the heat or cold required to develop the state is applied. However, when the application of heat or cold is no longer applied, the reversible thermochromic composition of the heat decoloring type that returns to the state exhibited in the normal temperature range and has a relatively small hysteresis width (ΔH = 1 to 7 ° C.) can be applied. (See FIG. 1). Such reversible thermochromic compositions are described in, for example, Japanese Patent Publication No. 51-44706, Japanese Patent Publication No. 51-44707, Japanese Patent Publication No. 1-29398, and the like.

  Further, the curve shape showing a large hysteresis characteristic (ΔH = 8 to 70 ° C.) and plotting a change in color density due to a temperature change is opposite to the case where the temperature is raised from a lower temperature side than the color change temperature range. The color changes by following a path that differs greatly depending on whether the temperature is lowered from the high temperature range, and exhibits a first hue in the low temperature range (coloring state) or a second hue in the high temperature range (disappears) It is also possible to use a heat decoloring reversible thermochromic composition having color memory that can maintain the color state in a specific temperature range (see FIG. 2). Such reversible thermochromic compositions include, for example, JP-B-4-17154, JP-A-7-179777, JP-A-7-33997, JP-A-8-39936, JP-A-2005-1369. It is described in Japanese Patent Laid-Open No. 2006-137886, Japanese Patent Laid-Open No. 2006-188660, and the like.

  The hysteresis characteristics in the color density-temperature curve of the reversible thermochromic composition will be described with reference to the graph of FIG.

In FIG. 2, the vertical axis represents color density and the horizontal axis represents temperature. The change in color density due to the temperature change proceeds along the arrow. Here, A is a point indicating a density at a temperature t ₄ (hereinafter referred to as a complete decoloring temperature) reaching a completely decolored state, and B is a temperature t ₃ (hereinafter referred to as a decoloring start temperature) at which decoloring starts. C is a point indicating a density at a temperature t ₂ at which color development starts (hereinafter referred to as a color development start temperature), and D is a temperature t ₁ at which a fully colored state is reached (hereinafter referred to as a color development start temperature). , Referred to as a complete color development temperature).

  The length of the line segment EF is a scale indicating the discoloration contrast, and the length of the line segment HG is a temperature width indicating the degree of hysteresis (hereinafter referred to as hysteresis width ΔH). It is easy to maintain each state before and after the color change.

Here, the difference between t ₄ and t ₃ , or the difference between t ₂ and t ₁ (Δt) is a scale indicating the sensitivity of discoloration.

Furthermore, in order to allow only one specific state to exist in the normal temperature region among the color development / decoloration states of the reversible thermochromic composition, and to easily discolor the handwriting by the reversible thermochromic composition by friction, it is necessary to completely erase the color. The color temperature (t ₄ ) is 45 to 90 ° C., and the color development start temperature (t ₂ ) is −50 to 10 ° C.

Here, the discoloration state can be maintained in a normal temperature range, and in order to facilitate discoloration due to friction of handwriting, the complete decolorization temperature (t ₄ ) is 45 to 95 ° C., and the color development start temperature (t ₂ ). Is not more than −50 to 10 ° C. When the heating is stopped from the color development state through the decolorization start temperature (t ₃ ) and not reaching the complete decolorization temperature (t ₄ ), the first The phenomenon of returning to the state occurs, and even if the cooling is stopped in the state where the color development start temperature (t ₂ ) has not reached the complete color development temperature (t ₁ ) from the decolored state, the color developed state is maintained. Therefore, if the complete color erasing temperature (t ₄ ) is 45 ° C. or more exceeding the normal temperature range, the color development state is maintained in the normal use state, and the color development start temperature (t ₂ ) is within the normal temperature range. If the temperature is below -50 to 10 ° C, the decolored state is in normal use Maintained.

Further, when the handwriting is erased by friction, if the complete color erasing temperature (t ₄ ) is 95 ° C. or less, the handwriting formed on the writing surface can be sufficiently discolored by frictional heat due to several times of friction by the friction member. .
When the complete decolorization temperature (t ₄ ) exceeds 95 ° C., the frictional heat obtained by friction with the friction member is difficult to reach the complete decolorization temperature, so that it is difficult to discolor easily and the number of friction increases. Alternatively, the writing surface tends to be damaged because the load tends to be excessively rubbed.
Therefore, the temperature setting is an important requirement for a heat erasable writing instrument that selectively displays a discolored handwriting on the writing surface and can satisfy convenience and practicality. In the temperature setting of the complete color erasing temperature (t ₄ ), a higher temperature is preferable in order to maintain the color development state in a normal use state, and the frictional heat due to friction is a complete color erasure temperature ( In order to exceed t ₄ ), a low temperature is preferred. Therefore, the complete decoloring temperature (t ₄ ) is preferably 50 to 90 ° C., more preferably 60 to 80 ° C.

Further, in the temperature setting of the color development start temperature (t ₂ ) described above, it is preferably a lower temperature in order to maintain the decolored state in a normal use state, and −50 to 5 ° C. is preferable. -50-0 degreeC is more suitable. In order to make the reversible thermochromic composition dispersed in the cursive body into a colored state in advance, it is preferable to cool in a general-purpose freezer as a cooling means, but considering the cooling capacity of the freezer,- Up to 30 ° C. is the limit, and therefore the complete color development temperature (t ₁ ) is −30 ° C. or higher. In the present invention, the hysteresis width (ΔH) is in the range of 50 to 80 ° C., preferably 55 to 80 ° C., more preferably 60 to 80 ° C.

  Specific examples of the compounds constituting the reversible thermochromic composition in the present invention are as follows.

  In the present invention, the component (a), that is, the electron donating color-forming organic compound includes diphenylmethane phthalides, phenyl indolyl phthalides, indolyl phthalides, diphenyl methane azaphthalides, phenyl indolyl azaphthalide And fluoranes, stylinoquinolines, 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-d) Pyrimidine-5,1 '(3'H) isobenzofuran] -3'-one, 2- (di-n-butylamino) -8- (di-n-butylamino) -4-methyl-, spiro [5H -(1) Benzopyrano (2,3-d) pyrimidine-5,1 '(3'H) isobenzofuran] -3'-one, 2- (di-n-butylamino) -8- (diethylamino) -4 -Methyl-, spiro [5H- (1) Nzopyrano (2,3-d) 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-d) pyrimidine-5,1 '(3'H) isobenzofuran] -3'-one, 2- (di-n- Butylamino) -8- (di-n-butylamino) -4-phenyl, 3- (2-methoxy-4-dimethylaminophenyl) -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-diethyl) Minofeniru) -3- (1-pentyl-2-methylindole-3-yl) -4,5,6,7-tetrachloro phthalide, and the like.

  Furthermore, pyridine-based, quinazoline-based, bisquinazoline-based compounds and the like that are effective in developing fluorescent yellow to red color development can be mentioned. Specifically, 4- [2,6-bis (2 -Ethoxyphenyl) -4-pyridinyl] -N, N-dimethylbenzenamine and the like.

  As the electron-accepting compound of component (b), a group of compounds having active protons, a group of pseudo-acidic compounds (a group of compounds that are not acids but act as an acid in the composition and cause component (a) 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. Alternatively, those having an amide group, a halogen group, etc., and bis-type and tris-type phenols, phenol-aldehyde condensation resins and the like can be mentioned. Moreover, the metal salt of the compound which has the said phenolic hydroxyl group may be sufficient.

  Specific examples of such component (b) include phenol, o-cresol, tertiary butylcatechol, nonylphenol, n-octylphenol, n-dodecylphenol, n-stearylphenol, p-chlorophenol, p-bromophenol, o-phenylphenol, n-butyl p-hydroxybenzoate, n-octyl p-hydroxybenzoate, resorcin, dodecyl gallate, 2,2-bis (4-hydroxyphenyl) propane, 4,4-dihydroxydiphenylsulfone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) sulfide, 1-phenyl-1,1-bis (4 -Hydroxyphenyl) ethane, 1,1-bis ( -Hydroxyphenyl) -3-methylbutane, 1,1-bis (4-hydroxyphenyl) -2-methylpropane, 1,1-bis (4-hydroxyphenyl) n-hexane, 1,1-bis (4-hydroxy) Phenyl) 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) ethyl propionate, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-hydroxy) Phenyl) n- heptane, 2,2-bis (4-hydroxyphenyl) n- nonane, and the like.

  The compound having a phenolic hydroxyl group can develop the most effective thermochromic property, but aromatic carboxylic acids and aliphatic carboxylic acids having 2 to 5 carbon atoms, carboxylic acid metal salts, acidic phosphate esters and their It may be a compound selected from metal salts, 1,2,3-triazole and derivatives thereof.

  The (c) component of the reaction medium that causes the electron transfer reaction by the (a) component and the (b) component to occur reversibly in a specific temperature range is as follows. As the component (c), alcohols, esters, ketones, ethers, and acid amides can be used.

  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 are used.

  Also, fatty acid ester compounds obtained from an odd aliphatic monohydric alcohol having 9 or more carbon atoms and an aliphatic carboxylic acid having an even number of carbon atoms, n-pentyl alcohol or n-heptyl alcohol, and an even 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 is also effective.

  Specifically, n-pentadecyl acetate, n-tridecyl butyrate, n-pentadecyl butyrate, n-undecyl caproate, n-tridecyl caproate, n-pentadecyl caproate, n-nonyl caprylate, n-undecyl caprylate, N-tridecyl caprylate, n-pentadecyl caprylate, n-heptyl caprate, n-nonyl caprate, n-undecyl caprate, n-tridecyl caprate, n-pentadecyl caprate, n-pentyl laurate, lauric acid n-heptyl, n-nonyl laurate, n-undecyl laurate, n-tridecyl laurate, n-pentadecyl laurate, n-pentyl myristate, n-heptyl myristate, n-nonyl myristate, n-myristate Undecyl, n-tridecyl myristate, N-pentadecyl ristinate, n-pentyl palmitate, n-heptyl palmitate, n-nonyl palmitate, n-undecyl palmitate, n-tridecyl palmitate, n-pentadecyl palmitate, n-nonyl stearate, stearic acid n-undecyl, n-tridecyl stearate, n-pentadecyl stearate, n-nonyl eicosanoate, n-undecyl eicosanoate, n-tridecyl eicosanoate, n-pentadecyl eicosanoate, n-nonyl behenate, n-behenate Examples include undecyl, n-tridecyl behenate, and n-pentadecyl behenate.

  As the ketones, aliphatic ketones having a total carbon number of 10 or more are effective, and 2-decanone, 3-decanone, 4-decanone, 2-undecanone, 3-undecanone, 4-undecanone, and 5-undecanone. 2-dodecanone, 3-dodecanone, 4-dodecanone, 5-dodecanone, 2-tridecanone, 3-tridecanone, 2-tetradecanone, 2-pentadecanone, 8-pentadecanone, 2-hexadecanone, 3-hexadecanone, 9-heptadecanone, 2 -Pentadecanone, 2-octadecanone, 2-nonadecanone, 10-nonadacanone, 2-eicosanone, 11-eicosanone, 2-heneicosanone, 2-docosanone, laurone, stearone and the like.

  Further, arylalkyl ketones having 12 to 24 carbon atoms in total, for example, n-octadecanophenone, n-heptadecanophenone, n-hexadecanophenone, n-pentadecanophenone, n-tetradecano Phenone, 4-n-dodecanacetophenone, n-tridecanophenone, 4-n-undecanoacetophenone, n-laurophenone, 4-n-decanoacetophenone, n-undecanophenone, 4-n-nonylacetophenone, n -Decanophenone, 4-n-octylacetophenone, n-nonanophenone, 4-n-heptylacetophenone, n-octanophenone, 4-n-hexylacetophenone, 4-n-cyclohexylacetophenone, 4-tert-butylpropiophenone, n-heptaphenone, 4-n-pentylacetopheno , Mention may be made of phenyl ketone, benzyl -n- butyl ketone, 4-n-butyl acetophenone, n- hexanophenone, 4-isobutyl acetophenone, 1-acetonaphthone, 2-acetonaphthone, cyclopentyl phenyl ketone.

  As ethers, aliphatic ethers having 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、ｑ１は０〜２の整数を示し、Ｘ^１のいずれか一方は−（ＣＨ_２）_ｋＯＣＯＲ’又は−（ＣＨ_２）_ｋＣＯＯＲ’であり、他方は水素原子であり、ｋ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、Ｙ^１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、ｐ１はそれぞれ独立に１〜３の整数を示す。〕 Furthermore, as the component (c), a compound represented by the following general formula (1) described in JP-A No. 2006-137886 is preferably used.

[Wherein R ¹ represents a hydrogen atom or a methyl group, q ¹ represents an integer of 0 to 2, and ^one of X ¹ is — (CH ₂ ) _k OCOR ′ or — (CH ₂ ) _k COOR ′ And the other is a hydrogen atom, k represents an integer of 0 to 2, R ′ represents an alkyl group or an alkenyl group having 4 or more carbon atoms, and Y ¹ is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. An alkyl group, a methoxy group, or a halogen is shown, p1 shows the integer of 1-3 each independently. ]

Among the compounds represented by the formula (1), when R ¹ is a hydrogen atom, it is preferable because a reversible thermochromic composition having a wider hysteresis width can be obtained, and R ¹ is a hydrogen atom, and , Q1 is more preferably 0.

（式中のＲは炭素数８以上のアルキル基又はアルケニル基を示すが、好ましくは炭素数１０〜２４のアルキル基、更に好ましくは炭素数１２〜２２のアルキル基である。） Of the compounds represented by the general formula (1), a compound represented by the following general formula (1a) is more preferably used.

(In the formula, R represents an alkyl group or alkenyl group having 8 or more carbon atoms, preferably an alkyl group having 10 to 24 carbon atoms, more preferably an alkyl group having 12 to 22 carbon atoms.)

  Specific examples of the compound include octanoic acid-4-benzyloxyphenylethyl, nonanoic acid-4-benzyloxyphenylethyl, decanoic acid-4-benzyloxyphenylethyl, undecanoic acid-4-benzyloxyphenylethyl, and dodecanoic acid. -4-benzyloxyphenylethyl, tridecanoic acid-4-benzyloxyphenylethyl, tetradecanoic acid-4-benzyloxyphenylethyl, pentadecanoic acid-4-benzyloxyphenylethyl, hexadecanoic acid-4-benzyloxyphenylethyl, heptadecanoic acid Examples thereof include -4-benzyloxyphenylethyl and octadecanoic acid-4-benzyloxyphenylethyl.

〔式中、Ｒ^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のアルキル基を示し、ｐ２はそれぞれ独立に１〜３の整数を示し、Ｘ^２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、またはハロゲンを示す。〕 Furthermore, the compound shown by following General formula (2) described in Unexamined-Japanese-Patent No. 2006-188660 can also be used as said (c) component.

[Wherein, R ² represents an alkyl group or alkenyl group having 8 or more carbon atoms, preferably an alkyl group having 10 to 24 carbon atoms, more preferably an alkyl group having 12 to 22 carbon atoms; 3 represents an integer of 3 and each X ² independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or halogen. ]

  Examples of the compound include octanoic acid-4-benzyloxyphenylethyl, nonanoic acid-4-benzyloxyphenylethyl, decanoic acid-4-benzyloxyphenylethyl, undecanoic acid-4-benzyloxyphenylethyl, dodecanoic acid-4- Benzyloxyphenylethyl, tridecanoic acid-4-benzyloxyphenylethyl, tetradecanoic acid-4-benzyloxyphenylethyl, pentadecanoic acid-4-benzyloxyphenylethyl, hexadecanoic acid-4-benzyloxyphenylethyl, heptadecanoic acid-4- Benzyloxyphenylethyl, octadecanoic acid-4-benzyloxyphenylethyl, 1,1-diphenylmethyl octanoate, 1,1-diphenylmethyl nonanoate, 1,1-diphenylmethyl decanoate, 1,1-didecanoic acid Phenylmethyl, dodecanoic acid 1,1-diphenylmethyl, tridecanoic acid 1,1-diphenylmethyl, tetradecanoic acid 1,1-diphenylmethyl, pentadecanoic acid 1,1-diphenylmethyl, hexadecanoic acid 1,1-diphenylmethyl, heptadecanoic acid Examples include 1,1-diphenylmethyl and 1,1-diphenylmethyl octadecanoate.

（式中、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、メトキシ基、またはハロゲン原子のいずれかを示し、ｐ３はそれぞれ独立に１〜３の整数を示し、ｑ３は１〜２０の整数を示す。） Furthermore, a compound represented by the following general formula (3) can also be used as the component (c).

(In the formula, X ³ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, or a halogen atom; p 3 independently represents an integer of 1 to 3; 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^４はそれぞれ独立に炭素数１〜２１のアルキル基又はアルケニル基を示し、ｐ４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 (4) can also be used as the component (c).

(In the formula, each R ⁴ independently represents an alkyl group or an alkenyl group having 1 to 21 carbon atoms, and p 4 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^５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、またはハロゲン原子のいずれかを示し、ｐ５はそれぞれ独立に１〜３の整数を示し、ｑ５は１〜２０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, each X ⁵ 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, and p5 is each independently an integer of 1 to 3) Q5 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.

  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 (see FIG. 3).

The component ratio of the component (b), component (b), and component (c) depends on the concentration, the color change temperature, the color change form, and the type of each component. The ratio is in the range of (b) component 1 to (b) component 0.1 to 50, preferably 0.5 to 20, (c) component 1 to 800, preferably 5 to 200 (the ratio). Are based on mass).
Each component may be a mixture of two or more.

  In the present invention, the reversible thermochromic composition comprising the above three components is used in a microcapsule. For this reason, the reversible thermochromic composition is maintained in the same composition under various use conditions, and the same effects can be achieved.

  The reversible thermochromic microcapsule pigment used in the solid cursive of the present invention has an antioxidant, an ultraviolet absorber, an infrared absorber, a dissolution aid, an antiseptic / antifungal agent, etc., as long as the function is not affected. These various additives can be added.

  Although the said microcapsule is not specifically limited, It is preferable that an average particle diameter is 0.1-50 micrometers. If it is smaller than this range, the color density tends to be lowered, and 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 0.3-20 micrometers, More preferably, it is 0.5-10 micrometers, If it exists in this range, a coloring state will also be favorable and dispersion stability and workability will become further better.

  The average particle diameter of the microcapsule pigment and the endothermic microcapsule referred to in the present invention is represented by the value of D50 expressed on a volume basis when the outer diameter of the particle is measured. Here, the laser diffraction / scattering formula is used. A value obtained by measuring using a 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.

  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 microencapsulation includes an isocyanate-based interfacial polymerization method, an in situ polymerization method such as melamine-formalin, a liquid curing coating method, a phase separation method from an aqueous solution, a phase separation method from an organic solvent, a melt dispersion cooling method, There are an air suspension coating method, a spray drying method, and the like, which are appropriately selected according to the application. Further, a secondary resin film may be provided on the surface of the microcapsule according to the purpose to impart durability, or the surface characteristics may be modified for practical use.

  The form of the microcapsule does not refuse application of a circular cross section, but a non-circular cross section is effective.

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

  The compounding ratio of the shaping material, the basic group-containing resin, and the microcapsules is not particularly limited, but the shaping material is generally 0.1 to 5, preferably 0.5 to the microcapsule 1. 2 and the basic group-containing resin is 0.01 to 10, preferably. 02-2. (All of the above ratios are based on mass).

  Various additives can be added to the solid cursive of the present invention as necessary. Examples of the additive include an extender, a viscosity modifier, a fungicide, an antiseptic, an antibacterial agent, an ultraviolet light inhibitor, a light stabilizer, and a fragrance. Examples of the extender include talc, clay, silica, calcium carbonate, barium sulfate, alumina, mica, boron nitride, potassium titanate, and glass flakes, and talc and calcium carbonate are particularly preferred from the viewpoint of formability. Good. The extender is blended for the purpose of improving the strength and adjusting the writing quality of the solid cursive of the present invention.

  The solid cursive of the present invention can be achieved by blending a non-thermochromic colorant such as a dye or pigment when changing between colored (1) and colored (2).

  The solid cursive of 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 tool or a 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 warm water, and a hair dryer, but it is preferable that a friction member is used as a means for easily changing the color. .

  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 butadiene 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 a friction member on the exterior of the writing instrument, it becomes excellent in portability.

  The present invention will be described below by examples.

Example 1
<Manufacture of microcapsules>
(I) 2- (dibutylamino) -8- (dipentylamino) -4-methyl-spiro [5H- [1] benzopyrano [2,3-g] pyrimidine-5,1 ′ (3′H) — 1.0 part of isobenzofuran] -3-one,
(B) As a component, 4,4 ′-(2-ethylhexane-1,1-diyl) diphenol 3.0 parts, 2,2-bis (4′-hydroxyphenyl) -hexafluoropropane 5.0 parts,
(C) A reversible thermochromic composition comprising 50.0 parts by mass of capric acid-4-benzyloxyphenylethyl as a component is heated and dissolved, and 30.0 parts by mass of an aromatic isocyanate prepolymer as a wall film material, a cosolvent The solution in which 40.0 parts by mass was mixed was emulsified and dispersed in an 8% aqueous polyvinyl alcohol solution. After stirring while heating, 2.5 parts by mass of a water-soluble aliphatic modified amine was added, and further stirring was continued. Thus, a reversible thermochromic microcapsule suspension was obtained. The suspension was centrifuged to isolate reversible thermochromic microcapsules. The average particle size of the microcapsules is 2.3 μm, t ₁ : −20 ° C., t ₂ : −10 ° C., t ₃ : 48 ° C., t ₄ : 58 ° C., ΔH: 68 ° C., reversible heat. Color change composition: wall film = 2.6: 1.0. The macrocapsules exhibited hysteresis characteristics that reversibly change color from pink to colorless and from colorless to pink with temperature changes.

<Manufacture of solid cursive>
Microcapsule pigment A 40 parts by mass Polyolefin wax 30 parts by mass (Sanwax 131-P (trade name) manufactured by Sanyo Chemical Industries, Ltd.)
10 parts by weight of nylon 20 parts by weight of kaolin (extrinsic material) 20 parts by weight The above blend is kneaded with a kneader, and the resulting kneaded product is compression-molded with a press to form an outer diameter of 3 mm and a length of 60 mm to produce a solid cursive body Got.

Examples 2-9 and Comparative Examples 1-2
In the production of the solid cursive material, a solid cursive material was obtained in the same manner as in Example 1 except that the blending amount (part by mass) of each component was changed as shown in Table 1.

Solid Cursive Evaluation Method The handwriting erasability and handwriting erasing stability of the solid writing instrument were evaluated by the following methods.

<Handwriting erasability>
The handwriting on which writing was written on the writing paper A was abraded using a SEBS friction member, and the erasability at that time was evaluated by self-view.
A: The handwriting is easily erased and remains completely erased.
○: The handwriting is erased, but the written characters cannot be confirmed.
Δ: A part of the handwriting disappeared and the rest was seen, and the written characters could not be confirmed.
X: An afterimage of the handwriting is seen, and the written characters can be confirmed.
XX: Handwriting cannot be erased.

t ₁ complete color development temperature t ₂ color development start temperature t ₃ color erase start temperature t ₄ complete color erase temperature T ₁ complete color erase temperature T ₂ color erase start temperature T ₃ color development start temperature T ₄ complete color development temperature ΔH hysteresis width

Claims (5)

(1) 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 component (a) and the component (b) in a specific temperature range;
A solid cursive comprising: a reversible thermochromic microcapsule pigment encapsulating a reversible thermochromic composition comprising: (2) a shaping material; and (3) a basic group-containing resin.   The basic group contained in the basic group-containing resin is selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, an amide group, an amide bond, and an imide bond. Solid cursive.   The solid writing material according to claim 1 or 2, comprising a non-color-changing dye or pigment.   The solid cursive according to any one of claims 1 to 3, further comprising a friction member.   A solid cursive set comprising the solid cursive body according to any one of claims 1 to 3 and a friction body.

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