JP6168930B2 - Solid cursive and solid cursive set using the same - Google Patents

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.

  Furthermore, as an improved invention of Patent Documents 1 to 3, Patent Document 4 adds a hindered amine light stabilizer to suppress a residual color that is visually recognized when the handwriting is erased by heating, thereby improving rewriteability. Techniques for making them disclosed are disclosed.

On the other hand, in order to improve the strength and impact resistance of the solid cursive, a so-called multilayered solid cursive that surrounds the solid cursive with the outer shell is disclosed in Patent Documents 5 and 6.
Patent Document 5 describes a multi-layer core having a coating material coated on the outer peripheral surface of the core material with a material that is more easily worn than the core material. Further, the core core and the periphery are surrounded by a core envelope. There is a description of the multilayer core made.

In order to improve the strength and impact resistance of an excellent solid cursive material as described in Patent Document 4, the present inventors have used the technique related to the coating material described in Patent Documents 5 and 6. According to these studies, it was difficult to apply simply.
This is considered to be because a specific process necessary for producing a solid cursive body using the reversible thermochromic composition is affected. That is, the solid cursive is generally produced by pressing and molding the composition at a high temperature and extruding. In this process, a small amount of the reversible thermochromic composition bleeds out from the microcapsule, and therefore, irreversible color formation may occur when the component moves to the outer shell over time. For this reason, the color of the outer shell may be visually recognized as a residual color (afterimage) when the handwriting is erased.

Japanese Utility Model Publication No. 7-6248 JP 2008-291048 A JP 2009-166310 A JP 2013-91744 A JP 2007-246605 A JP 2006-205730 A JP 11-129623 A JP 2001-105732 A JP 2003-253149 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 object of the present invention is to maintain a high erasability without causing a residual color at the time of erasing handwriting even after lapse of time, and a solid writing excellent in strength and impact resistance. Is to provide a body.

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. An inner core comprising a reversible thermochromic microcapsule pigment encapsulating a temperature-sensitive color-changing color memory composition comprising a reversibly occurring reaction medium, a shaping material, and a hindered amine light stabilizer; and a shaping material And a hindered amine light stabilizer, and an outer shell covering the outer peripheral surface of the inner core.
Furthermore, the addition amount of the hindered amine light stabilizer is 0.05 to 5% by mass in the total amount of the outer shell, the molecular weight of the hindered amine light stabilizer is 1000 or less, and the outer shell contains a filler. It is a requirement that
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, by adding a hindered amine light stabilizer to the outer shell covering the periphery of the inner core, a small amount of the reversible thermochromic composition can be obtained by being pressurized at a high temperature during solid writing. Even when bleeding out from inside the microcapsule, it is possible to suppress irreversible color development when the component moves to the outer shell over time. Therefore, it is possible to maintain a high erasability without producing a residual color (afterimage) during handwriting erasing even after lapse of time, and to provide a solid cursive body excellent in strength and impact resistance. Further, since the initial hue can be maintained by suppressing the discoloration (coloring) of the outer shell over time, high designability can be maintained for a long period of time, particularly when the outer shell does not contain a colorant.

It is the figure which showed typically a part of cross section in the longitudinal direction of the solid cursive by this invention. It is the figure which showed typically the cross section in the vertical direction with the longitudinal direction of the solid cursive body by this invention. 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, a shaping material, and a hindered amine light containing a thermosensitive color-changing color memory composition comprising at least the components (a), (b), and (c). One characteristic is that an outer shell covering the outer peripheral surface is provided on the writable inner core containing the stabilizer, and a hindered amine light stabilizer is used in the outer shell.

  The configuration of the solid cursive body according to the present invention will be described below with reference to FIGS. 1 and 2. A cross-sectional view in the length direction of a typical solid cursive body (1) according to the present invention is as shown in FIG. 1, and a cross-sectional view in the direction perpendicular to the length direction is as shown in FIG. Specifically, the solid cursive according to the present invention includes an inner core (2) and an outer shell (3) that covers the outer peripheral surface thereof. The outer shell (3) contains a shaping material and a hindered amine light stabilizer.

  As a shaping material that can be used for the outer shell of the solid cursive according to the present invention, for example, a wax, a gelling agent, or the like can be used. Any wax may be used as long as it is conventionally known. Specifically, carnauba wax, wax, beeswax, microcrystalline wax, montan wax, candelilla wax, sucrose fatty acid ester, dextrin fatty acid ester. , Polyolefin wax, styrene-modified polyolefin wax, paraffin wax, 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.

（式中、Ｒ_１は炭素数１乃至３０のアルキル基を示し、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５はそれぞれ炭素数１乃至５のアルキル基を示し、ｎは１以上の整数を示し、Ｒ_６はｎ価の有機残基を示す。）
前記ヒンダードアミン系光安定剤の分子量が１０００以下であることにより賦形材との相溶性に富み、ブリードアウトし難くなるため、経時後も明瞭な筆跡を形成することができる。
尚、前記ヒンダードアミン系光安定剤の融点が１２０℃以下あると製造時に過度の熱を加えることなく固形筆記体を製造することができるため、可逆熱変色性マイクロカプセル顔料や各種添加剤が劣化することを防止できる。 Specific examples of the hindered amine light stabilizer added to the outer shell and the inner core are shown below.
Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate,
Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate,
A mixture of bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate;
Bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate 2- (3,5 -Di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl),
Tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate,
1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4 , 8,10-tetraoxaspiro [5.5] undecane mixed esterified product,
Mixed esterified product of 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol,
1,2,2,6,6-pentamethyl-4-piperidyl-methacrylate,
N, N ′, N ″, N ′ ″-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino)- Triazin-2-yl) -4,7-diazadecane-1,10-diamine,
N-methyl-3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperezinyl) pyrrolidine-2,5-dione,
Poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {2,2,6,6-tetramethyl-4-piperidyl} Imino] hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}),
Polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol,
Polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and N, N ′, N ″, N ′ ″-tetrakis- (4,6-bis −
(Butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine Reaction products of
Dibutylamine, 1,3-triazine, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6- Polycondensate with tetramethyl-4-piperidyl) butylamine,
Reaction product of decanedioic acid bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester (1,1-dimethylethyl hydroperoxide) and octane;
A reaction product of cyclohexane and peroxide N-butyl-2,2,6,6-tetramethyl-4-piperidineamine-2,4,6-trichloro-1,3,5-triazine and 2-aminoethanol The reaction product of can be illustrated.
In addition, as the hindered amine light stabilizer, a compound represented by the following general formula (A) is preferably used.

(In the formula, R ₁ represents an alkyl group having 1 to 30 carbon atoms, R ₂ , R ₃ , R ₄ and R ₅ each represents an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 1 or more. , R ₆ represents an n-valent organic residue.)
Since the hindered amine light stabilizer has a molecular weight of 1000 or less, it 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 light stabilizer is 120 ° C. or lower, a solid cursive material can be produced without applying excessive heat during production, so that the reversible thermochromic microcapsule pigment and various additives deteriorate. Can be prevented.

The amount of the hindered amine light stabilizer added to the inner core is preferably 0.1 to 5% by mass in the total amount of the inner core. 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.
On the other hand, the addition amount to the outer shell is preferably 0.05 to 5% by mass in the total amount of the outer shell. In the outer shell, the bleed-out component from the microcapsule pigment blended in the core causes irreversible color development when it moves to the outer shell over time. Since the migration amount of the component can be reduced by the light stabilizer, it may be 0.05% by mass or more, which is smaller than the addition amount to the core, and an equivalent amount is sufficient.
In addition, when blending microcapsule pigments in the outer shell, the amount of hindered amine light stabilizer added to the outer shell should be blended with the microcapsule pigment in order to effectively suppress the residual color during handwriting decoloration. It is preferable to add more than when not.

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 additives include colorants, fungicides, 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.
Further, if necessary, a reversible thermochromic microcapsule pigment described below can be added. 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.

  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 the solid cursive according to the present invention will be described with reference to FIG. In FIG. 3, 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 for the inner core of the solid writing material according to the present invention, a so-called leuco dye that is usually used for 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.

  The electron accepting compound of the component (b) encapsulated in the microcapsule pigment used for the inner core of the solid cursive according to the present invention includes a group of compounds having an active proton, a group of pseudo-acidic compounds (not an acid, but in the composition And a group of compounds having electron vacancies, and the like. 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.

  Furthermore, the specific alkoxyphenol compound (patent document 7) which has a C3-C18 linear or side chain alkyl group as an electron-accepting compound, specific hydroxybenzoic acid ester (patent document 8), gallic acid ester (patent) It is also possible to apply a heat-developing reversible thermochromic composition using literature 9).

  As component (c), which is a reaction medium for reversibly causing an electron transfer reaction by the component (a) and component (b) included in the microcapsule pigment used for the inner core of the solid cursive according to the present invention in a specific temperature range. Specific examples include alcohols, esters, ketones, and 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 blending ratio of the three components (A), (B), and (C) included in the microcapsule pigment used for the inner core of 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. However, the compounding ratio at which desired characteristics are generally obtained is (m) component: (b) component: (c) component = 1: 0.1-50: 1-800, preferably (B) 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 for the inner core of the solid cursive material according to the present invention includes an antioxidant, an ultraviolet absorber, an infrared absorber, a dissolution aid, an antiseptic / antifungal agent, etc., as long as the function is not affected. Various additives 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 for the inner core of the solid cursive according to the present invention is not particularly limited, but preferably has an average particle diameter of 0.1 to 50 μm. 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 workability tend to be inferior when used for the inner core of the 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 blending ratio of the microcapsule pigment used for the inner core of the solid cursive according to the present invention is preferably 1 to 70% by mass with respect to the total mass of the inner core of the solid cursive. If it is smaller than this range, the color density tends to decrease, and if it is larger than this range, the strength of the inner core of the solid cursive tends to decrease. Preferably, it is 5-50 mass%, More preferably, it is 10-40 mass%. If it exists in this range, the intensity | strength and handwriting density | concentration of a solid cursive body can be made compatible.

  For the microcapsule pigment, a generally known method as described in Non-Patent Document 1, for example, can be used as a production method. Specifically, 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.

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

  In particular, among the polyolefin waxes, those having a softening point in the range of 100 ° C. to 130 ° C. and a penetration of 10 or less are preferably used because of high writing feeling. When the penetration exceeds 10, there is a tendency that the inner core of the solid cursive body is too soft and difficult to write, and the handwriting is stretched on the paper surface during rubbing and erasing (wax is thinned). For this reason, the blank part of the writing surface is contaminated, and color transfer and stains to other papers occur.

  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, the smaller the number is, the harder the core is, and the larger the softer is the inner core of the solid cursive.

  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 core according to the present invention contains at least one sucrose fatty acid ester or 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 for the inner core of 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. It is. Specifically, Chiba Flour Milling Co., Ltd .: Leopard series, etc. are mentioned.

  The blending ratio of the shaping material used for the inner core of the solid cursive according to the present invention is preferably 0.2 to 70% by mass with respect to the total mass of the inner core. 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 within this range, both the shape of the inner core of the solid cursive and the handwriting density can be achieved.

  Various additives can be added to the inner core of the solid cursive according to the present invention, if necessary. Examples of the additives include resins, fillers, viscosity modifiers, fungicides, preservatives, antibacterial agents, ultraviolet light inhibitors, and fragrances. The resin is blended for the purpose of improving the strength of the inner core of the solid cursive material, and 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. Examples of the filler include talc, clay, silica, calcium carbonate, barium sulfate, alumina, mica, boron nitride, potassium titanate, and glass flakes. From this point, talc and calcium carbonate are preferable. The filler is blended for the purpose of improving the strength of the inner core of the solid cursive according to the present invention and adjusting the writing quality. As a compounding ratio of the filler used for the inner core of the solid cursive body by this invention, 10-55 mass% is preferable with respect to the inner core total mass. If it is smaller than this range, the strength of the inner core tends to be lowered, and if it is larger than this range, the color developability tends to be lowered or the writing quality tends to be poor.

  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.

  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, a solid cursive body provided with an outer shell covering the outer peripheral surface of the inner core by arranging an outer shell on the outer peripheral surface of the inner core lump and compressing it with a press. Can be obtained. In addition, the solid cursive according to the present invention typically has a two-layer structure of an inner core and an outer shell, but it can also have a multilayer structure higher than that. For example, the affinity between the inner core and the outer shell can be further increased by providing an intermediate layer having an appropriate hardness, thermal expansion coefficient, etc. between the inner core and the outer shell. Such an intermediate layer may be composed of a component containing a temperature-sensitive color-changing color memory composition similar to that of the inner core, or may not be writable. Two or more such intermediate layers may be provided. Furthermore, you may form the coating layer which consists of another coating component in an outer shell.

  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. Also, 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, while if the outer shell is thin, the inner shell is thin. Since the amount of exposure of the lead increases, 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 inner core of the solid cursive according to the present invention is preferably harder and more easily worn than the outer shell from the viewpoint of maintaining a good writing concentration. When an elastic resin such as ethylene vinyl acetate copolymer and its derivative or ethylene / acrylate copolymer is used at a high ratio as the material of the inner core, the core is less likely to be worn, and the writing concentration tends to decrease. Because there is, attention is necessary.

  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.

(Production of microcapsule pigment A)
(Ii) 9-ethyl (3-methylbutyl) amino-spiro [12H-benzo (α) xanthen-12,1 ′ (3′H) -isobenzofuran] -3′-one 5.0 parts as component (B) ) As components, 3.0 parts of 4,4 '-(2-ethylhexane-1,1-diyl) diphenol, 5.0 parts of 2,2-bis (4'-hydroxyphenyl) -hexafluoropropane, ) A temperature-sensitive color-changing color memory 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. To obtain a thermochromic microcapsule suspension. The suspension was centrifuged to isolate 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., temperature-sensitive discoloration. Sex color memory composition: wall film = 2.6: A behavior having a hysteresis characteristic of 1.0 was exhibited, and the color changed reversibly from pink to colorless and from colorless to pink.

(Production of microcapsule pigment B)
(I) Benzenamine, 4- [2,6bis (2,4-diethoxyphenyl) -4-pyridinyl] -N, N-dimethyl (2.5 parts) as component (2,) 2,2-bis ( 4'-hydroxyphenyl) hexafluoropropane (5.0 parts), 4,4 '-(2-methylpropylidene) bisphenol (3.0 parts), and (c) component 4-benzyloxyphenylethyl caprate from 50.0 parts A solution in which 30.0 parts by mass of an aromatic isocyanate prepolymer and 40.0 parts by mass of a co-solvent are mixed as a wall film material in an 8% aqueous solution of polyvinyl alcohol. After emulsifying and dispersing and stirring while heating, 2.5 parts by mass of a water-soluble aliphatic modified amine was added, and stirring was further continued to obtain a thermochromic microcapsule suspension. The suspension was centrifuged to isolate reversible thermochromic microcapsules.
The average particle diameter of the microcapsules is 2.2 μm, t ₁ : −16 ° C., t ₂ : −8 ° C., t ₃ : 48 ° C., t ₄ : 58 ° C., ΔH: 65 ° C., temperature-sensitive discoloration. Sex color memory composition: wall film = 2.6: 1.0 A behavior having a hysteresis characteristic was exhibited, and the color changed reversibly from yellow to colorless and from colorless to yellow.

Example 1
(Manufacture of inner core kneaded product)
Microcapsule pigment A (colorant) 20 parts by mass Polyolefin wax (shaping material) 15 parts by mass (Sanwax 131-P (trade name) manufactured by Sanyo Chemical Industries, Ltd., softening point 110 ° C., penetration 3.5 )
Sucrose fatty acid ester (shaped material) 15 parts by mass (Ryoto Sugar Ester P-170 (trade name) manufactured by Mitsubishi Chemical Foods Co., Ltd.)
Polyvinyl alcohol (resin) 2 parts by mass Talc (filler) 47 parts by mass Hindered amine light stabilizer 1 part by mass (TINUVIN 770DF (trade name) manufactured by BASF, melting point 81-85 ° C, molecular weight 480.7)
The above blend was kneaded with a kneader to obtain a kneaded product with an inner core.

(Manufacture of outer shell kneaded material)
Talc (filler) 69 parts by mass Sucrose fatty acid ester (shaped material) 10 parts by mass (Ryoto Sugar Ester P-170 (trade name) manufactured by Mitsubishi Chemical Foods Co., Ltd.)
Polyolefin wax (shaped material) 10 parts by mass (Sanyo Chemical Industries, Ltd. Sun Wax 131-P (trade name), softening point 110 ° C., penetration 3.5)
Ethylene vinyl acetate copolymer (elastic resin) 10 parts by mass (Evaflex EV150 (trade name), durometer A hardness 68 manufactured by Mitsui DuPont Polychemical Co., Ltd.)
1 part by weight of hindered amine light stabilizer (TINUVIN770DF (trade name) manufactured by BASF, melting point 81-85 ° C., molecular weight 480.7)
The above blend was kneaded with a kneader to obtain a kneaded product of the outer shell.

(Manufacture of solid cursive letters)
The outer shell kneaded material is wound around the outer peripheral surface of the obtained inner core kneaded material, and compression molded with a press. The outer diameter is 3 mm, the length is 60 mm (the inner core is 2 mm, and the outer shell has a coating thickness of A solid cursive body provided with an outer shell that was molded to 0.5 mm) and covered the outer peripheral surface of the inner core was obtained.

Example 2
(Manufacture of inner core)
Microcapsule pigment B (colorant) 25 parts by mass Polyolefin wax (shaping material) 15 parts by mass (Sunwax 131-P (trade name) manufactured by Sanyo Chemical Industries, Ltd., softening point 110 ° C., penetration 3.5 )
Sucrose fatty acid ester (shaped material) 15 parts by mass (Ryoto Sugar Ester P-170 (trade name) manufactured by Mitsubishi Chemical Foods Co., Ltd.)
Polyvinyl alcohol (resin) 2 parts by weight Talc (filler) 40 parts by weight Hindered amine light stabilizer 3 parts by weight (TINUVIN 144 (trade name) manufactured by BASF, melting point 146-150 ° C., molecular weight 685)
The above blend was kneaded with a kneader to obtain a kneaded product.
The obtained kneaded material was compression-molded with a press and molded into an outer diameter of 2 mm and a length of 60 mm to obtain an inner core.

(Manufacture of solid cursive letters)
The outer shell kneaded material of Example 1 is wound around the inner core, compression-molded by a press, and provided with an outer shell covering the outer peripheral surface of the inner core, thereby providing an outer diameter of 3 mm and a length of 60 mm (inner core Is a solid cursive body having a diameter of 2 mm and a coating thickness of the outer shell of 0.5 mm.

Example 3
(Manufacture of outer shell kneaded material)
Talc (filler) 69.8 parts by mass Sucrose fatty acid ester (shaped material) 10 parts by mass (Ryoto Sugar Ester P-170 (trade name) manufactured by Mitsubishi Chemical Foods Co., Ltd.)
Polyolefin wax (shaped material) 10 parts by mass (Sanyo Chemical Industries, Ltd. Sun Wax 131-P (trade name), softening point 110 ° C., penetration 3.5)
Ethylene vinyl acetate copolymer (elastic resin) 10 parts by mass (Evaflex EV150 (trade name), durometer A hardness 68 manufactured by Mitsui DuPont Polychemical Co., Ltd.)
0.2 parts by mass of hindered amine light stabilizer (TINUVIN 144 (trade name) manufactured by BASF, melting point: 146 to 150 ° C., molecular weight: 685)
The above blend was kneaded with a kneader to obtain a kneaded product of the outer shell.

(Manufacture of solid cursive letters)
The outer shell kneaded material was wound around the outer peripheral surface of the inner core kneaded material obtained in Example 2 and subjected to compression molding with a press. The outer diameter was 3 mm, the length was 60 mm (the inner core was 2 mm, the outer A solid cursive body having a shell thickness of 0.5 mm) provided with an outer shell covering the outer peripheral surface of the inner core was obtained.

Example 4
A solid cursive material was obtained in the same manner as in Example 1 except that 10 parts by mass of microcapsule pigment A was added and 59 parts by mass of talc was added in the production of the kneaded product of the outer shell.

Comparative Examples 1-4
Solid cursives were obtained in the same manner as in Examples 1 to 4, except that the hindered amine light stabilizer in the kneaded material of the outer shell was added to the same amount of talc and added.

After each solid writing material obtained in the examples and comparative examples was allowed to stand at room temperature for 90 days, a handwriting with an outer shell and an inner core was drawn on white fine paper, and erased by frictional heat using a friction body made of SEBS resin. Then, the residual color (afterimage) of the erased portion was visually observed. Moreover, about the solid cursives of Examples 1-3 and Comparative Examples 1-3, the hue of the outer shell 90 days after was observed visually, and compared with the initial stage.
The results of the test are shown below.

In addition, the evaluation regarding the symbol in the said table | surface is as follows.
Presence or absence of residual color ○: No residual color is seen.
X: A residual color is seen.
Hue hue ○: No change from initial.
X: Change in hue is observed.

Preparation of pencil Using the solid cursives obtained in Examples 1 to 4, a pencil was obtained by housing and forming it in a round outer shaft (wood shaft).
When writing on the paper surface using the pencil, a pink or yellow 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 the four pencils 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.

DESCRIPTION OF SYMBOLS 1 Solid cursive body according to the present invention 2 Inner core of the solid cursive body according to the present invention 3 Outer shell of the solid cursive body according to the present invention t ₁ Complete coloring temperature of the handwriting of the heat-erasable solid cursive body according to the present invention t ₂ Present invention Color development start temperature t of the heat-erasable type solid cursive handwriting by t ₃ Temperature of color erase start of the handwriting of the heat-erasable type solid handwriting according to the present invention t ₄ Complete decoloring temperature 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; An inner core comprising a reversible thermochromic microcapsule pigment encapsulating a temperature-sensitive color-changing color memory composition, a shaping material and a hindered amine light stabilizer, and a shaping material and a hindered amine light stabilizer. A solid cursive comprising an outer shell covering the outer peripheral surface of the inner core.   The solid cursive according to claim 1, wherein the amount of the hindered amine light stabilizer added is 0.05 to 5% by mass in the total amount of the outer shell. The solid cursive according to claim 2 , wherein the hindered amine light stabilizer added to the outer shell has a molecular weight of 1000 or less.   The solid cursive according to any one of claims 1 to 3, wherein the outer shell comprises a filler.   A solid cursive set comprising the solid cursive body according to claim 1 and a friction body.

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