JP2012206264A - Manual printing set - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manual printing set which does not need a rubber eraser when erasing or correcting handwriting in the manual printed matter, thereby being full of usefulness because of not degrading hygiene or not affecting operation of devices when desired operation is performed.SOLUTION: The manual printing set includes a manual printing material such as a cook book with a method to make an object or a method to manipulate an object determined thereon, and a writing instrument 1 using, as a coloring material, a micro capsule pigment to make a color change from colored to colorless by heat, which includes reverse heat discoloring compound consisting at least of an electron-donating coloring organic compound (A), an electron-receiving compound (B), and a reactive medium (C) to control coloring reactions of these compounds (A) and (B), as thermally decolorable, reversible heat discoloration material.

Description

  The present invention relates to a manual print set. Specifically, the present invention relates to a manual printed material set including a printed material on which a manual is printed and a writing instrument that gives a handwriting that changes color from colorless to colorless by heating.

Conventionally, there are many manual printed materials such as books describing recipes for dishes such as side dishes and sweets, and books describing operation methods of mobile phones, personal computers, personal computer software, and the like (for example, see Patent Document 1). .
After reading and understanding the contents of the manual printed matter, the user cooks the desired operation or action, for example, in the case of a cookbook, or in the case of a PC software book, If the operation is performed on a personal computer, but the content of the printed material is insufficient, missing, or difficult to understand when reading the content of the printed material and performing the desired operation Had to write to.
At that time, when a pencil or a mechanical pencil is used, it is necessary to use an eraser for erasing, and an erasing residue is generated by rubbing, and a handwriting spreads at the time of rubbing to contaminate the periphery of the erased portion. Further, in the case of cooking, the generation of erased waste is unsanitary, and in the case of a device such as a personal computer, the attachment of the erased waste may cause a malfunction in the operation of the device.

Japanese Patent Application Laid-Open No. 11-165481

  Since the present invention does not use an eraser when erasing or correcting the handwriting written on the manual printed matter, it does not impair hygiene or affect the operation of the device when performing a desired operation. A manual print set is provided.

The present invention requires a manual printed material set including a manual printed material on which a manufacturing method or an operation method is described and a writing instrument using a reversible thermochromic material that can be erased by heating as a coloring material.
Further, the reversible thermochromic material controls (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) controls the color reaction of (a) and (b). A microcapsule pigment that contains a reversible thermochromic composition comprising at least a reaction medium that changes color from colorless to colorless by heating, and the microcapsule pigment is in a colored state in a color density-temperature curve relationship. When the temperature rises from the start of erasing, when the temperature reaches the erasing start temperature (t ₃ ), the erasing starts. When the temperature is higher than the complete erasing temperature (t ₄ ), the color is completely erased. When the starting temperature (t ₂ ) is reached, color starts to develop, and when the temperature is less than the complete color developing temperature (t ₁ ), the color develops a hysteresis characteristic. The temperature t ₁ is in the range of −30 to 10 ° C., and the temperature t ₄ is 40 In the range of ~ 95 ℃ And the writing instrument is provided with a friction member, and the manual print is a cookbook.

  Since the present invention does not use an eraser when erasing or correcting handwriting written on a manual print, it does not impair hygiene when performing a desired operation, and does not affect the operation of the device. It is possible to provide a manual print set that is rich in nature.

It is explanatory drawing which shows the discoloration behavior of the microcapsule pigment which included the reversible thermochromic composition. It is explanatory drawing which shows the discoloration behavior of the microcapsule pigment which included the reversible thermochromic composition which has color memory property. It is longitudinal section explanatory drawing which shows an example of the writing instrument used for the manual printed matter set of this invention. It is longitudinal section explanatory drawing which shows the other example of the writing instrument used for the manual printed matter set of this invention. It is longitudinal section explanatory drawing which shows the other example of the writing instrument used for the manual printed matter set of this invention. It is longitudinal section explanatory drawing which shows the other example of the writing instrument used for the manual printed matter set of this invention. It is longitudinal section explanatory drawing which shows the other example of the writing instrument used for the manual printed matter set of this invention. It is longitudinal section explanatory drawing which shows the other example of the writing instrument used for the manual printed matter set of this invention.

The manual printed material set of the present invention includes a manual printed material on which a manufacturing method or an operation method is described, and a writing instrument using a reversible thermochromic material that can be erased by heating as a coloring material.
As the manual printed matter, books describing recipes for cooking methods such as side dishes and sweets, books describing how to raise animals and plants, books describing childcare and education methods, electronic devices such as mobile phones and personal computers. A book describing an operation method, a book describing an operation method of a vehicle, a book describing an operation method of software for a personal computer, and the like can be exemplified.
The manual printed material may be in a single sheet form in addition to a booklet form in which a plurality of manual prints are bound together.

The writing instrument uses a reversible thermochromic material that can be erased by heating as a coloring material.
The coloring material includes at least three essential components of (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reaction medium that determines the temperature at which the coloring reaction of the two occurs. A pigment in which a reversible thermochromic composition is encapsulated in microcapsules is effective.
Examples of the reversible thermochromic composition include those described in Japanese Patent Publication No. 51-44706, Japanese Patent Publication No. 51-44707, Japanese Patent Publication No. 1-29398, etc., at a predetermined temperature (discoloration point). Discolored before and after, decolored state in the temperature range above the high temperature side discoloration point, color development state in the temperature range below the low temperature side discoloration point, only one specific state exists in the normal temperature range among the two states, The other state is maintained as long as the heat or cold required to develop the state is applied, but when the heat or cold is no longer applied, the hysteresis width returns to the state exhibited in the normal temperature range. A reversible thermochromic composition having a relatively small characteristic (ΔH = 1 to 7 ° C.) (discolored by heating and developed by cooling) can be applied (see FIG. 1).

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

The hysteresis characteristic in the color density-temperature curve of the reversible thermochromic composition will be described.
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) that reaches a completely decolored state, and B is a temperature t ₃ (hereinafter referred to as a decoloring start temperature). 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 complete color development state is reached (hereinafter referred to as a complete color development state). This is a point indicating a density at a color development temperature).
Discoloration temperature region is a temperature range between the t ₁ and t _4, it is possible to exhibit any of the states of the colored state and the decolored state, between t ₂ and t ₃ is a region having a large difference in color density The temperature range is substantially the discoloration temperature range.
The length of the line segment EF is a scale indicating the discoloration contrast, and the length of the line segment HG passing through the midpoint of the line segment EF is a temperature width indicating the degree of hysteresis (hereinafter referred to as hysteresis width ΔH). If this ΔH value is small, only one specific state can exist in the normal temperature range among both states before and after the color change. Further, when the ΔH value is large, it is easy to maintain each state before and after the color change.

Specifically, as the reversible thermochromic composition having color memory, a complete color development temperature t ₁ can be obtained only in a freezing room, a cold district, etc., that is, −50 to 0 ° C., preferably −40 to − 5 ° C., more preferably −30 to −10 ° C., and the temperature at which the complete decoloring temperature t ₄ is obtained from a frictional heat generated by a friction body, a heating body such as a hair dryer, that is, 45 to 95 ° C., preferably 50 to 90
By specifying the temperature in the range of 60 ° C., more preferably in the range of 60 to 80 ° C., and specifying the ΔH value in the range of 40 to 100 ° C., it is possible to effectively function to maintain the color exhibited in the normal state (daily life temperature range).
If the complete color erasing temperature t ₄ is 45 ° C. or higher, the state before discoloration can be maintained even under high temperature conditions such as summer, and if it is 95 ° C. or lower, the handwriting formed on the writing surface Can be sufficiently erased by frictional heat due to several rubbing by the friction member.
Complete decoloring If the temperature t ₄ is a temperature exceeding 95 ° C., since the frictional heat obtained by rubbing due to friction member is less likely to reach the complete decoloring temperature, easily becomes difficult to erase, or increased abrasion number, or Since the load tends to be excessively rubbed, the writing surface may be damaged.
Further, in the temperature setting of the complete coloring temperature t _1, is preferably a lower temperature to be maintained in the decolored state is normal use, is preferably 0 ℃ less.
Furthermore, it is necessary to make the reversible thermochromic composition filled in the writing instrument into a colored state. Therefore, it is necessary to cool the writing instrument, the ink composition, or the microcapsule pigment in advance to develop the reversible thermochromic composition.
As a cooling means in the production process, it is preferable to cool with a general-purpose freezer, but considering the cooling capacity of the freezer, the limit is up to −50 ° C.

Examples of the compounds (a), (b), and (c) of the reversible thermochromic composition are shown below.
Examples of the electron donating color-forming organic compound as component (a) of the present invention include diphenylmethane phthalides, phenyl indolyl phthalides, indolyl phthalides, diphenyl methane azaphthalides, and phenyl indolyl azaphthalides. , Fluorans, stylinoquinolines, diazarhodamine lactones and the like.
Examples of these compounds are given below.
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-cyclohexylaminofluorane,
2-methyl-6-cyclohexylaminofluorane,
2- (2-chloroamino) -6-dibutylaminofluorane,
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,
1,2-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) pyrimidine-5,1 ' (3′H) isobenzofuran] -3-one,
2- (Dibutylamino) -8- (dipentylamino) -4-methyl-spiro [5H- (1) benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran] -3 -On,
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-diethylaminophenyl) -3- (1-pentyl-2-methylindol-3-yl) -4,5,6,7-tetrachlorophthalide,
4,5,6,7-Tetrachloro-3- [4- (dimethylamino) -2-methylphenyl] -3- (1-ethyl-2-methyl-1H-indol-3-yl) -1 (3H ) -Isobenzofuranone,
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,
And 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 which are effective for developing a fluorescent yellow to red color, such as 4- [2,6-bis (2-ethoxyphenyl). -4-pyridinyl] -N, N-dimethylbenzenamine.

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

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

The component (c) of the reaction medium that causes the electron transfer reaction by the components (a) and (b) to occur reversibly in a specific temperature range will be described.
Examples of the component (c) 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 alcohols or branched aliphatic alcohols, dibenzyl cinnamate, heptyl stearate, didecyl adipate, dilauryl adipate, dimyristyl adipate, dicetyl adipate, distearyl adipate, trilaurin, trimyristin, tristearin, Dimyristin, distearin and the like are used.

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

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

  As ethers, aliphatic ethers having a total carbon number of 10 or more are effective, and dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, dinonyl ether, didecyl ether, diundecyl ether, didodecyl ether. , Ditridecyl ether, ditetradecyl ether, dipentadecyl ether, dihexadecyl ether, dioctadecyl ether, 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、ｍは０〜２の整数を示し、Ｘ_１、Ｘ_２のいずれか一方は−（ＣＨ_２）_ｎＯＣＯＲ_２又は−（ＣＨ_２）_ｎＣＯＯＲ_２、他方は水素原子を示し、ｎは０〜２の整数を示し、Ｒ_２は炭素数４以上のアルキル基又はアルケニル基を示し、Ｙ_１及びＹ_２は水素原子、炭素数１〜４のアルキル基、メトキシ基、又は、ハロゲンを示し、ｒ及びｐは１〜３の整数を示す。〕
前記式（１）で示される化合物のうち、Ｒ_１が水素原子の場合、より広いヒステリシス幅を有する可逆熱変色性組成物が得られるため好適であり、更にＲ_１が水素原子であり、且つ、ｍが０の場合がより好適である。
なお、式（１）で示される化合物のうち、より好ましくは下記一般式（２）で示される化合物が用いられる。

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

[Wherein, R ₁ represents a hydrogen atom or a methyl group, m represents an integer of 0 to 2, and _one of X ₁ and X ₂ represents — (CH ₂ ) _n OCOR ₂ or — (CH ₂ ) _n COOR ₂ , the other represents a hydrogen atom, n represents an integer of 0 to 2, R ₂ represents an alkyl or alkenyl group having 4 or more carbon atoms, Y ₁ and Y ₂ represent a hydrogen atom, 1 to 4 carbon atoms An alkyl group, a methoxy group, or halogen, and r and p each represent an integer of 1 to 3. ]
Among the compounds represented by the formula (1), when R ₁ is a hydrogen atom, it is preferable because a reversible thermochromic composition having a wider hysteresis width can be obtained, and R ₁ is a hydrogen atom, and , M is more preferably 0.
Of the compounds represented by the formula (1), a compound represented by the following general formula (2) is more preferably used.

R in the formula represents an alkyl group or alkenyl group having 8 or more carbon atoms, preferably an alkyl group having 10 to 24 carbon atoms, more preferably an alkyl group having 12 to 22 carbon atoms.
Specific examples of the compound include octanoic acid-4-benzyloxyphenylethyl, nonanoic acid-4-benzyloxyphenylethyl, decanoic acid-4-benzyloxyphenylethyl, undecanoic acid-4-benzyloxyphenylethyl, and dodecanoic acid. -4-benzyloxyphenylethyl, tridecanoic acid-4-benzyloxyphenylethyl, tetradecanoic acid-4-benzyloxyphenylethyl, pentadecanoic acid-4-benzyloxyphenylethyl, hexadecanoic acid-4-benzyloxyphenylethyl, heptadecanoic acid Examples thereof include -4-benzyloxyphenylethyl and octadecanoic acid-4-benzyloxyphenylethyl.

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

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

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

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

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

(In the formula, R represents an alkyl group or alkenyl group having 1 to 21 carbon atoms, and n represents an integer of 1 to 3).
Examples of the compound include a diester of 1,3-bis (2-hydroxyethoxy) benzene and capric acid, a diester of 1,3-bis (2-hydroxyethoxy) benzene and undecanoic acid, and 1,3-bis (2 -Hydroxyethoxy) benzene and lauric acid diester, 1,3-bis (2-hydroxyethoxy) benzene and myristic acid diester, 1,4-bis (hydroxymethoxy) benzene and butyric acid diester, 1,4 Diesters of bis (hydroxymethoxy) benzene and isovaleric acid, diesters of 1,4-bis (2-hydroxyethoxy) benzene and acetic acid, and 1,4-bis (2-hydroxyethoxy) benzene and propionic acid Diester, diester of 1,4-bis (2-hydroxyethoxy) benzene and valeric acid Diester of 1,4-bis (2-hydroxyethoxy) benzene and caproic acid, diester of 1,4-bis (2-hydroxyethoxy) benzene and caprylic acid, 1,4-bis (2-hydroxyethoxy) benzene And diester of capric acid, 1,4-bis (2-hydroxyethoxy) benzene and lauric acid, and 1,4-bis (2-hydroxyethoxy) benzene and myristic acid.

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

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

  The blending ratio of the components (a), (b), and (c) depends on the concentration, the color change temperature, the color change form, and the type of each component. In general, the component ratio at which a desired color change characteristic is obtained is as follows. (B) Component 1 is in the range of (b) Component 0.1-50, preferably 0.5-20, (c) Component 1-800, preferably 5-200. Part by mass).

The reversible thermochromic composition is effective when applied as it is, but is preferably used as a microcapsule pigment encapsulated in microcapsules. This is because the reversible thermochromic composition can be kept in the same composition under the various use conditions and can exhibit the same effects.
Methods for microencapsulating the reversible thermochromic composition include interfacial polymerization, interfacial polycondensation, in situ polymerization, in-liquid curing coating, phase separation from aqueous solution, and phase separation from organic solvent. There are a melt dispersion cooling method, an air suspension coating method, a spray drying method, and the like, which are appropriately selected according to use. Further, a secondary resin film may be provided on the surface of the microcapsule according to the purpose to impart durability, or the surface characteristics may be modified for practical use.

The microcapsule pigment may have a circular cross section or a non-circular cross section.
Here, the reversible thermochromic composition: microcapsule wall film = 7: 1 to 1: 1 (mass ratio), preferably 6: 1 to 1: 1.
When the ratio of the reversible thermochromic composition to the wall film is larger than the above range, the thickness of the wall film becomes too thin, and the resistance to pressure and heat tends to decrease, and the ratio of the wall film to the reversible thermochromic composition When the value is larger than the above range, color density and sharpness during color development tend to be reduced.

The microcapsule pigment has an average particle size of 0.01 to 5.0 [mu] m, preferably 0.1 to 4.0 [mu] m, more preferably 0.5 to 3.0 [mu] m, which satisfies the practicality.
When the average particle diameter exceeds 5.0 μm, when accommodated in a ballpoint pen for practical use, the gap between the ball and the ball holding portion is clogged with the microcapsule pigment, causing clogging, and ink ejection properties are easily impaired. On the other hand, in a system of less than 0.01 μm, it is difficult to show a high density color developability.
The particle diameter is measured using a laser diffraction / scattering particle size distribution measuring apparatus (manufactured by Horiba, Ltd .; LA-300), and the average particle diameter (median diameter) is calculated based on the numerical value. .

  As the writing instrument using the coloring material, a writing instrument such as a ballpoint pen, a marking pen, and a writing pen containing the ink composition containing the coloring material, a crayon, a pencil lead, and a sharp pencil in which the coloring material is dispersed in a base material. Examples include solid writing instruments such as pencil lead.

The medium used in the ink composition may be an organic solvent, but water and, if necessary, a water-soluble organic solvent are preferably used.
Examples of the water-soluble organic solvent include ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, and ethylene glycol monomethyl. Ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, sulfolane, 2-pyrrolidone, N-methyl-2- Pyrrolidone, or the like is used.
Note that the microcapsule pigment encapsulating the reversible thermochromic composition having a large hysteresis width has a specific gravity of more than 1, so that the water-soluble organic solvent to be applied is preferably more than 1.1.
Examples of the ink composition include a shear-thinning ink containing a shear-thinning agent, a cohesive ink containing a water-soluble polymer flocculant in a vehicle, and a pigment suspended in a loosely-aggregated state. it can.

By adding the shear thinning agent, it is possible to suppress aggregation and sedimentation of the pigment, and it is possible to suppress bleeding of the handwriting, so that a good handwriting can be formed.
Furthermore, when the writing instrument filled with the ink composition is a ballpoint pen, the ink leakage from the gap between the ball and the ball holding part when not in use is prevented, or the writing tip is left facing up (upright state) Ink back flow can be prevented.
Examples of the shear thinning agent include xanthan gum, welan gum, succinoglycan (average molecular weight of about 1 to 8 million) whose constituent monosaccharide is an organic acid-modified heteropolysaccharide of glucose and galactose, guar gum, locust bean gum and derivatives thereof , Hydroxyethyl cellulose, alginic acid alkyl esters, polymers having a molecular weight of 100,000 to 150,000, mainly composed of alkyl esters of methacrylic acid, thickening agent having gelling ability extracted from seaweed such as glucomannan, agar and carrageenan Sugars, benzylidene sorbitol and benzylidene xylitol or their derivatives, crosslinkable acrylic acid polymer, inorganic fine particles, polyglycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester, polio Shi ethylene alkyl ethers, polyoxypropylene alkyl ethers, polyoxyethylene alkyl phenyl ether, nonionic HLB value, such as fatty acid amide is 8-12 surfactants, salts of dialkyl or dialkenyl sulfosuccinic acid. Examples thereof include a mixture of N-alkyl-2-pyrrolidone and an anionic surfactant, and a mixture of polyvinyl alcohol and an acrylic resin.

Examples of the water-soluble polymer flocculant include polyvinyl pyrrolidone, polyethylene oxide, and water-soluble polysaccharides.
Examples of the water-soluble polysaccharides include tragacanth gum, guar gum, pullulan, cyclodextrin, water-soluble cellulose derivatives and the like. Specific examples of water-soluble cellulose derivatives include methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose. Etc.
Two or more kinds of the polymer flocculants can be used in combination.

Combining the polymer flocculant with a comb polymer dispersant having a carboxyl group in the side chain and an organic nitrogen sulfur compound improves dispersibility of loose aggregates of microcapsule pigments by the polymer flocculant. be able to.
The comb polymer dispersant having a carboxyl group in the side chain is not particularly limited as long as it is a comb polymer compound having a plurality of carboxyl groups in the side chain, but a plurality of carboxyl groups in the side chain. An acrylic polymer compound having the following formula is suitable. Examples of the compound include trade name: Solsperse 43000 manufactured by Nippon Lubrizol Corporation.

When the organic nitrogen sulfur compound is used in combination, when the ink composition is filled in a writing instrument and put to practical use, the precipitation of the microcapsule pigment due to vibration is further suppressed.
This further improves dispersibility in which loose aggregates of microcapsule pigments are dispersed by a comb-type polymer dispersant having a carboxyl group in the side chain.
As the organic nitrogen sulfur compound, a compound selected from thiazole compounds, isothiazole compounds, benzothiazole compounds, and benzoisothiazole compounds is used.
Specific examples of the organic nitrogen sulfur compound include 2- (4-thiazoyl) -benzimidazole (TBZ), 2- (thiocyanatomethylthio) -1,3-benzothiazole (TCMTB), 2-methyl-4-isothiazoline- One or more compounds selected from 3-one and 5-chloro-2-methyl-4-isothiazolin-3-one are used, preferably 2- (4-thiazoyl) -benzimidazole (TBZ), 2 One or more compounds selected from -methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one are used.
As the organic nitrogen sulfur compound, manufactured by Permachem Asia Co., Ltd., trade names: Topside 88, 133, 170, 220, 288, 300, 400, 500, 600, 700Z, 800, 950, manufactured by Hokuko Sangyo Co., Ltd., trade names: Hokuster HP, E50A, Hokuside P200, 6500, 7400, MC, 369, and R-150.
The mass ratio of the comb-type polymer dispersant having a carboxyl group in the side chain and the organic nitrogen sulfur compound is 1: 1 to 1:10, preferably 1: 1 to 1: 5, and satisfies the above range. Thus, the dispersibility of loose aggregates of the microcapsule pigment and the suppression of sedimentation of the microcapsule pigment due to vibration can be sufficiently expressed.

Furthermore, addition of a water-soluble resin can provide adhesion and viscosity to the paper surface, and increase the stability of the above-described comb polymer dispersant having a carboxyl group in the side chain and organic nitrogen sulfur compound in ink. Functions can be added.
Examples of the water-soluble resin include alkyd resins, acrylic resins, styrene maleic acid copolymers, cellulose derivatives, polyvinyl pyrrolidone, polyvinyl alcohol, dextrin, and preferably polyvinyl alcohol is used.
Furthermore, when a partially saponification type polyvinyl alcohol having a saponification degree of 70 to 89 mol% is used as the polyvinyl alcohol, the ink composition is more soluble even in an acidic region, and thus is more preferably used.
The addition amount of the water-soluble resin is 0.3 to 3.0% by mass, preferably 0.5 to 1.5% by mass in the ink composition.

The ink composition does not contain the water-soluble polymer flocculant, specifically, a water-soluble organic solvent, a comb-type polymer dispersant having a carboxyl group in the side chain, an organic nitrogen sulfur compound, and a water-soluble By containing the resin, an ink composition having excellent dispersibility of the microcapsule pigment can be obtained.
Glycerin is preferably used as the water-soluble organic solvent, and can be blended in an amount of 5 to 40% by weight, preferably 25 to 40% by weight, more preferably 30 to 35% by weight based on the total amount of the ink composition.
For the comb polymer dispersant having a carboxyl group in the side chain, the organic nitrogen sulfur compound, and the water-soluble resin, the same compounds as described above are used.

  In addition, when the ink composition is used by filling a ballpoint pen, a higher fatty acid such as oleic acid, a nonionic surfactant having a long-chain alkyl group, a polyether-modified silicone oil, a thiophosphorous acid tri (alkoxycarbonylmethyl ester) ) And thiophosphite triester (alkoxycarbonylethyl ester), etc., polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether phosphate monoester, polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether It is preferable to prevent wear of the ball seat by adding a lubricant such as a phosphoric acid diester or a metal salt, ammonium salt, amine salt or alkanolamine salt thereof.

  In addition, pH adjusters such as inorganic salts such as sodium carbonate, sodium phosphate and sodium acetate, organic basic compounds such as water-soluble amine compounds, benzotriazole, tolyltriazole, dicyclohexylammonium nitrite, diisopropylammonium night as necessary Rust prevention agent such as light, saponin, coalic acid, sodium salt of 1,2-benzthiazolin-3-one, sodium benzoate, sodium dehydroacetate, potassium sorbate, propyl paraoxybenzoate, 2,3,5,6-tetra Preservatives or fungicides such as chloro-4- (methylsulfonyl) pyridine, urea, nonionic surfactants, reduced or non-reduced starch hydrolysates, oligosaccharides such as trehalose, sucrose, cyclodextrin, glucose, dextrin , Sorbit, N'nitto, wetting agents such as sodium pyrophosphate, defoamers, dispersing agents, a surfactant may be added a fluorine-based surfactant or a nonionic improve the ink permeability.

In order for the ink composition to form a handwriting that can be visually recognized at the time of writing, it is preferable that a color material (a microcapsule pigment including a reversible thermochromic composition) contained in the ink is in a colored state.
The microcapsule pigments may be used alone or in combination of two or more, and used in the ink composition in the range of 10 to 50% by mass, preferably 15 to 45% by mass, more preferably 20 to 45% by mass. It is done.

When filling the ballpoint pen with the ink composition, the structure and shape of the ballpoint pen itself are not particularly limited. For example, the ink pendant has an ink containing tube filled with shear-thinning ink in a shaft tube. Can be exemplified by a ballpoint pen in which a ball is in communication with a pen mounted on the tip, and a liquid stopper for backflow prevention is in close contact with the end face of the ink.
The pen body will be described in more detail. A pen body in which a ball is held in a ball holding portion in which the vicinity of the tip of a metal pipe is pressed and deformed inward from the outer surface, or a metal material is cut by a drill or the like. A pen body formed by holding a ball in a ball holding section formed by processing, a pen body provided with a resin ball receiving seat inside a metal or plastic ball holding section, or held by the pen body A ball or the like that is urged forward by a spring body can be applied.
The ball is 0.3 to 3.0 mm, preferably 0.4 to 1.5 mm, more preferably 0.5 to 1.0 mm, such as cemented carbide, stainless steel, ruby, ceramic, resin, and rubber. A thing of a diameter is applicable.
For example, a molded body made of a thermoplastic resin such as polyethylene, polypropylene, polyethylene terephthalate, or nylon is used as the ink storage tube for storing the ink composition.
In addition to directly connecting the pen body to the ink storage tube, the ink storage tube and the pen body may be connected via a connecting member.
The ink storage tube may be in the form of a refill, and the refill may be accommodated in a shaft cylinder made of resin, metal, or the like, or the shaft cylinder itself with a pen body attached to the tip is used as an ink container. The shaft cylinder may be filled directly with ink.
In addition, when the ink composition is housed in a retractable ballpoint pen, the structure and shape of the retractable ballpoint pen are not particularly limited, and the writing tip provided on the ballpoint pen refill is exposed to the outside air. Any structure can be used as long as it is housed in the cylinder and the writing tip protrudes from the shaft cylinder opening by the operation of the retracting mechanism.
Examples of the operation method of the retracting mechanism include a knock type, a rotary type, and a slide type.
The knock type has a knock portion on the rear end portion of the shaft cylinder and the side surface of the shaft tube, and a configuration in which the ball-point pen tip is projected and retracted from the opening at the tip end of the shaft tube by pressing of the knock portion, or a clip portion provided on the shaft tube A configuration in which the ball-point pen tip is projected and retracted from the opening at the tip of the shaft cylinder can be exemplified by pressing.
The rotary type has a rotating part at the rear part of the shaft cylinder, and can be exemplified by a configuration in which the ball-point pen tip is projected and retracted from the opening part of the shaft cylinder tip by turning the rotating part.
The slide type has a slide part on the side surface of the shaft tube, and by operating the slide, the ballpoint pen tip is projected and retracted from the tip end of the shaft tube, or by sliding a clip part provided on the shaft tube A configuration in which the ballpoint pen tip is projected and retracted from the opening at the tip of the shaft cylinder can be exemplified.
The retractable ballpoint pen is a compound type retractable ballpoint pen in which a plurality of ballpoint pen refills are accommodated in a shaft cylinder, and the writing tip portion of any of the ballpoint pen refills protrudes and retracts from the shaft tube tip opening portion by the operation of the retractable mechanism. May be.

An ink backflow preventer is filled at the rear end of the ink stored in the ink storage tube.
The ink backflow prevention body composition is composed of a non-volatile liquid or a hardly volatile liquid.
Specifically, petroleum jelly, spindle oil, castor oil, olive oil, refined mineral oil, liquid paraffin, polybutene, α-olefin, α-olefin oligomer or co-oligomer, dimethyl silicone oil, methylphenyl silicone oil, amino-modified silicone oil, A polyether modified silicone oil, a fatty acid modified silicone oil, etc. are mentioned, 1 type, or 2 or more types can also be used together.
The non-volatile liquid and / or the hardly volatile liquid is preferably thickened to a suitable viscosity by adding a thickener. As the thickener, the surface is treated with hydrophobic silica, and the surface is methylated. Fine particle silica, aluminum silicate, swellable mica, hydrophobic thickener such as bentonite and montmorillonite, fatty acid metal soap such as magnesium stearate, calcium stearate, aluminum stearate, zinc stearate, tribenzylidene sorbitol, Examples thereof include fatty acid amide, amide-modified polyethylene wax, hydrogenated castor oil, dextrin compounds such as fatty acid dextrin, and cellulose compounds.
Furthermore, the liquid ink backflow prevention body and the solid ink backflow prevention body can be used in combination.

When filling the marking pen with the ink composition, the structure and shape of the marking pen itself are not particularly limited. For example, an ink occlusion body consisting of a fiber bundling body is built in the shaft cylinder to form a capillary gap. A pen body made of a processed fiber body is mounted on a shaft cylinder directly or via a relay member, and the ink storage body of the marking pen formed by connecting the ink storage body and the pen body is impregnated with cohesive ink. An example is a marking pen in which a pen body and an ink storage tube are disposed via a marking pen that has been moved, or a valve body that is opened when the pen body is pressed, and ink is directly stored in the ink storage tube.
The pen body is a porous member having continuous ventilation holes selected from the range of generally 30 to 70% of general porosity, such as a resin processed body of fibers, a fusion processed body of hot melt fibers, and a felt body. One end is processed into a shape corresponding to the purpose such as a bullet shape, a rectangular shape, a chisel shape, etc.
The ink occlusion body is formed by converging crimped fibers in the longitudinal direction, and is configured to be included in a covering body such as a plastic cylinder or a film and to adjust the porosity to a range of approximately 40 to 90%. Is done.
Moreover, although the said valve body can use a general purpose pumping type | formula, what was set to the spring pressure which can be press-released with writing pressure is suitable.

  Furthermore, the form of the ballpoint pen or the marking pen is not limited to the one described above, but a composite writing instrument (a double-headed type or a nib with a pen body having a different shape or a pen point for deriving different colors of ink). It may be a pay-out type or the like.

Next, solid writing instruments such as a crayon, a pencil lead, and a mechanical pencil lead in which the coloring material is dispersed in a base material will be described.
The solid cursive is obtained by dispersing and solidifying a coloring material in a shapeable wax, and commonly used waxes are effective as the excipient.
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 vegetable 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 such as esters, higher alcohols, ketones, fatty acids, palm oil, liquid paraffin, polybutene, polybutadiene, styrene oligomers, etc. And hydrocarbons.
In the case of lead wicks such as pencil wicks and mechanical pencil wicks, build and improve strength such as talc, mica, kaolin, clay, precipitated barium sulfate, calcium carbonate, boron nitride, and potassium titanate whiskers. Blended for the purpose of adjusting taste.

The handwriting formed by the writing instrument can be discolored by rubbing with a finger, heating, or application of a cooling / heating 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.
As the friction member, an elastic body such as an elastomer or a plastic foam which is rich in elasticity and can generate frictional heat by rubbing at the time of rubbing is suitable.
Although it is possible to rub the handwriting using an eraser, the above-mentioned friction member that hardly generates erase scraps is preferably used because erase scraps are generated during friction.
As the material of the friction member, silicone resin, SEBS resin (styrene ethylene butylene styrene block copolymer), polyester resin, or the like is used.
The friction member can be obtained by combining a writing instrument and a member of arbitrary shape (friction body) separately to obtain a writing instrument set. However, by providing the writing instrument with a friction member, it is excellent in portability.
In the case of a writing instrument having a cap, the location where the friction member is provided is not particularly limited. For example, when the cap itself is formed of a friction member, the shaft tube itself is formed of a friction member, or a clip is provided. The clip itself can be formed of a friction member, or the friction member can be provided at the tip end (top) of the cap or the rear end of the shaft cylinder (the portion where the writing tip is not provided).
In the case of a retractable writing instrument, the location where the friction member is provided is not particularly limited, but for example, the shaft cylinder itself is formed with a friction member, or when the clip is provided, the clip itself is formed with a friction member, A friction member can be provided in the vicinity of the shaft tube opening, the rear end portion of the shaft tube (the portion where the writing tip portion is not provided) or the knock portion.
Examples of the cooling / heating tool include a cooling / heating discoloration tool using a Peltier element, a cooling / heating discoloration tool filled with a coolant such as cold water and ice pieces, a refrigerator and a freezer.

Examples are shown below, but the present invention is not limited to these examples.
In addition, the part in an Example is a weight part.
Example 1
Preparation of reversible thermochromic ink composition 4.5 parts of 2- (2-chloroanilino) -6-di-n-butylaminofluorane as component (a) and 1,1-bis (4 ′ as component (b) -Hydroxyphenyl) 4.5 parts of n-decane, 7.5 parts of 2,2-bis (4'-hydroxyphenyl) hexafluoropropane, and (ha) from 50.0 parts of 4-benzyloxyphenylethyl caprate A microcapsule pigment (t ₁ : −20 ° C., t ₂ : −9 ° C., t ₃ : 40 ° C., t ₄ : 57 ° C., ΔH: 63 ° C. (Average particle size: 2.5 μm, reversible thermochromic composition / wall film = 2.6 / 1.0, color change from black to colorless).
The microcapsule pigment (which was previously cooled to −20 ° C. or less and colored the microcapsule pigment in black) was used as a coloring material (coloring agent).
25.0 parts of the above microcapsule pigment, 0.2 part of succinoglycan (shear thinning agent), 5.5 parts of urea, 7.5 parts of glycerin, 0.03 part of a nonionic permeability imparting agent, a modified silicone type A reversible thermochromic ink composition was prepared by mixing 0.15 part of an antifoaming agent, 0.1 part of an antifungal agent, 0.5 part of a lubricant, 0.5 part of triethanolamine and 60.52 parts of water. .

Writing instrument production (see Figure 3)
The ink composition 7 was filled in a polypropylene ink containing tube 3 and connected to a pen body 6 (ballpoint pen tip) through a resin holder 4.
Next, an ink backflow prevention body 8 (liquid stopper) having a viscoelastic property mainly composed of polybutene is filled from the rear part of the ink containing pipe, and the tail plug 5 is fitted to the rear part of the ink containing pipe to form the refill 2. did.
The refill 2 was assembled in a shaft tube 9 (comprised of a front shaft tube and a rear shaft tube), and a cap 10 was fitted to obtain a writing instrument 1 (ballpoint pen).
The shaft tube is provided with a SEBS resin member as a friction member 11 at the rear.
The pen body includes a stainless steel ball having a diameter of 0.7 mm held at the tip end of a tip formed by pressing and deforming the vicinity of the tip of a metal pipe inward from the outer surface, and the ball is a spring. It is energized forward by the body.

Production of Manual Printed Material Set A manual printed material set was obtained by combining the writing instrument and a book describing a recipe for cooking.
Using the writing instrument, the amount for three people was entered in the blank on the page where the ingredients used for cooking and the amount (for four people) and the cooking procedure were written. At that time, when the mistakenly written portion was abraded with a friction member, the characters disappeared and were not visually recognized. This state could be maintained at room temperature, and the correct amount could be written in the erased location.
In addition, it is possible to erase all the handwriting by heating the whole using a hair dryer, and it is visually recognized as if it had returned to the printed matter before filling in the amount, and it is an excellent manual that can be rewritten. A printed set was obtained.
In addition, in the process of erasing the handwriting, no erase residue such as an eraser was produced, and the sanitary property was excellent.

Example 2
Writing instrument production (see Fig. 4)
The ink composition 7 obtained in Example 1 is filled into a polypropylene shaft tube 9 having a pen body 6 fixed to the tip thereof via a holder 4, then filled with an ink backflow prevention body 8, and the tail plug 5 is fitted. I let you.
Furthermore, a writing instrument 1 (ballpoint pen) was obtained by fitting a cap 10 containing a rubber seal.
The pen body includes a stainless steel ball having a diameter of 0.7 mm held by a ball holding portion formed by cutting a metal material with a drill, and the ball is biased forward by a spring body. The cap is formed by mounting a SEBS resin member as the friction member 11 at the tip.

Production of Manual Printed Material Set A manual printed material set was obtained by combining the writing instrument and a book describing a recipe for cooking.
Using the writing instrument, a portion that was difficult to understand in the cooking procedure was added to the blank space on the page where the ingredients used for cooking, the amount of the ingredients, and the cooking procedure were written. At that time, when the mistakenly written portion was abraded with a friction member, the characters disappeared and were not visually recognized. This state could be maintained at room temperature and the correct procedure could be written to the erased location.
In addition, it is possible to erase all the handwriting by heating the whole using a hair dryer, and it is visually recognized as if it had returned to the printed matter before entering the procedure, and it is a convenient manual that can be rewritten. A printed set was obtained.
In addition, in the process of erasing the handwriting, no erase residue such as an eraser was produced, and the sanitary property was excellent.

Example 3
Preparation of reversible thermochromic ink composition (I) 2- (Butylamino) -8- (diphenylamino) -4-methylspiro [5H- [1] benzopyrano [2-3-g] pyrimidine-5,1 2.0 parts of (3'H) -isobenzofuran] -3-one, 5.0 parts of 2,2-bis (4'-hydroxyphenyl) hexafluoropropane as component (b), 1,1-bis (4 A microcapsule pigment encapsulating a reversible thermochromic composition having color memory consisting of 3.0 parts of '-hydroxyphenyl) n-decane and 50.0 parts of 4-benzyloxyphenylethyl caprate as component (c) ( t ₁ : −16 ° C., t ₂ : −8 ° C., t ₃ : 48 ° C., t ₄ : 58 ° C., ΔH: 65 ° C., average particle size: 2.5 μm, reversible thermochromic composition / wall film = 2 .6 / 1.0, no color from pink Color change).
The microcapsule pigment (which was cooled in advance to −16 ° C. or less to make the microcapsule pigment develop a pink color) was used as a coloring material (coloring agent).
Uniformly dispersed in an aqueous medium comprising 20.0 parts of the microcapsule pigment, 5.0 parts of glycerin, 0.7 part of the antifungal agent, 0.1 part of the silicone-based antifoaming agent and 56.2 parts of water. After that, 8 parts of a 5% by weight aqueous solution of hydroxyethyl cellulose (Union Carbide Japan Co., Ltd., trade name: Cellosize WP-09L, water-soluble polymer flocculant) was added to the dispersion while stirring. Thus, a reversible thermochromic ink was prepared by suspending the reversible thermochromic pigment in a gentle aggregate state.

Writing instrument production (see Fig. 5)
The fiber composition ink occlusion body 12 (porosity of about 80%) covered with a synthetic resin film on a polyester sliver is impregnated with the ink composition and accommodated in the shaft tube 9. The polyester fiber resin processing pen body 6 (porosity of about 50%) was assembled in contact, and the cap 10 was fitted to obtain a writing instrument 1 (marking pen).
The shaft tube is provided with a SEBS resin member as a friction member at the rear.

Preparation of Manual Printed Material Set A manual printed material set was obtained by combining the writing instrument and a childcare book.
Using the above-mentioned writing instrument, a portion that was difficult to understand by the method of childcare was added to the blank of the page on which the method of childcare was described. At that time, if the frictional member was used to scrape the wrongly written portion, the character disappeared and was not visually recognized. This state could be maintained at room temperature and the correct method could be written to the erased location.
In addition, it is possible to erase all the handwriting by heating the whole using a hair dryer, and it is visually recognized as if it had returned to the printed matter before entering the method, and it is a convenient manual that can be rewritten. A printed set was obtained.
In addition, in the process of erasing the handwriting, no erase residue such as an eraser was produced, and the sanitary property was excellent.

Example 4
Writing instrument production (see Fig. 6)
The ink composition 7 obtained in Example 1 was filled in a polypropylene ink containing tube 3 and connected to a pen body 6 (ballpoint pen tip) through a resin holder 4.
Next, from the rear part of the ink containing tube, an ink backflow prevention body 8 (liquid stopper) having viscoelasticity mainly composed of polybutene is filled, and the tail plug 5 is fitted to the rear part of the ink containing tube to form a refill. .
The pen body includes a stainless steel ball having a diameter of 0.5 mm held at the tip end of a tip formed by pressing and deforming the vicinity of the tip of a metal pipe inward from the outer surface, and the ball is a spring. It is energized forward by the body.
The refill was incorporated into the shaft tube 9 to obtain a retractable ballpoint pen 8.
The retractable ballpoint pen is housed in the shaft cylinder with the writing tip provided on the ballpoint pen refill exposed to the outside air, and a clip-shaped retracting mechanism (slide mechanism) provided on the side surface of the shaft cylinder. In this structure, the writing tip protrudes from the shaft tube tip opening.
The handwriting obtained by writing in a state where the ball-point pen tip was retracted from the opening at the tip of the shaft tube by the operation of the retracting mechanism was black.
In addition, the said handwriting can be decolored by rubbing using the friction member 11 made from SEBS resin provided in the rear-end part of the axial cylinder.

Preparation of Manual Printed Material Set A manual printed material set was obtained by combining the writing instrument and a book describing a method for operating a mobile phone.
Using the writing instrument, a portion that was difficult to understand by the operation method was added to the blank of the page on which the operation method of the mobile phone was described. At that time, when the mistakenly written portion was abraded with a friction member, the characters disappeared and were not visually recognized. This state could be maintained at room temperature and the correct method could be written to the erased location.
In addition, it is possible to erase all the handwriting by heating the whole using a hair dryer, and it is visually recognized as if it had returned to the printed matter before entering the method, and it is a convenient manual that can be rewritten. A printed set was obtained.
In the process of erasing the handwriting, no erase residue like an eraser was produced, and the operation of the device was not affected.

Example 5
Preparation of reversible thermochromic ink composition 20.0 parts of microcapsule pigment obtained in Example 3, xanthan gum [trade name: Kelzan ST, manufactured by Sanki Co., Ltd.] 0.3 part, sugar mixture [trade name: Sandeck 30, Sanwa Starch Co., Ltd.] 1.5 parts, Lubricant [trade name: Prisurf AL, Daiichi Kogyo Seiyaku Co., Ltd.] 1.0 part, Triethanolamine 1.0 part, Water 76 2 parts were mixed to obtain a reversible thermochromic ink composition.

Writing instrument production (see Figure 7)
The ink composition and the ink composition obtained in Example 4 were each filled into a polypropylene ink storage tube and connected to a pen body (ballpoint pen tip) through a resin holder.
Next, from the rear part of the ink containing tube, an ink backflow prevention body (liquid stopper) having viscoelasticity mainly composed of polybutene was filled to form a refill.
The pen body includes a stainless steel ball having a diameter of 0.5 mm held by a ball holding portion formed by cutting a metal material with a drill, and the ball is biased forward by a spring body. It is a thing.
The ball pen refill is incorporated into the light-shielding shaft tube 9 and the writing tool 1 (intrusion type) in which the writing tip portion of any of the ball pen refills protrudes and retracts from the shaft tube tip opening portion by operating the operating body 13 of the retracting mechanism. Ballpoint pen) was obtained.
The shaft cylinder rear end is provided with a friction member 11 made of SEBS resin.
The handwriting obtained by writing with the ball-point pen tip in and out of the opening at the end of the barrel by the operation of the in / out mechanism was pink and black.
The handwriting can be decolored by rubbing with a friction member.

Preparation of Manual Printed Material Set A manual printed material set was obtained by combining the writing instrument and a book describing an operation method of a personal computer.
Using the writing instrument, a portion that was difficult to understand by the operation method was added to the blank of the page on which the operation method of the personal computer was described. At that time, when the mistakenly written portion was abraded with a friction member, the characters disappeared and were not visually recognized. This state could be maintained at room temperature and the correct method could be written to the erased location.
In addition, it is possible to erase all the handwriting by heating the whole using a hair dryer, and it is visually recognized as if it had returned to the printed matter before entering the method, and it is a convenient manual that can be rewritten. A printed set was obtained.
In the process of erasing the handwriting, an eraser such as an eraser was not generated, and the operation of the personal computer and its equipment was not affected.

Example 6
Writing instrument production (see Fig. 8)
Each of the ink compositions obtained in Example 4 and Example 5 was filled into a light-shielding ink storage tube and connected to a pen body (ballpoint pen tip) through a resin holder.
Next, an ink backflow prevention body (liquid stopper) having viscoelasticity mainly composed of polybutene was filled from the rear portion of the ink storage tube, and the operation body 13 was fitted to the rear portion of the ink storage tube to form a refill.
The pen body has a stainless steel ball having a diameter of 0.4 mm held at the tip of a tip formed by pressing and deforming the vicinity of the tip of a metal pipe inward from the outer surface, and the ball is a spring. It is energized forward by the body.
The refill is incorporated into a transparent shaft tube 9 having a lid portion 14 that can be opened and closed at the rear, and after closing the lid portion, the writing tip of any ballpoint pen refill is turned into a shaft tube by the operation of the operation mechanism of the retracting mechanism. A writing instrument 1 (in / out type ballpoint pen) that appears and disappears from the tip opening was obtained.
The lid is provided with a friction member 11 made of SEBS resin.
The handwriting obtained by writing with the ball-point pen tip in and out of the opening at the end of the barrel by the operation of the in / out mechanism was pink and black.
The handwriting can be decolored by rubbing with a friction member.

Preparation of Manual Printed Material Set A manual printed material set was obtained by combining the writing instrument and a book describing how to operate software on a personal computer.
Using the writing instrument, a portion of the page where the usage method of the software is described was added to the blank space on the page where the usage method was difficult to understand. At that time, when the mistakenly written portion was abraded with a friction member, the characters disappeared and were not visually recognized. This state could be maintained at room temperature and the correct method could be written to the erased location.
In addition, it is possible to erase all the handwriting by heating the whole using a hair dryer, and it is visually recognized as if it had returned to the printed matter before entering the method, and it is a convenient manual that can be rewritten. A printed set was obtained.
In the process of erasing the handwriting, no erase residue such as an eraser was produced, and the operation of the personal computer and its peripheral devices was not affected.

Example 7
Preparation of solid cursive material Implemented in a formable wax consisting of 74 parts of polyethylene wax (softening point 107 ° C., manufactured by Sanyo Chemical Co., Ltd., trade name Sun Wax 131-P) and 13 parts of ethylene vinyl acetate copolymer wax 13 parts of the microcapsule pigment obtained in Example 3 was added, heated, mixed and melted, and molded, cooled, and dried by extrusion molding to obtain a solid cursive body (lead core).
The lead core was cooled to −16 ° C. or lower to develop the reversible thermochromic microcapsule pigment in pink, and then incorporated into a wooden shaft to obtain a writing instrument (pencil).
A friction body made of SEBS resin is provided at the rear of the shaft.
When writing on the paper using the pencil, a pink handwriting could be formed.
The handwriting can be decolored by rubbing with a friction member.

Preparation of Manual Printed Material Set A manual printed material set was obtained by combining the writing instrument and a book on animal rearing methods.
Using the writing instrument, a place that was difficult to understand by the breeding method was added to the blank of the page where the breeding method was described. At that time, if the frictional member was used to scrape the wrongly written portion, the character disappeared and was not visually recognized. This state could be maintained at room temperature and the correct method could be written to the erased location.
In addition, it is possible to erase all the handwriting by heating the whole using a hair dryer, and it is visually recognized as if it had returned to the printed matter before entering the method, and it is a convenient manual that can be rewritten. A printed set was obtained.
In addition, in the process of erasing the handwriting, no erase residue such as an eraser was produced, and the sanitary property was excellent.

t ₁ complete coloring temperature t ₂ coloring start temperature t ₃ decoloring start temperature t ₄ complete decoloring temperature ΔH hysteresis width 1 writing instrument 2 refill 3 ink containing tube 4 holder 5 tail plug 6 pen body 7 ink composition 8 ink backflow preventer 9 Shaft cylinder 10 Cap 11 Friction member 12 Ink occlusion body 13 Operation body 14 Lid

Claims (5)

  A set of manual prints consisting of a manual print describing how to make or manipulate the product and a writing instrument using a reversible thermochromic material that can be erased by heating as a colorant.   The reversible thermochromic material comprises (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reaction medium that controls the color reaction of (a) and (b). The manual print set according to claim 1, which is a microcapsule pigment which contains a reversible thermochromic composition comprising: When the microcapsule pigment reaches the decoloring start temperature (t ₃ ) in the process of increasing the temperature from the colored state in the relationship of the color density-temperature curve, the microcapsule pigment starts decoloring, and at the complete decoloring temperature (t ₄ ) When the temperature reaches the color development start temperature (t ₂ ) in the process of temperature erasing from the color erased state, the color starts to develop, and below the complete color development temperature (t ₁ ), the color develops completely and exhibits a hysteresis characteristic. The manual print set according to claim 2, wherein ₁ is in the range of −50 to 0 ° C. and the temperature t ₄ is in the range of 45 to 95 ° C. ₄ .   The manual printed material set according to claim 1, wherein the writing instrument includes a friction member.   The manual printed material set according to claim 1, wherein the manual printed material is a cookbook.

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