JP2012183690A - Ballpoint pen refill and ballpoint pen using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a ballpoint pen refill which is so convenient that it can be discriminated that the ballpoint pen refill can form thermochromic handwriting without writing, and provide a ballpoint pen using the same.SOLUTION: The ballpoint pen refill is formed by connecting an operation body to a rear end of the ballpoint pen refill which houses a thermochromic ink composition, can be removed from and inserted in a shaft cylinder, and can make a writing tool tip end part appear from a tip end opening part of the shaft cylinder by operating the operation body in an inserted state. The ballpoint pen refill 1 is characterized by that a color of the operation body 5 is changed depending on a viewing angle. The ballpoint pen uses the ballpoint pen refill.

Description

  The present invention relates to a ballpoint pen refill and a ballpoint pen using the same. More specifically, the present invention relates to a ballpoint pen refill containing a reversible thermochromic ink composition and a ballpoint pen using the same.

Conventionally, a ballpoint pen tip holding a ball is fixed to the front end, and an ink containing tube containing an ink composition inside and an operation body colored in ink color are connected to the rear end of the ink containing tube, A ballpoint pen refill is disclosed in which a writing tip is projected and retracted from the opening of the tip of the shaft tube by being housed in the shaft tube during use, protruding from the side wall of the shaft tube, and sliding the operation body (for example, Patent Document 1).
The ballpoint pen refill can obtain a composite ballpoint pen excellent in convenience in which handwriting of various colors can be formed by housing a plurality of refills having operation bodies colored in different ink colors in a shaft barrel. it can.
However, in the case of a ballpoint pen refill containing a thermochromic ink composition in an ink containing tube, the function of identifying whether the handwriting formed by the ballpoint pen refill is a thermochromic handwriting is poor. It was necessary to check if the color changed.

JP 2007-45139 A

  The present invention relates to a defect in a ballpoint pen refill containing a thermochromic ink composition in the ink containing tube, that is, when identifying whether the handwriting formed by the ballpoint pen refill is a thermochromic handwriting, A ball-point pen refill that can identify a ball-point refill that can form a thermochromic handwriting without the need for confirmation of the point and a ball-point pen using the same.

The present invention eliminates the problems of the composite writing instrument described above, that is, an operating body is connected to the rear end of a ballpoint refill containing a thermochromic ink composition, and is removed from the shaft cylinder. It is a refill for a ballpoint pen that allows a writing tip portion to be projected and retracted from a tip opening portion of a shaft cylinder by operating the operation body in the inserted state, and changes color depending on an angle viewed by the operation body. A ballpoint pen refill characterized by this is a requirement.
Furthermore, the surface of the operation body is provided with a metallic luster layer containing a transparent metallic luster pigment having color flop, and the surface of the operation body is divided into a plurality of strips. Requirement that each strip is placed adjacent to each other in sequence, a lenticular lens is provided on the image, and that any color exhibited by the operating body is the same color as the ink composition in the ink container And
Furthermore, a ball-point pen that accommodates one or more ball-point pen refills is a requirement.

  INDUSTRIAL APPLICABILITY The present invention can provide a convenient ballpoint pen refill that can be identified without writing that it is a ballpoint pen refill capable of forming a thermochromic handwriting, and a ballpoint pen using the same.

It is explanatory drawing which shows the discoloration behavior of a heat decoloring type reversible thermochromic microcapsule pigment. It is explanatory drawing which shows the discoloration behavior of the heat decoloring type reversible thermochromic microcapsule pigment having color memory. It is explanatory drawing which shows the discoloration behavior of a heat coloring type reversible thermochromic microcapsule pigment. It is explanatory drawing which shows one Example of the ball-point refill which accommodated the thermochromic ink composition of this invention. It is sectional drawing of the ball-point pen which accommodated the ball-point pen refill of FIG. It is explanatory drawing which shows the other Example of the ball-point refill which accommodated the thermochromic ink composition of this invention.

The ballpoint pen refill of the present invention contains a thermochromic ink composition in an ink containing tube, and is formed by communicating a writing tip (ballpoint tip) directly or through a connecting member at the tip of the ink containing tube, An operating body is connected to the rear end of the ink containing tube.
The ballpoint pen tip has a general-purpose structure, a structure in which the ball is held in a ball holding portion formed by pressing and deforming the vicinity of the tip of a metal pipe inward from the outer surface, cutting using a metal material drill or the like Thus, a structure in which the chip portion is formed and the ball is held in the ball holding portion, a structure in which the ball is urged forward by a spring body, or a resin ball receiving seat inside the metal or plastic chip is provided. The provided structure can be illustrated.
The ball may be about 0.1 to 1.5 mm in diameter, such as cemented carbide, stainless steel, ruby, ceramic, resin, rubber, etc., preferably 0.3 to 1.0 mm, more preferably 0. .3 to 0.7 mm is used.
As the ink containing tube for containing the ink composition, a molded body made of a thermoplastic resin such as polyethylene, polypropylene, polyethylene terephthalate or nylon, or a tube made of a metal such as stainless steel is used.
In the case of containing a reversible thermochromic ink composition, it is preferable to prevent light resistance deterioration of the ink composition by using an ink containing tube having a light shielding property, and is made of metal or a thermoplastic resin containing a colorant. A molded body is used. Moreover, when using the ink containing tube which has transparency, it is preferable that the axial cylinder which accommodates a refill is light shielding.
In addition, it is preferable to closely arrange the ink backflow preventer composition on the end face of the ink composition housed in the ink housing tube.

The operation body is connected to the rear end of the ink storage tube, and the operation body protrudes from the side wall of the shaft cylinder when it is accommodated in the shaft cylinder.
By sliding the projecting operation body, the writing tip (ballpoint pen tip) appears and disappears from the opening at the tip of the barrel.
The operating body is not limited as long as the color changes depending on the viewing angle, for example, by providing a metallic luster layer containing a transparent metallic luster pigment having color flop on the surface of the operating body, A configuration in which the color changes depending on the viewing angle can be given.
Examples of the transparent metallic luster pigment having color flop include a cholesteric liquid crystal type transparent metallic luster pigment and a transparent metallic luster pigment obtained by coating silicon oxide with one or more metal oxides.
The cholesteric liquid crystal type transparent metallic luster pigment will be described.
The liquid crystal polymer used as the cholesteric liquid crystal type transparent metallic luster pigment has a property that only a part of the incident light is reflected in a wide spectral region due to the interference effect of light, and the light is transmitted through all other regions. The region of the reflection spectrum is determined by the pitch width of the helical polymer and the refractive index of the reversible thermochromic material, and the reflection spectral region is divided into light components polarized in the left and right spirals, with the spiral being Depending on the direction of rotation, one is reflected and the other can be transmitted. As a result, the cholesteric liquid crystal type transparent metallic luster pigment has the property of transmitting and reflecting over the entire spectral region, that is, the color flop property in which the color tone changes depending on the excellent metallic luster and the viewing angle.
Further, the cholesteric liquid crystal type transparent metallic luster pigment has transparency as well as glitter.
Specific examples of the cholesteric liquid crystal type transparent metallic luster pigment include pigments based on a siloxane skeleton having a mesogen in the side chain.
As the cholesteric liquid crystal type transparent metallic luster pigment, specifically, trade name “Helicone HC” manufactured by Wacker Chemie, product number: Sapphire (30 μm: blue → dark color), Scarabeus (30 μm: green → blue), Jade (30 μm) : Gold → green blue), Maple (30 μm: Bronze color → Green) and the like.
The parentheses in the product number indicate the average particle diameter and color tone, and the average thickness is 5 μm.

The transparent metallic luster pigment in which the silicon oxide is coated with one or more kinds of metal oxides has light transmissivity and expresses various colors depending on the viewing angle and the light hitting angle due to the light interference effect. Color flop and excellent metal gloss.
Further, when silicon oxide is coated in multiple layers with two or more kinds of metal oxides, color flop properties and metal gloss can be more effectively imparted by using metal oxides having different light reflectivities.
Examples of the metal oxide include tin oxide, titanium oxide, and iron oxide.
As the metallic luster pigment, trade name: Colorstream T10-01 Viola Fantasy (20 μm: purple → silver color → green → blue), Colorstream T10-02 Artic Fire (20 μm: green blue → silver color → red → gold) Colorstream T10-03 Tropic Sunrise (20 μm: green → silver → red → orange) and the like.
The parentheses in the product number indicate the average particle diameter and color tone, and the average thickness is 0.01 to 1.0 μm.

A transparent metallic luster pigment having color flop properties is dispersed in a vehicle containing a binder resin in an appropriate amount to prepare a metallic luster ink or paint, and known coating methods such as screen printing, offset printing, gravure printing, etc. A metallic gloss layer is formed on the operation body by means of printing such as coater, tampo printing, transfer, brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, dip coating and the like.
The metallic gloss layer is not limited to a solid print, and may be an image such as a letter, a number, a symbol, or a design.

In addition, by dividing a plurality of images into a large number of strips on the surface of the operating body, and arranging each strip in order to adjoin, and providing a lenticular lens on the image, the color changes depending on the viewing angle It can also be set as the structure to do.
In the case where the lenticular lens is provided, the color may change and the image may change depending on the viewing angle.

The thermochromic ink composition includes (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reversible heat comprising a reaction medium that determines the temperature at which the color reaction occurs. An ink composition using as a colorant a reversible thermochromic microcapsule pigment that changes color from colorless to colorless in which the color-changing composition is encapsulated is suitable.
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 = 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. In other words, the shape of the curve plotting the change in color density due to the temperature change is the case where the temperature is raised from the lower temperature side than the color change temperature range and the case where the temperature is lowered from the higher temperature side than the color change temperature range. The color changes in a significantly different path at a low temperature range below the complete color development temperature (t ₁ ) or the color erase state at a 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) Applicable (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 (friction member) frictional heat, a heating element such as a hair dryer, that is, 50 to 95 ° C., It is effective in maintaining the color exhibited in the normal state (daily life temperature range) by specifying the range of preferably 55 to 90 ° C, more preferably 60 to 80 ° C, and the ΔH value of 40 to 100 ° C. Can be made.
If the complete color erasing temperature t ₄ is 50 ° C. or higher, the state before discoloration can be maintained even under high temperature conditions such as in 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 refill, 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,
3 ', 6'-bis [phenyl (3-ethylphenyl) amino] -spiro [isobenzofuran-1 (3H), 9'-[9H] xanthen] -3-one,
4- [2,6-bis (2-ethoxyphenyl) -4-pyridinyl] -N, N-dimethylbenzenamine and the like can be mentioned.

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。 Furthermore, a compound represented by the following general formula (1) is preferably used as the component (c).

[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 (5) 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.

  Further, as the electron-accepting compound, a specific alkoxyphenol compound having a linear or side chain alkyl group having 3 to 18 carbon atoms may be used (Japanese Patent Laid-Open Nos. 11-129623 and 11-5973), Hydroxybenzoic acid esters (Japanese Patent Laid-Open No. 2001-105732), gallic acid esters and the like (Japanese Patent Publication No. 51-44706, Japanese Patent Laid-Open No. 2003-253149) are used. A microcapsule pigment containing a reversible thermochromic composition that is decolored by cooling) can also be applied (see FIG. 3).

  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).

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.
Here, a non-thermochromic dye or pigment may be blended in the microcapsule pigment so as to exhibit a tautomatic color change from colored (1) to colored (2).
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, the microcapsule pigment clogs the gap between the ball and the ball holding portion when it is put into practical use by being accommodated in a ballpoint pen, and ink ejection properties are liable to be 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. .

The microcapsule pigment may have a circular cross section or a non-circular cross section.
Here, it is preferable that the reversible thermochromic composition: 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 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.

The medium used in the ink composition may be an organic solvent, but preferably water and, if necessary, a water-soluble organic solvent.
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.
By adding the shear thinning agent, it is possible to suppress agglomeration and sedimentation of the microcapsule 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.
In addition, even when the writing tip of the refill containing ink is left in the air for a long time by using a polysaccharide and inorganic particles such as smectite or hectorite as the shear thinning agent, the writing tip It is possible to suppress the occurrence of scumming or inability to write due to drying.
The polysaccharide is contained in the ink composition in an amount of 0.2 to 0.5% by mass, and the mass ratio of the polysaccharide to the inorganic particles is 1: 0.2 to 1: 1.5. Satisfying both the effect of suppressing the aggregation and sedimentation of microcapsule pigments and the effect of suppressing the occurrence of scumming and inability to write due to drying of the writing tip, and a refill exhibiting good writing performance even after aging Can be obtained.
Among the shear thinning agents, if the polysaccharide is less than 0.2% by mass in the total amount of the ink composition, the ink viscosity is too low and the effect of suppressing aggregation and sedimentation of the microcapsule pigment is poor. If it exceeds 0.5% by mass in the total amount of the ink composition, the ink viscosity is too high and the handwriting tends to fade.
Furthermore, when the mass ratio of the inorganic particles is less than 0.2 with respect to the mass of the polysaccharide, the synergistic effect with the polysaccharide is poor, and only the same effect as when the polysaccharide is used alone is obtained. . On the other hand, when the mass ratio of the inorganic particles is more than 1.5 with respect to the mass of the polysaccharide, the handwriting is likely to be blurred.
In addition, it is more preferable that the polysaccharide is contained in an amount of 0.2 to 0.3% by mass in the total amount of the ink composition, and the mass ratio of the polysaccharide to the inorganic particles is 1: 0.4 to 1: 1. More preferably 0.

In the ink composition, it is preferable to contain a sugar mixture containing at least 30% by mass of a starch saccharified product of 8 or more sugars and / or a reduced product thereof, which can improve the drying resistance, A sagging prevention performance can be imparted.
As the sugar mixture, those containing 50% or more of saccharides having 8 or more sugars are preferably used, and more preferably those containing 70% or more of 8 or more sugars are used.
In order to impart dry resistance, it is necessary to form a dry film to some extent, but monosaccharides and disaccharides are not sufficient to form a dry film, so the effect on dry resistance is small and water absorption is high. When applied to a ballpoint pen, dripping is likely to occur when the writing tip is left facing down (inverted). In addition, in the case of about 3 to 7 sugars, the water absorption is lower than that of monosaccharides or disaccharides, but sufficient drying resistance cannot be obtained.
Furthermore, if a large amount of addition is attempted in order to obtain sufficient drying resistance, the water absorption increases and causes dripping, or the added sugar cannot be completely dissolved and the solid content in the ink increases, resulting in drying resistance. May decrease.
Since the saccharides have the characteristics that the hygroscopicity decreases as the molecular weight increases and a dry film is easily formed, the use of saccharides of 8 or more sugars can prevent drooping under high humidity and resistance to drying. Will also improve.
Furthermore, performances such as heat resistance, acid resistance, and microbial resistance are improved, and a stable state can be maintained in the ink.
As the saccharides having 8 or more sugars, a starch saccharified product obtained by enzymatic decomposition of starch or a reduced starch saccharified product obtained by reducing the terminal group of the starch saccharified product can be used.
Further, when starch is decomposed, saccharides having various degrees of polymerization are generated, and therefore it is technically difficult to completely isolate only saccharides having 8 or more sugars, and manufacturing costs are also increased. Therefore, in a sugar mixture containing 7 or less saccharides, the above performance can be sufficiently obtained in the ink by containing 30% by mass or more of the 8 or more saccharides, and is resistant to dripping and dripping prevention. Can be granted.
The said sugar mixture is mix | blended in 0.5-10.0 mass% with respect to the ink composition whole quantity, Preferably it is 1.0-8.0 mass%. If the amount is less than 0.5% by mass, it is difficult to obtain the effect of improving the drying resistance. If the amount is more than 10.0% by mass, the viscosity of the ink increases, which may cause crying or blurring, and hinder followability. There is. Furthermore, drying resistance may be deteriorated.

  Further, if necessary, an alkyd resin, an acrylic resin, a styrene maleic acid copolymer, a cellulose derivative, polyvinyl pyrrolidone, polyvinyl alcohol or the like may be added for fixing to the paper surface or imparting viscosity.

  Also, higher fatty acids such as oleic acid, nonionic surfactants having a long chain alkyl group, polyether-modified silicone oil, thiophosphite tri (alkoxycarbonylmethyl ester) and thiophosphite tri (alkoxycarbonylethyl ester) Thiophosphorous acid triester, polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether phosphoric acid monoester, polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether phosphoric acid diester, or metal salt or ammonium salt thereof It is preferable to add a lubricant such as an amine salt or an alkanolamine salt to prevent wear of the ball seat.

  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.

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.
It is preferable to add a gelling agent to the nonvolatile liquid and / or the hardly volatile liquid to increase the viscosity to a suitable viscosity. The surface of the silica is hydrophobized, the surface is methylated fine particle silica, and aluminum silicate. , Swellable mica, hydrophobic thickeners such as bentonite and montmorillonite, fatty acid metal soaps such as magnesium stearate, calcium stearate, aluminum stearate, zinc stearate, tribenzylidene sorbitol, fatty acid amide, amide modified Examples include dextrin compounds such as polyethylene wax, hydrogenated castor oil, fatty acid dextrin, and cellulose compounds.
Furthermore, the liquid ink backflow prevention body composition and a solid ink backflow prevention body composition can be used in combination.

The ball-point pen refill is stored in the shaft cylinder, and the writing tip of the refill appears and disappears from the opening of the tip of the shaft cylinder by the operation of the retracting mechanism.
Examples of the shaft cylinder include resin, metal, and ceramic.
The slide type has a slide part on the side surface of the shaft tube, and the slide part is operated to slide the clip portion provided on the shaft tube. By doing so, a configuration in which the writing tip of the refill is caused to appear and disappear from the tip opening of the shaft tube can be exemplified.
One or two or more refills containing the thermochromic ink composition are contained in the shaft cylinder.

The handwriting obtained by writing with the ballpoint pen can be discolored by friction 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 or a friction body that can change color by a simple method is used. Is used.
The friction member or the friction body is preferably an elastic body such as an elastomer or a plastic foam which is rich in elasticity and can generate frictional heat by generating appropriate friction during friction. Wood, metal, and fabric may be used.
Although the handwriting can be rubbed using an eraser, the above-mentioned friction member is preferably used because erase scraps are generated at the time of 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.
Although the said friction member can also obtain a writing instrument set combining a writing instrument and the member (friction body) of another arbitrary shape, it is excellent in portability by providing a writing instrument with a friction member.
The location where the friction member is provided is not particularly limited. A friction member can be provided at the rear end portion of the shaft cylinder (the portion where the writing tip portion is not provided).
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.

  The ballpoint pen contains a non-color-changing ink composition in an ink containing tube, and a ballpoint pen tip is provided at the front end of the ink containing tube directly or via a connecting member, and the rear end of the ink containing tube The part can be used in combination with a ballpoint pen refill connected with a colored operation body of the same color as the ink color.

Next, examples of the colorant for the non-color-changing ink composition include general dyes and pigments, fluorescent pigments, metallic luster pigments, and white pigments such as titanium dioxide.
The medium used in the ink composition may be an organic solvent, but preferably water and, if necessary, a water-soluble organic solvent.
As the water-soluble organic solvent, the same ones as described above are used.
Examples of the ink composition include a shear thinning ink containing a shear thinning agent.
As the shear thinning agent, the same ones as described above are used.
In the ink composition, a sugar mixture containing at least 30% by mass of a starch saccharified product of 8 or more sugars and / or a reduced product thereof as described above, a resin, a lubricant, a pH adjuster, an antirust An agent, antiseptic or antifungal agent, wetting agent, antifoaming agent, surfactant and the like can also be added.

One or two or more ballpoint pen refills containing the non-color-changing ink composition are contained in the shaft cylinder.
Specifically, a configuration in which one refill containing a thermochromic ink composition is accommodated in the shaft cylinder and one refill containing a non-color-changing ink composition is accommodated in the shaft cylinder, thermochromic ink One refill containing the composition is contained in the shaft cylinder, and two to four refills containing non-color-changing ink compositions of different colors are contained in the shaft cylinder, thermochromic ink having different colors The structure which accommodates 2 thru | or 4 refills which accommodated the composition in a shaft cylinder, and accommodates one refill which accommodated the non-color-changeable ink composition in a shaft cylinder is mentioned.

Example 1
Preparation of reversible thermochromic ink composition A (ii) 4.5 parts of 2- (2-chloroanilino) -6-di-n-butylaminofluorane as component (4), 4,4 ′-(2 -Methylpropylidene) 4.5 parts of bisphenol, 7.5 parts of 2,2-bis (4'-hydroxyphenyl) hexafluoropropane, and 50.0 parts of 4-benzyloxyphenylethyl caprate as component (c). Microcapsule pigment (T ₁ : −20 ° C., T ₂ : −9 ° C., T ₃ : 40 ° C., T ₄ : 57 ° C., ΔH) containing a heat decolorable reversible thermochromic composition having color memory : 63 ° C., average particle diameter: 2.5 μm, reversible thermochromic composition / wall film = 2.6 / 1.0, color change from black to colorless 20.0 parts, xanthan gum (shear thinning agent) ) 0.3 parts hectorite (shear A reversible thermochromic ink A comprising 0.15 parts of a viscosity reducing agent), 0.2 parts of an antifungal agent, 1.0 part of a lubricant, 1.0 part of triethanolamine and 77.35 parts of water was prepared.

Preparation of reversible thermochromic ink composition B (I) 2- (butylamino) -8- (diphenylamino) -4-methylspiro [5H- [1] benzopyrano [2-3-g] pyrimidine-5 as component (a) 2.0 parts of 1 (3'H) -isobenzofuran] -3-one, 5.0 parts of 2,2-bis (4'-hydroxyphenyl) hexafluoropropane as component (b), 4,4 '-( A microcapsule pigment (T) containing a reversible thermochromic composition having color memory composed of 3.0 parts of 2-methylpropylidene) bisphenol and 50.0 parts of 4-benzyloxyphenylethyl caprate as the component (c) 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, from pink 10.0 parts of xanthan gum (shear thinning agent), 0.15 parts of hectorite (shear thinning agent), 0.2 parts of antifungal agent, lubricant A reversible thermochromic ink B consisting of 0 part, 1.0 part of triethanolamine and 77.35 parts of water was prepared.

Preparation of reversible thermochromic ink composition C (I) 3- (4-Diethylamino-2-hexyloxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide 2 as component 0.0 part, 3.0 parts of 4,4 '-(2-methylpropylidene) bisphenol as component (b), 5.0 parts of 2,2-bis (4'-hydroxyphenyl) hexafluoropropane, (c) A microcapsule pigment (T ₁ : −14 ° C., T ₂ : −6 ° C., T ₃₎ encapsulating a reversible thermochromic composition having color memory consisting of 50.0 parts of 4-benzyloxyphenylethyl caprate as an ingredient : 48 ° C., T ₄ : 60 ° C., ΔH: 64 ° C., average particle size: 2.5 μm, reversible thermochromic composition / wall film = 2.6 / 1.0, color change from blue to colorless) 20 .0 parts, xanthanga (Shear thinning agent) 0.3 part, hectorite (shear thinning agent) 0.15 part, antifungal agent 0.2 part, lubricant 1.0 part, triethanolamine 1.0 part, A reversible thermochromic ink C consisting of 77.35 parts of water was prepared.

Preparation of non-discoloring ink composition a: Black dye 5.0 parts, xanthan gum (shear thinning agent) 0.5 parts, N-vinyl-2-pyrrolidone oligomer 10.0 parts, antifungal agent 0.3 parts, A non-color-changing ink a comprising 0.5 part of a lubricant, 1.0 part of triethanolamine and 82.7 parts of water was prepared.

Preparation of non-color-changeable ink composition b Red dye 5.0 parts, N-vinyl-2-pyrrolidone oligomer 10.0 parts, mildew-proofing agent 0.3 parts, lubricant 0.5 parts, triethanolamine 1.0 Part, 82.7 parts of water was prepared.

Preparation of non-color-changing ink composition c Blue dye 5.0 parts, N-vinyl-2-pyrrolidone oligomer 10.0 parts, mildew-proofing agent 0.3 parts, lubricant 0.5 parts, triethanolamine 1.0 Part non-color-changing ink c consisting of 82.7 parts of water was prepared.

Example 1 (see FIGS. 4 and 5)
Preparation of a ballpoint pen refill containing a thermochromic ink composition The reversible ink cartridge 4 has a ballpoint tip 2 holding a ball in a ball holding part formed by cutting a metal, and is fixed to the ink containing tube 4 fixed via a connecting member 3. The thermochromic ink A was filled, and then an ink follower mainly composed of polybutene was filled, and the operation body 5 was attached to the rear end of the ink containing tube to obtain a ballpoint refill 1.
The operating body is composed of a transparent resin luster pigment coated with titanium oxide on the surface of a black resin molded body (Merck, Colorstream T10-01 (Viola Fantasy), particle size: 5 to 50 μm) and 10 parts of binder resin. An oil-based spray ink comprising 90 parts of the ink vehicle is spray-coated to provide a metallic gloss layer.
According to the viewing angle of the operation body, gold, silver, green and purple metallic luster colors are visually recognized on a black background.

Preparation of a ballpoint pen refill containing a non-color-changing ink composition The non-color-changing ink a is filled in an ink-holding tube in which a ballpoint chip holding a ball is fixed to a ball-holding portion formed by cutting a metal. Next, an ink follower mainly composed of polybutene was filled, and an operation body made of a black resin molded body was attached to the rear end of the ink containing tube to obtain a ballpoint pen refill.

Ballpoint Pen Production Each refill is housed in the light-shielding shaft tube 7, and the writing tip of each refill is selectively projected and retracted by sliding operation of an operating body (lever) protruding from a window hole provided on the shaft tube side wall. A composite ballpoint pen 6 was obtained.
The composite ballpoint pen is provided with a friction member 8 made of SEBS resin at the rear end of the shaft tube.
The composite writing instrument can form a black thermochromic handwriting and a black non-coloring handwriting with a single writing tool, and the thermochromic handwriting can be easily erased by rubbing with a friction member.
The composite writing instrument is capable of refill operation without the need to write once and check the handwriting when judging the state capable of forming a thermochromic handwriting and the state capable of forming a non-color-changing handwriting when writing. It was easy to distinguish by confirming the color change of the part.

Example 2
Preparation of a ballpoint pen refill containing a thermochromic ink composition The reversible thermochromic property in an ink containing tube in which a ballpoint tip holding a ball is fixed to a ball holding part formed by cutting a metal through a connecting member Ink A was filled, and then an ink follower mainly composed of polybutene was filled. An operation body was attached to the rear end portion of the ink containing tube to obtain a ballpoint refill.
The operating body is a black resin molding surface, a cholesteric liquid crystal type transparent metallic luster pigment (manufactured by Wacker Chemie, Helicone HC (Scarabeus, SLM90120), an average thickness of 5 μm, an average particle size of 30 μm) and a binder. An oil-based spray ink consisting of 90 parts of an ink vehicle containing a resin is spray-coated and a metallic gloss layer is provided.
Depending on the viewing angle of the operating body, green and blue metallic luster colors with high luminance are visually recognized on a black background.

Preparation of a ballpoint pen refill containing a non-color-changing ink composition The non-color-changing ink b was filled in an ink-holding tube in which a ball-point pen tip holding a ball was fixed to a ball-holding portion formed by cutting a metal. Next, an ink follower mainly composed of polybutene was filled, and an operation body made of a red resin molded body was attached to the rear end portion of the ink containing tube to obtain a ballpoint pen refill.

Production of ballpoint pen Each refill is housed in a light-shielding shaft tube, and the writing tip of each refill is selectively projected and retracted by a sliding operation of an operating body (lever) projecting from a window hole provided on the side wall of the shaft tube. A composite ballpoint pen was obtained.
The composite ballpoint pen is provided with a friction member made of SEBS resin at the rear end portion of the shaft tube.
The composite writing instrument can form a black thermochromic handwriting and a red non-coloring handwriting with a single writing instrument, and the thermochromic handwriting can be easily erased by rubbing with a friction member.
The composite writing instrument is capable of refill operation without the need to write once and check the handwriting when judging the state capable of forming a thermochromic handwriting and the state capable of forming a non-color-changing handwriting when writing. It was easy to distinguish by confirming the color change of the part.

Example 3
The reversible thermochromic ink A5 is filled in an ink containing tube in which a ballpoint pen tip holding a ball is fixed to a ball holding portion formed by cutting a metal via a connecting member, and then polybutene is used as a main component. The ink follower to be filled was filled, and an operation body was attached to the rear end of the ink containing tube to obtain a ballpoint refill.
The operating body is a black resin molding surface, a cholesteric liquid crystal type transparent metallic luster pigment (manufactured by Wacker Chemie, Helicone HC (Jade, SLM90220), average thickness 5 μm, average particle size 30 μm) and 10 parts binder. An oil-based spray ink comprising 90 parts of an ink vehicle containing a resin is spray-coated to provide a metallic gloss layer.
Depending on the viewing angle of the operation body, the gold and green metallic luster colors are visually recognized on a black background.

Preparation of a ballpoint pen refill containing a non-color-changing ink composition The non-color-changing ink a is filled in an ink-holding tube in which a ballpoint chip holding a ball is fixed to a ball-holding portion formed by cutting a metal. Next, an ink follower mainly composed of polybutene was filled, and an operation body made of a black resin molded body was attached to the rear end of the ink containing tube to obtain a ballpoint pen refill.

Preparation of a ballpoint pen refill containing a non-color-changing ink composition The non-color-changing ink b was filled in an ink-holding tube in which a ball-point pen tip holding a ball was fixed to a ball-holding portion formed by cutting a metal. Next, an ink follower mainly composed of polybutene was filled, and an operation body made of a red resin molded body was attached to the rear end portion of the ink containing tube to obtain a ballpoint pen refill.

Preparation of a ballpoint pen refill containing a non-color-changing ink composition The non-color-changing ink c is filled in an ink-holding tube in which a ballpoint chip holding a ball is fixed to a ball-holding portion formed by cutting a metal. Next, an ink follower mainly composed of polybutene was filled, and an operation body made of a blue resin molded body was attached to the rear end portion of the ink containing tube to obtain a ballpoint pen refill.

Production of ballpoint pen Each refill is housed in a light-shielding shaft tube, and the writing tip of each refill is selectively projected and retracted by a sliding operation of an operating body (lever) projecting from a window hole provided on the side wall of the shaft tube. A composite ballpoint pen was obtained.
The composite ballpoint pen is provided with a friction member made of SEBS resin at the rear end portion of the shaft tube.
The composite writing instrument is capable of forming a black thermochromic handwriting, a black non-color-changing handwriting, a red non-color-changing handwriting, and a blue non-color-changing handwriting with a single writing tool. The handwriting can be easily erased by rubbing with a friction member.
The composite writing instrument is a refill operation unit that does not require the trouble of once writing and checking the handwriting when determining the state in which thermochromic handwriting can be formed and the state in which non-color-changing handwriting can be formed when writing. It was possible to easily identify the color change.

Example 4
Preparation of a ballpoint pen refill containing a thermochromic ink composition The reversible thermochromic property in an ink containing tube in which a ballpoint tip holding a ball is fixed to a ball holding part formed by cutting a metal through a connecting member Ink A was filled, and then an ink follower mainly composed of polybutene was filled. An operation body was attached to the rear end portion of the ink containing tube to obtain a ballpoint refill.
The operating body is composed of a transparent resin luster pigment coated with titanium oxide on the surface of a black resin molded body (Merck, Colorstream T10-01 (Viola Fantasy), particle size: 5 to 50 μm) and 10 parts of binder resin. An oil-based spray ink comprising 90 parts of the ink vehicle is spray-coated to provide a metallic gloss layer.
According to the viewing angle of the operation body, gold, silver, green and purple metallic luster colors are visually recognized on a black background.

Preparation of a ballpoint pen refill containing a thermochromic ink composition The reversible thermochromic property in an ink containing tube in which a ballpoint tip holding a ball is fixed to a ball holding part formed by cutting a metal through a connecting member Ink B was filled, and then an ink follower mainly composed of polybutene was filled, and an operation body was attached to the rear end of the ink containing tube to obtain a ballpoint refill.
The operating body has a cholesteric liquid crystal type transparent metallic luster pigment (manufactured by Wacker Chemie, Helicone HC (Maple, SLM90320), average thickness 5 μm, average particle diameter 30 μm) 10 parts and binder on the surface of the red resin molded body. An oil-based spray ink comprising 90 parts of an ink vehicle containing a resin is spray-coated to provide a metallic gloss layer.
Depending on the viewing angle of the operating body, red and yellow-green metallic luster colors are visually recognized on a red background.

Preparation of a ballpoint pen refill containing a thermochromic ink composition The reversible thermochromic property in an ink containing tube in which a ballpoint tip holding a ball is fixed to a ball holding part formed by cutting a metal through a connecting member Ink C was filled, and then an ink follower mainly composed of polybutene was filled. An operation body was attached to the rear end of the ink containing tube to obtain a ballpoint refill.
The operating body is a blue resin molded body, 10 parts of a cholesteric liquid crystal type transparent metallic luster pigment (manufactured by Wacker Chemie, Helicone HC (Scarabeus, SLM90120), average thickness 5 μm, average particle diameter 30 μm) and a binder. An oil-based spray ink comprising 90 parts of an ink vehicle containing a resin is spray-coated to provide a metallic gloss layer.
According to the viewing angle of the operation body, green and blue metallic luster colors with high luminance are visually recognized on a blue background.

Production of ballpoint pen Each refill is housed in a light-shielding shaft tube, and the writing tip of each refill is selectively projected and retracted by a sliding operation of an operating body (lever) projecting from a window hole provided on the side wall of the shaft tube. A composite ballpoint pen was obtained.
The composite ballpoint pen is provided with a friction member made of SEBS resin at the rear end portion of the shaft tube.
The composite writing instrument can form a black thermochromic handwriting, a pink discoloring handwriting, and a blue discoloring handwriting with a single writing instrument, and the thermochromic handwriting is rubbed by a friction member. Easy to erase.
The composite ballpoint pen could easily recognize that different thermochromic handwriting could be formed by confirming the color change of the refill operation section.

Example 5
Preparation of a ballpoint pen refill containing a thermochromic ink composition (see FIG. 6)
The reversible thermochromic ink A is filled in the ink containing tube 4 in which the ballpoint pen tip 2 holding the ball is fixed to the ball holding portion formed by cutting the metal through the connecting member 3, and then the polybutene is added. An ink follower as a main component was filled, and an operation body was attached to the rear end of the ink containing tube to obtain a ballpoint refill 1.
The operation body is provided with a lenticular display body in which a lenticular lens is attached to an image printed in black and silver on a surface of a white resin molded body.
According to the viewing angle of the operation body, a black and silver color change is visually recognized on a white background.

Preparation of a ballpoint pen refill containing a non-color-changing ink composition The non-color-changing ink c is filled in an ink-holding tube in which a ballpoint chip holding a ball is fixed to a ball-holding portion formed by cutting a metal. Next, an ink follower mainly composed of polybutene was filled, and an operation body made of a blue resin molded body was attached to the rear end portion of the ink containing tube to obtain a ballpoint pen refill.

Production of ballpoint pen Each refill is housed in a light-shielding shaft tube, and the writing tip of each refill is selectively projected and retracted by a sliding operation of an operating body (lever) projecting from a window hole provided on the side wall of the shaft tube. A composite ballpoint pen was obtained.
The composite ballpoint pen is provided with a friction member made of SEBS resin at the rear end portion of the shaft tube.
The composite writing instrument can form a black thermochromic handwriting and a blue non-coloring handwriting with a single writing instrument, and the thermochromic handwriting can be easily erased by rubbing with a friction member.
The composite writing instrument is capable of refill operation without the need to write once and check the handwriting when judging the state capable of forming a thermochromic handwriting and the state capable of forming a non-color-changing handwriting when writing. It was easy to distinguish by confirming the color change of the part.

Example 6
Preparation of a ballpoint pen refill containing a thermochromic ink composition The reversible thermochromic property in an ink containing tube in which a ballpoint tip holding a ball is fixed to a ball holding part formed by cutting a metal through a connecting member Ink B was filled, and then an ink follower mainly composed of polybutene was filled, and an operation body was attached to the rear end of the ink containing tube to obtain a ballpoint refill.
The operating body is provided with a lenticular display body in which a lenticular lens is attached to an image obtained by printing red and gold strips on the surface of a white resin molded body.
The operating body visually recognizes red and gold color changes on a white background depending on the viewing angle.

Preparation of a ballpoint pen refill containing a non-color-changing ink composition The non-color-changing ink a is filled in an ink-holding tube in which a ballpoint chip holding a ball is fixed to a ball-holding portion formed by cutting a metal. Next, an ink follower mainly composed of polybutene was filled, and an operation body made of a black resin molded body was attached to the rear end of the ink containing tube to obtain a ballpoint pen refill.

Production of ballpoint pen Each refill is housed in a light-shielding shaft tube, and the writing tip of each refill is selectively projected and retracted by a sliding operation of an operating body (lever) projecting from a window hole provided on the side wall of the shaft tube. A composite ballpoint pen was obtained.
The composite ballpoint pen is provided with a friction member made of SEBS resin at the rear end portion of the shaft tube.
The composite writing instrument can form a pink thermochromic handwriting and a black non-discoloring handwriting with a single writing instrument, and the thermochromic handwriting can be easily erased by rubbing with a friction member.
The composite writing instrument is capable of refill operation without the need to write once and check the handwriting when judging the state capable of forming a thermochromic handwriting and the state capable of forming a non-color-changing handwriting when writing. It was easy to distinguish by confirming the color change of the part.

Example 7
Preparation of a ballpoint pen refill containing a thermochromic ink composition The reversible thermochromic property in an ink containing tube in which a ballpoint tip holding a ball is fixed to a ball holding part formed by cutting a metal through a connecting member Ink A was filled, and then an ink follower mainly composed of polybutene was filled. An operation body was attached to the rear end portion of the ink containing tube to obtain a ballpoint refill.
The operation body is provided with a lenticular display body in which a lenticular lens is attached to an image printed in black and silver on a surface of a white resin molded body.
According to the viewing angle of the operation body, a black and silver color change is visually recognized on a white background.

Preparation of a ballpoint pen refill containing a thermochromic ink composition The reversible thermochromic property in an ink containing tube in which a ballpoint tip holding a ball is fixed to a ball holding part formed by cutting a metal through a connecting member Ink B was filled, and then an ink follower mainly composed of polybutene was filled, and an operation body was attached to the rear end of the ink containing tube to obtain a ballpoint refill.
The operating body is provided with a lenticular display body in which a lenticular lens is attached to an image obtained by printing red and gold strips on the surface of a white resin molded body.
The operating body visually recognizes red and gold color changes on a white background depending on the viewing angle.

Preparation of a ballpoint pen refill containing a non-color-changing ink composition The non-color-changing ink a is filled in an ink-holding tube in which a ballpoint chip holding a ball is fixed to a ball-holding portion formed by cutting a metal. Next, an ink follower mainly composed of polybutene was filled, and an operation body made of a black resin molded body was attached to the rear end of the ink containing tube to obtain a ballpoint pen refill.

Production of ballpoint pen Each refill is housed in a light-shielding shaft tube, and the writing tip of each refill is selectively projected and retracted by a sliding operation of an operating body (lever) projecting from a window hole provided on the side wall of the shaft tube. A composite ballpoint pen was obtained.
The composite ballpoint pen is provided with a friction member made of SEBS resin at the rear end portion of the shaft tube.
The composite type writing instrument can form a black thermochromic handwriting, a pink thermochromic handwriting, and a black non-coloring handwriting with a single writing tool, and the thermochromic handwriting is rubbed by a friction member. Can be easily deleted.
The composite writing instrument is capable of refill operation without the need to write once and check the handwriting when judging the state capable of forming a thermochromic handwriting and the state capable of forming a non-color-changing handwriting when writing. It was easy to distinguish by confirming the color change of the part.

Example 8
Preparation of a ballpoint pen refill containing a thermochromic ink composition The reversible thermochromic property in an ink containing tube in which a ballpoint tip holding a ball is fixed to a ball holding part formed by cutting a metal through a connecting member Ink A was filled, and then an ink follower mainly composed of polybutene was filled. An operation body was attached to the rear end portion of the ink containing tube to obtain a ballpoint refill.
The operation body is provided with a lenticular display body in which a lenticular lens is attached to an image printed in black and white on a black resin molding surface.
The operating body visually recognizes a color change between black and white on a white background depending on the viewing angle.

Preparation of a ballpoint pen refill containing a thermochromic ink composition The reversible thermochromic property in an ink containing tube in which a ballpoint tip holding a ball is fixed to a ball holding part formed by cutting a metal through a connecting member Ink B was filled, and then an ink follower mainly composed of polybutene was filled, and an operation body was attached to the rear end of the ink containing tube to obtain a ballpoint refill.
The operating body is provided with a lenticular display body in which a lenticular lens is attached to an image printed on a black resin molded body in the form of a band of red and white.
The operating body visually recognizes a color change between red and white on a white background depending on the viewing angle.

Preparation of a ballpoint pen refill containing a thermochromic ink composition The reversible thermochromic property in an ink containing tube in which a ballpoint tip holding a ball is fixed to a ball holding part formed by cutting a metal through a connecting member Ink C was filled, and then an ink follower mainly composed of polybutene was filled. An operation body was attached to the rear end of the ink containing tube to obtain a ballpoint refill.
The operating body is provided with a lenticular display body in which a lenticular lens is attached to an image printed in a blue and white band shape on the surface of a black resin molded body.
According to the viewing angle of the operation body, a blue and white color change is visually recognized on a white background.

Production of ballpoint pen Each refill is housed in a light-shielding shaft tube, and the writing tip of each refill is selectively projected and retracted by a sliding operation of an operating body (lever) projecting from a window hole provided on the side wall of the shaft tube. A composite ballpoint pen was obtained.
The composite ballpoint pen is provided with a friction member made of SEBS resin at the rear end portion of the shaft tube.
The composite writing instrument can form a black thermochromic handwriting, a pink thermochromic handwriting, and a blue thermochromic handwriting with a single writing tool, and the thermochromic handwriting is rubbed with a friction member. Can be easily deleted.
The composite ballpoint pen could easily recognize that different thermochromic handwriting could be formed by confirming the color change of the refill operation section.

t ₁ Complete color development temperature of reversible thermochromic microcapsule pigment with heat decoloring type t ₂ Color development start temperature of reversible thermochromic microcapsule pigment with heat decoloration type t ₃ Reversible thermochromic microcapsule pigment with heat decoloration type Decoloration start temperature of t ₄ Complete decolorization temperature of reversible thermochromic microcapsule pigment of heat decoloring type T ₁ Complete decoloration temperature of reversible thermochromic microcapsule pigment of ₁ heating color developing type T ₂ Reversible heat of color developing type of heat decoloring type Discoloration start temperature of the color-changing microcapsule pigment T ₃ Color development start temperature of the reversible thermochromic microcapsule pigment of the ₃ heating coloring type T ₄ Color development temperature of the reversible thermochromic microcapsule pigment of the heating ₄ coloring type ΔH Hysteresis width 1 Ballpoint refill 2 Ball-point pen tip 3 Connection member 4 Ink storage tube 5 Operation body 6 Ball-point pen 7 Shaft cylinder 8 Friction member

Claims (7)

  An operation body is connected to the rear end of the ballpoint pen refill containing the thermochromic ink composition, and is removable and insertable into the shaft cylinder. By operating the operation body in the inserted state, A ballpoint pen refill that causes a writing tip portion to appear and disappear from a tip opening portion, wherein the color changes depending on an angle viewed by the operation body.   The ballpoint pen refill according to claim 1, wherein a metallic luster layer containing a transparent metallic luster pigment having a color flop property is provided on the surface of the operation body.   The ballpoint pen refill according to claim 1, wherein a plurality of images are divided into a number of strips on the surface of the operation body, and an image in which the strips are sequentially arranged adjacent to each other, and a lenticular lens is provided on the image. .   The ballpoint pen refill according to any one of claims 1 to 3, wherein any color exhibited by the operation body is the same color as the ink composition in the ink containing tube.   A ballpoint pen containing one or more ballpoint pen refills according to any one of claims 1 to 4.   A ballpoint pen containing one or more ballpoint pen refills according to any one of claims 1 to 4 and one or more ballpoint pen refills containing a non-color-changing ink composition.   The ballpoint pen according to claim 5 or 6, comprising a friction member.

Images