JP2011140125A - Ball-point pen refill and retractable ball-point pen using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a ball-point pen refill which does not show a discoloring of an early handwriting obtained by writing operation after removing a resin coating film formed at the apex of a ball-point pen chip and can form a handwriting which shows successful thermal discoloring function, as well as a retractable ball-point pen using the ball-point pen refill. <P>SOLUTION: This ball-point pen refill 1 includes: microcapsule pigment which encapsulates a composition which is reversibly susceptible to thermal discoloration in a color developing state and can selectively retain either a colored state or a colorless state, inside an ink storage tube 5 to which the a ball-point pen chip 2 is fitted; a resin coating film 3, for antidrying of a pen tip, which is composed of an ultraviolet-curable resin composition, seals the apex of the ball-point pen chip apex of the ball-point pen refill which accommodates an ink composition 6 made of a vehicle containing a shear-rate thinning property donating agent. The retractable ball-point pen using the ball-point pen refill 1 is provided. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a ballpoint pen refill and a retractable ballpoint pen using the same. More specifically, the present invention relates to a ballpoint pen refill provided with a resin coating (seal peel) at the tip end of a ballpoint pen refill containing ink that changes color by heating, and a retractable ballpoint pen using the same.

Conventionally, an approximately spherical resin film is formed by adhering a hot-melt hot-melt adhesive to the tip of a ballpoint pen tip, and a ball at the tip of the tip, a ball holding portion, and a gap between the ball and the ball holding portion. An attempt to prevent the tip end of the chip from drying and to prevent the solvent in the ink from volatilizing has been disclosed (see, for example, Patent Document 1).
The configuration in which the tip of the ball-point pen tip is provided with a resin film is useful for a ball-point pen refill in which the tip is left unused for a long period of time, and a retractable ball-point pen containing the ball-point pen refill.
On the other hand, there is disclosed a ballpoint pen that contains a ballpoint refill containing ink that changes color by heating and that has a friction member (see, for example, Patent Document 2). The handwriting formed on the writing surface using the ballpoint pen can be discolored by frictional heat generated by rubbing with a friction member.
When a resin coating is provided on the tip of a ballpoint pen tip of a ballpoint pen refill containing ink that changes color by heating, the ink located near the tip of the tip of the ballpoint tip changes color when a hot melt adhesive is applied. The initial handwriting obtained by removing the film and writing is problematic in that the color tone after discoloration is visually recognized.

Japanese Patent Laid-Open No. 2001-225584 JP 2005-213361 A

  The present invention provides a ballpoint pen refill in which the color tone before the color change is visually recognized even if a resin film is provided at the tip of the ballpoint pen tip of the ballpoint pen refill containing the ink that changes color by heating, and a retractable ballpoint pen using the same. It is something to be offered.

The present invention provides an ink containing tube in which a ballpoint pen tip holding a ball rotatably is mounted directly or via a connecting member, and (b) an electron-donating color-forming organic compound, and (b) an electron-accepting compound. And (c) a reaction medium that controls the color reaction of (i) and (b) above, exhibiting hysteresis characteristics with respect to the color density-temperature curve, exhibiting tautomerism between the colored state and the colorless state, in the process the temperature rises, it starts to decoloring to reach decoloring starting temperature t _3, become completely colorless state at complete decoloring temperature t ₄ above temperature range, in the course of temperature from colorless state is lowered, start color development When the temperature reaches t ₂ , the color starts to be colored and becomes completely colored in a temperature range below the complete coloring temperature t ₁ , and the colored state and the colorless state are selectively maintained in the temperature range between the temperature t ₂ and the temperature t _3. Hysteresis characteristics A reversible thermochromic microcapsule pigment encapsulating a reversibly thermochromic composition in a colored state and a ballpoint pen tip of a ballpoint pen refill containing an ink composition comprising at least a vehicle containing a shear thinning agent. A ball-point refill made by adhering a resin film for preventing drying of a nib made of an ultraviolet curable resin composition is a requirement.
Furthermore, the complete color erasing temperature t ₄ is 50 to 90 ° C., the complete color developing temperature t ₁ is 0 ° C. or less, and the removal force when removing the resin coating from the chip is 50 to 1000 gf. It is a requirement that the ink composition contains a non-discoloring colorant.
Furthermore, a retractable ballpoint pen is required which accommodates the ballpoint pen refill in a shaft tube and is configured so that a ballpoint pen tip can be protruded and retracted from the opening at the front end of the shaft tube.

  The present invention provides a ballpoint pen capable of forming a handwriting exhibiting a good thermochromic function without discoloring the initial handwriting obtained by forming a resin film at the tip of a ballpoint pen tip and removing the resin film during use. A refill and a retractable ballpoint pen using the same can be provided.

It is a graph explaining the hysteresis characteristic in the color density-temperature curve of the reversible thermochromic microcapsule pigment used for this invention. It is explanatory drawing which shows the state which provided the resin film in the ball-point pen refill of one Example of this invention. It is explanatory drawing which shows the retractable ball-point pen which accommodated the ball-point refill of FIG. It is explanatory drawing which shows the retractable ball-point pen which accommodated the ball-point refill of FIG. It is explanatory drawing which shows the retractable ball-point pen which accommodated the ball-point refill of FIG. It is explanatory drawing which shows the state which provided the resin film in the ball-point pen refill of the comparative example.

The ballpoint pen tip is a ball holder formed by cutting with a tip holding a ball in a ball holding portion formed by pressing and deforming the vicinity of the tip of a metal pipe inward from the outer surface, a metal material drill or the like. Examples include a chip holding a ball in the holding portion, a chip holding a ball by providing a resin ball receiving seat inside a metal or plastic molded body, and the like.
The tip may be configured to bias the ball forward by a spring body.
The ball may be about 0.3 to 3.0 mm in diameter, such as cemented carbide, stainless steel, ruby, ceramic, resin, rubber, etc., preferably 0.3 to 1.5 mm, more preferably 0. 3 to 1.0 mm are used.

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 that stores the ink composition.
The ball-point pen tip and the ink storage tube are fitted directly or via a connecting member.

The ink composition 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). An ink composition that changes color by heating at least comprising a microcapsule pigment encapsulating a reversible thermochromic composition that is decolored by heating and a vehicle containing a shear thinning agent.
Examples of the microcapsule pigment exhibit large hysteresis characteristics described in JP-A-2006-137886, JP-A-2006-188660, JP-A-2008-45062, JP-A-2008-280523, and the like. In other words, the shape of the curve plotting the change in color density due to temperature change differs greatly between when the temperature is raised from the lower temperature side than the color change temperature range and when the temperature is lowered from the higher temperature side than the color change temperature range. The color changes following the path, and the color development state in the low temperature region below the complete color development temperature (t ₁ ) or the color erase state in the high temperature region above the complete color erase temperature (t ₄ ) is a specific temperature range [t ₂ to A microcapsule pigment containing a reversible thermochromic composition having color memory in the temperature range between t ₃ (substantially two-phase holding temperature range)] is preferably used (see FIG. 1). See).

The hysteresis characteristic in the color density-temperature curve of the reversible thermochromic composition will be described.
In FIG. 1, the vertical axis represents color density and the horizontal axis represents temperature. The change in color density due to the temperature change proceeds along the arrow. Here, A is a point indicating a density at a temperature t ₄ (hereinafter 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, both states of the colored state and the decolored state can coexist, a temperature range of between t ₂ and t ₃ is a region having a large difference in color density It is a real 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.

Complete decoloring temperature t ₄ of the reversible thermal discoloration composition having a color-memory property, the temperature for decoloration than the frictional heat generated by rubbing between the friction member and the writing surface, i.e., 50 ° C. to 90 ° C., preferably 55 to 85 ° C., more preferably in the range of 60 to 80 ° C., and the complete color development temperature t ₁ is a temperature that can be obtained only in a freezing room, a cold district or the like, that is, 0 ° C. or less, preferably −50 to −5 ° C. More preferably, it is in the range of −50 to −10 ° C.

Specific examples of the compounds (a), (b) and (c) are shown below.
As the component (a) of the present invention, that is, the electron-donating color-forming organic compound, diphenylmethane phthalides, phenyl indolyl phthalides, indolyl phthalides, diphenyl methane azaphthalides, phenyl indolyl azaphthalide , Fluorans, stylinoquinolines, diazarhodamine lactones, etc., and these compounds are exemplified 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-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,
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,
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 that are effective in developing fluorescent yellow to red color development.

(B) Component electron-accepting compounds include active proton-containing compounds, pseudo-acidic compounds (compounds that are not acids but act as acids in the composition to cause component (I) to develop color), electrons There is a group of compounds having pores.
Examples of compounds having active protons include monophenols to polyphenols as compounds having phenolic hydroxyl groups, and alkyl groups, aryl groups, acyl groups, alkoxycarbonyl groups, carboxy groups and esters thereof as substituents. 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, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) ethylpropionate, 2,2-bis (4-hydroxyphenyl)- 4-methylpentane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-hydroxyphenyl) n-heptane, 2,2-bis It is 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.

〔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。 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. As the component (c), a compound represented by the following general formula (1) can be used.

[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)] di with ethanol It can be exemplified ester.

（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.

  The mixing 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. (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 microencapsulation of the reversible thermochromic composition includes interfacial polymerization method, interfacial polycondensation method, in situ polymerization method, submerged curing coating method, phase separation method from aqueous solution, phase separation method from organic solvent, melt dispersion There are a cooling method, an air suspension coating method, a spray drying method, and the like, which are appropriately selected according to the application. Furthermore, the surface of the microcapsule pigment can be provided with a secondary resin film according to the purpose to impart durability, or the surface characteristics can be modified for practical use.

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 vehicle is an oily vehicle comprising an organic solvent, a shear thinning agent and optionally various additives, or an aqueous solution comprising water, a shear thinning agent, and optionally an organic solvent and various additives. Vehicle.
Examples of the organic solvent include ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, ethylene glycol monomethyl ether, and 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, etc. It can gel.

By adding the shear thinning agent, it is possible to suppress aggregation and sedimentation of the microcapsule pigment, and it is possible to suppress bleeding of the handwriting, so that good marking can be formed.
Furthermore, when the ink composition is filled into the ballpoint pen, ink leakage from the gap between the ball and the tip when not in use is prevented, or the ink backflow occurs when the writing tip is left facing upward (upright state). 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 Nonionic surfactants having an HLB value of 8 to 12, such as ciethylene alkyl ether, polyoxypropylene alkyl ether, polyoxyethylene alkyl phenyl ether, fatty acid amide, salts of dialkyl or dialkenylsulfosuccinic acid, N-alkyl-2- Examples thereof include a mixture of pyrrolidone and an anionic surfactant, and a mixture of polyvinyl alcohol and an acrylic resin.

Furthermore, an alkyd resin, an acrylic resin, a styrene maleic acid copolymer, a cellulose derivative, polyvinyl pyrrolidone, polyvinyl alcohol, dextrin, and the like can be added as needed for fixing to the paper surface and imparting viscosity.
Various additives can be added to the vehicle as necessary.
Examples of the additive include 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). ), Etc., phosphoric acid monoesters of polyoxyethylene alkyl ethers or polyoxyethylene alkyl aryl ethers, phosphoric acid diesters of polyoxyethylene alkyl ethers or polyoxyethylene alkyl aryl ethers, or metal salts thereof It is preferable to add a lubricant such as an ammonium salt, an amine salt, or an alkanolamine salt to prevent wear of the ball seat.
Further, by adding a sulfur-based extreme pressure additive such as 2,5-dimercapto-1,3,4-thiadiazole and / or a salt thereof, the ink was once frozen even in the acidic or alkaline region. It is possible to suppress poor dispersion and aggregation of the microcapsule pigment that occurs after the ink is thawed again, thereby preventing an increase in ink viscosity, accompanying handwriting blurring and lightening, and preventing ball corrosion.
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 nitrite, saponin, etc. Rust preventive agent, coalic acid, sodium salt of 1,2-benzthiazolin-3-one, sodium benzoate, sodium dehydroacetate, potassium sorbate, propyl paraoxybenzoate, 2,3,5,6-tetrachloro-4- Preservatives or antifungal agents such as (methylsulfonyl) pyridine, urea, reduced or non-reduced starch hydrolyzate, oligosaccharides such as trehalose, sucrose, cyclodextrin, glucose, dextrin, sorbit, mannitol, sodium pyrophosphate, etc. of Junzai, defoamers, dispersing agents, a fluorine-based surfactant or a nonionic surface active agent for improving the ink permeability may be added.
In addition, a general dye or a general pigment can be added as a non-color-changing colorant to the ink composition to exhibit a color change from colored (1) to colored (2) having a different color tone.

The back end of the ink stored in the ink storage tube may be filled with an ink backflow prevention body.
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, Examples thereof include polyether-modified silicone oil and fatty acid-modified silicone oil, and one or more can be used in combination.

It is preferable to add a gelling agent to the non-volatile liquid or the hardly volatile liquid to increase the viscosity to a suitable viscosity. The surface is treated with hydrophobic silica, the surface is treated with methylated fine particle silica, aluminum silicate, swelling. Clay-based thickeners such as bentonite and montmorillonite treated with hydrophobic mica, fatty acid metal soaps such as magnesium stearate, calcium stearate, aluminum stearate, zinc stearate, tribenzylidene sorbitol, fatty acid amide, amide-modified polyethylene wax And dextrin compounds such as hydrogenated castor oil and 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 ultraviolet curable resin composition for forming the resin film (seal peel) comprises at least an ultraviolet curable resin and a photopolymerization initiator.
Known resins are used as the ultraviolet curable resin, and oligomers such as urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, unsaturated polyester, butadiene-based (meth) acrylate, polyol acrylate, and melamine acrylate Various modified products such as prepolymers, polymers and ethylene oxide adducts thereof, alkyl acrylates such as methyl, ethyl, 2-ethylhexyl, lauryl and stearyl, cyclic acrylates such as tetrahydrofurfuryl, isobornyl and cyclohexyl, aromatic Acrylate, hydroxyl group-containing acrylate, carboxyl group-containing acrylate, amino group-containing acrylate, phosphate group-containing acrylate, N-vinylpyrrolidone, acrylamide, N-mitylol Various monofunctional monomers such as chloramide, acryloylmorpholine, and diacrylates such as hexanediol, neopentyl glycol, and nonanediol, triacrylates such as trimethylolpropane, glycerin, and pentaerythritol, pentaerythritol, ditrimethylolpropane, and the like Examples include various polyfunctional monomers such as tetraacrylates, penta and hexaacrylates of dipentaerythritol, glycidyl methacrylate-acrylic acid adduct, and methylene bisacrylamide.

  Examples of the photopolymerization initiator include acetophenone, dimethoxyacetophenone, 2-phenyl-2,2-dimethoxyacetophenone, 2-hydroxy-2,2-dimethoxyacetophenone, trichloroacetophenone, p-methylthio-2-morpholino-2,2- Acetophenone initiators such as dimethylacetophenone and 1-hydroxycyclohexyl phenyl ketone, benzophenone, [4-[(4-methylphenyl) thio] phenyl] phenyl-methanone, Michler ketone, [4-phenylthiophenyl] phenyl-methanone, [ 4-phenylthiophenyl] -2'-chlorophenyl-methanone, [4-phenylthiophenyl] -4'-methoxyphenyl-methanone, [4-phenylthiophenyl] -2 ', 4'-dichlorophenyl-methanone Benzophenone initiators such as chloromethylbenzophenone, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, thioxanthone initiators such as 1-chloro-4-propoxythioxanthone, benzoin ether initiators, acylphosphine Examples thereof include oxide initiators and α-acyloxime ester initiators.

  In addition, as various additives, photosensitizers such as N-methyldiethanolamine, Michler's ketone, 4-dimethylaminoethylbenzoate and 4-dimethylaminoisoamylbenzoate, and cobalt octylate which is a metal compound such as cobalt, manganese, lead and iron , Oxidation polymerization catalysts such as cobalt naphthenate and lead monoxide, antifoaming agent, antioxidant, singlet oxygen quencher, anti-aging agent, antistatic agent, thixotropic agent, viscosity modifier, dispersant, rust prevention Various additives such as an agent, an adhesion-imparting agent, and a filler can be appropriately added.

After immersing the writing tip of the ballpoint pen refill in the ultraviolet curable resin composition, the resin film is formed by taking out and irradiating with ultraviolet rays.
The resin coating should be able to be easily removed without remaining on the chip surface when not needed, and to have a function that the resin coating does not easily peel off due to vibration during high temperature or low temperature environments or transportation. Therefore, the removal force when removing the resin coating from the chip is adjusted to 50 to 1000 gf, preferably 100 to 700 gf, more preferably 150 to 500 gf. If the pull-out force is less than 50 gf, it is easy to desorb and it is difficult to express a desired function, and if it exceeds 1000 gf, it cannot be easily removed at the time of use, and convenience is easily lost.

The ball-point pen refill can be accommodated in a shaft tube to obtain a retractable ball-point pen.
The ballpoint pen refill is housed in the shaft cylinder with the tip exposed to the outside air, and the writing tip protrudes from the opening of the shaft cylinder by the operation of the retracting mechanism.
Examples of the appearance 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 tube and the side surface of the shaft tube, and by pressing the knock portion, the writing tip portion of the ballpoint pen refill is projected and retracted from the front end opening portion of the shaft tube, or on the shaft tube. A configuration in which the writing tip portion of the ballpoint pen refill is projected and retracted from the front end opening portion of the shaft cylinder by pressing the provided clip portion can be exemplified.
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 writing tip part of the ballpoint pen refill is projected and retracted from the front end part of the shaft cylinder by turning the rotating part.
The slide type has a slide part on the side surface of the shaft cylinder, and the sliding tip of the writing point of the ballpoint pen refill is projected and retracted from the front end opening of the shaft cylinder by operating the slide, or the clip part provided on the shaft cylinder is slid. By doing so, it is possible to exemplify a configuration in which the writing tip portion of the ballpoint pen refill is projected and retracted from the opening at the front end of the shaft cylinder.
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 of one of the ballpoint pen refills protrudes and retracts from the opening at the front end of the shaft cylinder by operation of the retractable mechanism. May be.

The handwriting formed by the ballpoint pen containing the ballpoint refill can be erased by applying a friction member.
As the friction member, an elastic body such as an elastomer or plastic foam which is rich in elasticity and can generate frictional heat by generating appropriate friction during friction is suitable.
Although it is possible to rub the handwriting using an eraser, it is preferable to use a friction member as described above because erase scraps are generated during friction.
As the material of the friction member, silicone resin or SEBS resin (styrene ethylene butadiene styrene block copolymer) is preferably used.
The friction member can be obtained by combining a retractable ballpoint pen and a separate member (friction body) having an arbitrary shape to obtain a ballpoint pen set, but is excellent in portability by fixing the friction member to the retractable ballpoint pen.
The location where the friction member is fixed is not particularly limited, but examples include 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), and the knock portion.

A method for manufacturing the ballpoint pen refill and the retractable ballpoint pen of the present invention will be described.
In addition, the mixing | blending in an Example shows a mass part.
Preparation of UV curable resin composition A 93 parts of a mixture of a modified acrylic polymer and an acrylic ester (trade name: Beam Set 243, manufactured by Arakawa Chemical Industries, Ltd.) as an ultraviolet curable resin, and 6 parts of an acetophenone photopolymerization initiator Then, 1.0 part of an antifoaming agent was mixed and stirred to obtain an ultraviolet curable resin composition A.
Preparation of UV curable resin composition B 88 parts of a mixture of a modified acrylic polymer and an acrylic ester (trade name: Beam Set 267, manufactured by Arakawa Chemical Co., Ltd.) as an ultraviolet curable resin, and 11 parts of an acetophenone photopolymerization initiator And 0.05 part of blue dye [trade name: Oplus Blue 630, manufactured by Orient Chemical Co., Ltd.] and 0.95 part of antifoaming agent were mixed and stirred to obtain an ultraviolet curable resin composition B.
Preparation of UV curable resin composition C As an UV curable resin, 27 parts of epoxy acrylate [trade name: EB3703, manufactured by Daicel UC Corporation] and polyester acrylate [trade name: TP-56NA, manufactured by Nippon Kayaku Co., Ltd.] 64.5 parts, 7 parts of acylphosphine oxide photopolymerization initiator, 0.5 parts of blue pigment [trade name: PA-D-7502L blue, manufactured by Dainichi Seika Co., Ltd.], 1.0 defoamer The components were mixed and stirred to obtain an ultraviolet curable resin composition C.

Example 1
Preparation of microcapsule pigment (a) 4,5,6,7-tetrachloro-3- [4- (diethylamino) -2-methylphenyl] -3- (1-ethyl-2-methyl-1H-indole) as component -3-yl) -1 (3H) -isobenzofuranone 2.0 parts, (b) component 4,4 '-(2-ethylhexane-1,1-diyl) diphenol 3.0 parts, A reversible thermochromic composition having color memory composed of 5.0 parts of 2-bis (4′-hydroxyphenyl) -hexafluoropropane and 50.0 parts of 4-benzyloxyphenylethyl caprate as component (c) An encapsulated microcapsule pigment suspension was obtained.
The suspension was centrifuged to isolate the microcapsule pigment.
The microcapsule pigment has an average particle size of 1.8 μm, a complete color erasing temperature of 55 ° C., and a complete color development temperature of −20 ° C., which changes from blue to colorless according to the temperature change.

Preparation of ink composition 12.5 parts of the microcapsule pigment (previously cooled to −20 ° C. or lower to cause the microcapsule pigment to develop a blue color), 0.3 part of succinoglycan (shear thinning agent), 10 parts urea, 10 parts glycerin, 0.5 part phosphate ester surfactant, 0.6 part nonionic permeability imparting agent, 0.1 part modified silicone antifoaming agent, 0.1 part antifungal agent, An ink composition comprising 0.5 part of triethanolamine and 65.4 parts of water was prepared.

Preparation of ballpoint pen refill The ink composition 6 is sucked and filled into an ink containing tube 5 made of polypropylene resin, and the vicinity of the tip of a metal pipe is pressed and deformed inward from the outer surface through a resin connecting member (holder) 4. The ball holding portion formed in this manner was connected to a ballpoint pen tip 2 holding a stainless steel ball 3 having a diameter of 0.7 mm.
Next, an ink backflow preventer (liquid stopper) was filled from the rear end of the polypropylene pipe, and a tail plug was fitted to the rear part of the pipe to obtain a ballpoint pen refill 1.

Formation of Resin Film After immersing the tip of a ballpoint pen refill chip in the UV curable resin composition A, light irradiation was performed using a 120 w / cm metal halide lamp under conditions of a light irradiation distance of 10 cm and a line speed of 15 m / min. The resin film 7 was formed (see FIG. 2).
The initial handwriting obtained by removing the ballpoint refill resin film and writing it was blue.
The handwriting can be erased by rubbing with a friction body made of SEBS resin.

Example 2
Preparation of Microcapsule Pigment (I) 2- (Dibutylamino) -8- (dipentylamino) -4-methyl-spiro [5H- [1] benzopyrano [2,3-g] pyrimidine-5,1 ′ ( 3'H) -isobenzofuran] -3-one 1.0 part, (b) Component 4,4 '-(2-ethylhexane-1,1-diyl) diphenol 3.0 part, 2,2- A reversible thermochromic composition having color memory composed of 5.0 parts of bis (4′-hydroxyphenyl) -hexafluoropropane and 50.0 parts of 4-benzyloxyphenylethyl caprate as component (c) was included. A microcapsule pigment suspension was obtained.
The suspension was centrifuged to isolate the microcapsule pigment.
The microcapsule pigment has an average particle size of 2.3 μm, a complete color erasing temperature of 58 ° C., and a complete color development temperature of −20 ° C., which changes from pink to colorless according to temperature change.

Preparation of ink composition 12.5 parts of the microcapsule pigment (previously cooled to −20 ° C. or less to cause the microcapsule pigment to develop a pink color), 0.3 part of succinoglycan (shear thinning agent) , 10 parts of urea, 10 parts of glycerin, 0.5 part of phosphate ester surfactant, 0.6 part of nonionic permeability imparting agent, 0.1 part of modified silicone antifoaming agent, 0.1 part of antifungal agent An ink composition comprising 0.5 parts of triethanolamine and 65.4 parts of water was prepared.

Preparation of ballpoint pen refill The ink composition was sucked and filled into an ink containing tube made of polypropylene resin, and the vicinity of the tip of a metal pipe was pressed and deformed inward from the outer surface through a resin connection member (holder). The ball holding part was connected to a ballpoint pen tip holding a stainless steel ball having a diameter of 0.5 mm.
Next, an ink backflow preventer (liquid stopper) was filled from the rear end of the polypropylene pipe, and a tail plug was fitted to the rear part of the pipe to obtain a ballpoint pen refill.

Formation of Resin Film After immersing the tip of a ballpoint pen refill tip in the UV curable resin composition B, light irradiation was performed using a 160w / cm metal halide lamp under the conditions of a light irradiation distance of 20 cm and a line speed of 15 m / min. And a resin film was formed.
The initial handwriting obtained by removing the ballpoint refill resin film and writing it was pink.
The handwriting can be erased by rubbing with a friction body made of SEBS resin.

Example 3
Preparation of microcapsule pigment (a) 6 '-(dipentylamino) -2'-[(3- (trifluoromethyl) phenyl) amino] -spiro [isobenzofuran-1 (3H), 9 '-(9H ) Xanthen] -3-one 5.0 parts, (b) component 2,2-bis (4'-hydroxyphenyl) hexafluoropropane, 1,1-bis (4'-hydroxyphenyl) n -A microcapsule pigment suspension containing a reversible thermochromic composition having color memory composed of 4.0 parts of decane and 50.0 parts of capric acid-4-benzyloxyphenylethyl as component (c) was obtained. .
The suspension was centrifuged to isolate the microcapsule pigment.
The microcapsule pigment has an average particle size of 2.0 μm, a complete color erasing temperature of 58 ° C., and a complete color development temperature of −22 ° C., which changes from black to colorless according to temperature change.

Preparation of ink composition 12.5 parts of the microcapsule pigment (previously cooled to −22 ° C. or less to cause the microcapsule pigment to develop a black color), 0.3 part of succinoglycan (shear thinning agent), 10 parts urea, 10 parts glycerin, 0.5 part phosphate ester surfactant, 0.6 part nonionic permeability imparting agent, 0.1 part modified silicone antifoaming agent, 0.1 part antifungal agent, An ink composition comprising 0.5 part of triethanolamine and 65.4 parts of water was prepared.

Preparation of ballpoint pen refill The ink composition was sucked and filled into an ink containing tube made of polypropylene resin, and the vicinity of the tip of a metal pipe was pressed and deformed inward from the outer surface through a resin connection member (holder). The ball holding part was connected to a ballpoint pen tip holding a stainless steel ball having a diameter of 0.5 mm.
Next, an ink backflow preventer (liquid stopper) was filled from the rear end of the polypropylene pipe, and a tail plug was fitted to the rear part of the pipe to obtain a ballpoint pen refill.

Formation of Resin Film After immersing the tip of a ballpoint pen refill chip in the UV curable resin composition C, light irradiation was performed using a 120 w / cm metal halide lamp under conditions of a light irradiation distance of 15 cm and a line speed of 10 m / min. And a resin film was formed.
The initial handwriting obtained by removing the ballpoint refill resin film and writing it was black.
The handwriting can be erased by rubbing with a friction body made of SEBS resin.

Example 4
Preparation of Microcapsule Pigment (a) 2.5 parts of 1,3-dimethyl-6-diethylaminofluorane as component, (4) 4,4 '-(2-methylpropylidene) bisphenol as component (2), 2 , 2-bis (4'-hydroxyphenyl) -hexafluoropropane, and (c) a reversible thermochromic composition having color memory, comprising 50.0 parts of 4-benzyloxyphenylethyl caprate as component (c) To obtain a microcapsule pigment suspension encapsulating.
The suspension was centrifuged to isolate the microcapsule pigment.
The microcapsule pigment has an average particle size of 2.0 μm, a complete color erasing temperature of 60 ° C., and a complete color development temperature of −20 ° C., and changes from orange to colorless according to temperature change.

Preparation of ink composition 12.5 parts of the microcapsule pigment (preliminarily cooled to −20 ° C. or less to cause the microcapsule pigment to develop an orange color), 0.3 part of succinoglycan (shear thinning agent), 10 parts urea, 10 parts glycerin, 0.5 part phosphate ester surfactant, 0.6 part nonionic permeability imparting agent, 0.1 part modified silicone antifoaming agent, 0.1 part antifungal agent, An ink composition comprising 0.5 part of triethanolamine and 65.4 parts of water was prepared.

Preparation of ballpoint pen refill The ink composition was sucked and filled into an ink containing tube made of polypropylene resin, and the vicinity of the tip of a metal pipe was pressed and deformed inward from the outer surface through a resin connection member (holder). The ball holding portion was connected to a ballpoint pen tip holding a stainless steel ball having a diameter of 0.4 mm.
Next, an ink backflow preventer (liquid stopper) was filled from the rear end of the polypropylene pipe, and a tail plug was fitted to the rear part of the pipe to obtain a ballpoint pen refill.

Formation of Resin Film After immersing the tip of a ballpoint pen refill chip in the UV curable resin composition A, light irradiation was performed using a 120 w / cm metal halide lamp under conditions of a light irradiation distance of 10 cm and a line speed of 15 m / min. And a resin film was formed.
The initial handwriting obtained by removing the resin film of the ballpoint pen refill and writing it was orange.
The handwriting can be erased by rubbing with a friction body made of SEBS resin.

Comparative Example 1
The tip of a ballpoint pen refill chip obtained in the same manner as in Example 1 was immersed in a hot melt adhesive (150 ° C.) for 2.0 seconds, and then cooled and solidified to form a resin film (see FIG. 6).
The initial handwriting obtained by removing the resin film of the ballpoint pen refill and writing it was colorless, and no handwriting could be formed.

Comparative Example 2
The tip of a ballpoint pen refill chip obtained in the same manner as in Example 2 was immersed in the same hot melt adhesive (160 ° C.) for 2 seconds, and then cooled and solidified to form a resin film.
The initial handwriting obtained by removing the resin film of the ballpoint pen refill and writing it was colorless, and no handwriting could be formed.

Comparative Example 3
The tip of a ballpoint pen refill chip obtained in the same manner as in Example 2 was dipped in the same hot melt adhesive (180 ° C.) for 2 seconds, and then cooled and solidified to form a resin film.
The initial handwriting obtained by removing the resin film of the ballpoint pen refill and writing it was colorless, and no handwriting could be formed.

Comparative Example 4
A tip of a ballpoint pen refill obtained in the same manner as in Example 2 was immersed in the same hot melt adhesive (200 ° C.) for 1.5 seconds, and then cooled and solidified to form a resin film.
The initial handwriting obtained by removing the resin film of the ballpoint pen refill and writing it was colorless, and no handwriting could be formed.

Example 5
The ballpoint pen refill obtained in Example 1 was incorporated into the shaft tube 9 to obtain a retractable ballpoint pen 8 (see FIG. 3).
The retractable ballpoint pen is housed in the shaft cylinder in a state where the writing tip provided on the ballpoint pen refill is exposed to the outside air, and a retractable mechanism (knock mechanism) provided at the rear end of the shaft cylinder. It is a structure in which the writing tip protrudes from the opening at the front end of the barrel by operation.
The initial handwriting obtained by writing and writing the resin film in a state where the ballpoint pen tip was projected and retracted from the opening at the front end of the barrel by the operation of the projecting mechanism was blue.
In addition, the said handwriting can be decolored by rubbing using the friction member 10 made from SEBS resin provided around the axial cylinder tip opening part.

Example 6
The ballpoint pen refill obtained in Example 2 was incorporated into the shaft tube 9 to obtain a retractable ballpoint pen 8 (see FIG. 4).
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. Is a structure in which the writing tip protrudes from the opening at the front end of the shaft cylinder.
The initial handwriting obtained by writing the resin film in a state where the ball-point pen tip was projected and retracted from the opening at the front end of the shaft cylinder by the operation of the projecting mechanism was pink.
In addition, the said handwriting can be decolored by rubbing using the friction member 10 made from SEBS resin provided in the shaft cylinder rear end part.

Example 7
The ballpoint pen refill obtained in Example 3 was incorporated into the shaft tube 9 to obtain a retractable ballpoint pen 8 (see FIG. 5).
The retractable ballpoint pen is housed in the shaft cylinder in a state where the writing tip provided on the ballpoint pen refill is exposed to the outside air, and by the operation of the retracting mechanism (knock mechanism) provided at the rear portion of the shaft cylinder. This is a structure in which the writing tip protrudes from the opening at the front end of the barrel.
The initial handwriting obtained by writing and writing the resin film with the ball-point pen tip protruding and retracting from the opening at the front end of the barrel by the operation of the protruding and retracting mechanism was black.
In addition, the said handwriting can be decolored by rubbing using the friction member 10 made from SEBS resin provided in the intrusion mechanism.

Example 8
The resin film was removed from the ballpoint pen refill obtained in Example 4 and incorporated into the shaft tube to obtain a cap-type ballpoint pen.
The initial handwriting obtained by removing the cap from the cap-type ballpoint pen and writing it was orange.
The handwriting can be erased by rubbing using a friction body made of SEBS resin provided at the rear end of the shaft cylinder.

t ₁ Complete color development temperature of reversible thermochromic microcapsule pigment t ₂ Color development start temperature of reversible thermochromic microcapsule pigment t ₃ Decolorization start temperature of reversible thermochromic microcapsule pigment t ₄ Reversible thermochromic microcapsule pigment Complete decoloring temperature 1 Ballpoint pen refill 2 Ballpoint pen tip 3 Ball 4 Connection member 5 Ink receiving tube 6 Ink composition 7 Resin coating 8 Retractable ballpoint pen 9 Shaft tube 10 Friction member

Claims (5)

In an ink containing tube in which a ballpoint pen tip that rotatably holds a ball is mounted directly or via a connecting member, (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) It comprises a reaction medium that controls the color reaction of (A) and (B), exhibits a hysteresis characteristic with respect to the color density-temperature curve, exhibits tautomerism between the colored state and the colorless state, and the temperature rises from the colored state. in the process, begins to decoloring to reach decoloring starting temperature t _3, become completely colorless state at complete decoloring temperature t ₄ above temperature range, the process temperature is lowered from colorless state, in the color start temperature t ₂ When it reaches, it starts to be colored and becomes completely colored in the temperature range below the complete color development temperature t ₁ , and the hysteresis characteristic that selectively maintains the colored state and the colorless state in the temperature range between the temperature t ₂ and the temperature t _3. Indicates UV curing is applied to the tip of a ballpoint pen tip of a ballpoint refill containing an ink composition consisting of a reversible thermochromic microcapsule pigment encapsulating a reversible thermochromic composition in a microcapsule and a vehicle containing a shear thinning agent. Pen refill made by adhering a resin film for preventing drying of the nib made of a mold resin composition. The complete decoloring temperature t ₄ is the 50 to 90 ° C., the complete coloring temperature t ₁ is 0 ℃ less claim 1, wherein the ballpoint pen refill.   The ballpoint pen refill according to claim 1 or 2, wherein a removal force upon removing the resin coating from the chip is 50 to 1000 gf.   The ballpoint pen refill according to any one of claims 1 to 3, comprising a non-color-changing colorant in the ink composition.   A retractable ballpoint pen configured to accommodate the ballpoint pen refill according to any one of claims 1 to 4 in a shaft cylinder and to allow a ballpoint pen tip to be retracted from a front end opening of the shaft cylinder.

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