JP2010116425A - Refill for composite ballpoint pen and composite ballpoint pen housing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a refill for a composite ballpoint pen, the refill showing excellent dry-up resistant performance and good starting property upon writing in an initial period and after the lapse of time, and maintaining stable writing performance and forming good handwriting without causing thinning in handwriting or drooling. <P>SOLUTION: The refill for a composite ballpoint pen includes an ink housing tube to which a ballpoint pen chip rotatably holding a ball is attached directly or through a connecting member, the tube filled with the following aqueous ink composition for a ballpoint pen. The ink composition includes at least a pigment, water, a water-soluble organic solvent, a thixotropy-imparting agent, and an ionic substance, with the content of the ionic substance in the ink being not less than 1 mass% with respect to the entire amount of the ink composition; and the ink composition contains the water-soluble organic solvent by 1 to 20 mass% and contains a water-soluble organic solvent having a solubility parameter of 8 to 11 by 80 to 100 mass% in the entire amount of the water-soluble organic solvent. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a refill for a composite ballpoint pen and a composite ballpoint pen containing the same. More specifically, the present invention relates to a composite ballpoint pen refill excellent in dry-up resistance at the pen tip and a composite ballpoint pen containing the same.

In recent years, water-based ink compositions containing water as a main solvent have been widely used as ink compositions accommodated in ballpoint pens. Among them, ink compositions having shear thinning viscosity have the drawback that the handwriting of low-viscosity water-based ballpoint pens blur. It can be solved.
Examples of the substance that imparts shear thinning to the ink composition (shear thinning imparting agent) include polysaccharides such as xanthan gum (see, for example, Patent Document 1).
However, the shear thinning agent may impair dry-up performance, and attempts to improve dry-up performance by using additives such as wetting agents such as water-soluble organic solvents and solid wetting agents such as urea. However, the effect of preventing drying is insufficient, and the viscosity of the ink rises and writing defects such as fading tend to occur.
Specifically, when urea is added excessively, the moisture evaporates from the writing tip, the concentration of the water-soluble organic solvent rises, and a so-called flower bloom phenomenon occurs in which solid content is deposited on the writing tip. Appearance deteriorates and blurring occurs. Furthermore, when a large amount of a water-soluble organic solvent or urea is added, when the writing tip is left faced downward in a humid environment, it is liable to cause problems such as drooping.
As described above, although there are many means for improving the dry-up resistance in the ink composition, other performances required for the ballpoint pen, such as blurring and sagging of handwriting, may be caused.
In particular, when multiple refills for a composite ballpoint pen are housed in the shaft cylinder and used for a composite ballpoint pen with the writing tip (ballpoint tip) always open to the atmosphere when not writing, the handwriting will be blurred or drooping. If this occurs, there is a risk that the merchandise value will be greatly impaired as compared to a retractable ballpoint pen containing a single ballpoint pen refill.
JP 59-74175

  The present invention solves the problems of the above-mentioned composite ballpoint pen refill and the composite ballpoint pen containing the same, that is, the composite type satisfying dry-up resistance without impairing various writing performances. The object is to provide a ballpoint pen refill and a composite ballpoint pen containing the same.

The present invention provides a pigment pen, water, a water-soluble organic solvent, a shear thinning agent, an ionic property, in an ink containing tube in which a ballpoint pen tip holding a ball rotatably is mounted directly or via a connecting member. The content of the ionic substance in the ink is 1% by mass or more based on the total amount of the ink composition, the water-soluble organic solvent is 1 to 20% by mass in the ink composition, and A refill for a ballpoint pen filled with a water-based ink composition for ballpoint pens containing 80 to 100% by mass of a water-soluble organic solvent having a solubility parameter of 8 to 11 in the total amount of the organic solvent is required.
Furthermore, 90-100% by mass of a water-soluble organic solvent having a solubility parameter of 8-11 is contained in the total amount of the water-soluble organic solvent, and the ionic substance contained in the ink composition is dissociated in the ink. The cation formed in this way is a monovalent cation, the monovalent cation is selected from alkali metal ions and ammonium ions, and the content of the ionic substance in the ink composition is the total amount of the ink composition 2) to 15% by mass with respect to the pigment, and (a) the electron donating color-forming organic compound, (b) the electron-accepting compound, and (c) the reaction medium that determines the temperature at which the color reaction occurs A reversible thermochromic microcapsule pigment encapsulating a reversible thermochromic composition comprising the above, wherein the microcapsule pigment exhibits a large hysteresis characteristic with respect to a color density-temperature curve. Exhibit photochromic color state and the colorless state, pigment in the process of temperature increase from the colored state, it begins decolorized to reach a temperature t _3, completely at a temperature t ₄ above temperature range than the temperature t ₃ In the process where the colorless state is reached and the temperature is lowered from the colorless state, the coloring starts when the temperature reaches a temperature t ₂ lower than the temperature t ₃ , and becomes completely colored in a temperature range below the temperature t ₁ lower than the temperature t _2. It exhibits a hysteresis characteristic in which a colored state or a colorless state is selectively maintained in a temperature range between t ₂ and t ₃ , the temperature t ₁ is in the range of −50 to 0 ° C., and the temperature t ₄ is 50 to 90 An ink backflow prevention body that follows the ink consumption is disposed on the rear end surface of the ink composition contained in the refill for the ballpoint pen; It becomes a requirement to become.
Furthermore, the composite ball-point pen refill is accommodated in a plurality of shaft cylinders, and a composite ball-point pen in which the writing tip portion of any of the ball-point pen refills protrudes and retracts from the front end opening of the shaft cylinder by the operation of the retracting mechanism is a requirement. .

  In the present invention, since the shear thinning agent, the specific water-soluble organic solvent, and the ionic substance are used in combination, the ink viscosity does not increase excessively even when the water in the ink evaporates. For compound ballpoint pens that have excellent dry-up performance, good initial writing after the lapse of time, stable writing performance without causing blurring or sagging of the handwriting, and formation of good handwriting A refill and a composite ballpoint pen containing it are obtained.

The aqueous ink composition for ballpoint pens filled in the composite ballpoint pen refill of the present invention comprises 1 to 20% by mass of a water-soluble organic solvent in addition to water as a solvent in the total amount of the ink composition. The solvent contains 80 to 100% by mass, preferably 90 to 100% by mass, of a water-soluble organic solvent having a solubility parameter of 8 to 11, preferably 8 to 10.
When the water-soluble organic solvent having a solubility parameter of 8 to 11 in the water-soluble organic solvent is less than 80% by mass, it is difficult to sufficiently exhibit the effect of dry-up resistance.
Examples of the water-soluble organic solvent having a solubility parameter of 8 to 11 include butyl alcohol, polyhydric alcohols having 5 or 6 carbon atoms, glycol ethers having 4 to 13 carbon atoms, and glycol acetates having 5 to 9 carbon atoms. C5-C10 glycol monoether acetates, C5-C10 hydroxycarboxylic acid esters, C4-C12 carboxylic acid amides and the like are preferably used.
Examples of water-soluble organic solvents having suitable solubility parameters of 8 to 11 are shown below.
As the polyhydric alcohols, diols having two hydroxyl groups having 5 or 6 carbon atoms are preferable, and 1,2-pentanediol, 1,6-hexanediol, 1,2-hexanediol, hexylene glycol ( 2-methyl-2,4-pentanediol) and 3-methyl-1,5-pentanediol.
Examples of the glycol ethers include ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol mono t-butyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, ethylene glycol mono 2-ethylhexyl ether, ethylene glycol monophenyl ether. , Ethylene glycol monobenzyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono 2-ethylhexyl ether, diethylene glycol Monobenzyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol monomethyl ether , Propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono t-butyl ether, propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol No ethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, 3-methoxybutanol, 3-methoxy-3-methyl-1-butanol Etc.
Examples of glycol acetates include diethylene glycol monoacetate, ethylene glycol diacetate, propylene glycol diacetate, glycerol diacetate, and glycerol triacetate.
As glycol monoether acetates, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate , Propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methoxy-3-methyl-1-butyl acetate and the like.
Lactic acid esters are suitable as the hydroxycarboxylic acid esters, and examples thereof include ethyl lactate, butyl lactate, isobutyl lactate, amyl lactate, and isoamyl lactate.
Carboxylic acid amides include N, N-dimethylacetamide, N, N-diethylacetamide, N-vinyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-vinyl-2-pyrrolidone oligomer, ε-caprolactam Etc.
The water-soluble organic solvent having a solubility parameter of 8 to 11 is used in the range of 1 to 20% by mass, preferably 2 to 20% by mass, more preferably 3 to 10% by mass with respect to the total amount of the ink. If it is less than 1% by mass, the effect of dry-up resistance is small, and if it is more than 20% by mass, the shear thinning agent is poorly swelled in the ink from the beginning, and it is difficult to exhibit the desired ink viscosity.
In addition, although other organic solvents can be used in combination with the water-soluble organic solvent having the solubility parameter of 8 to 11, it is less than 20% by mass, preferably less than 10% by mass in the total amount of the water-soluble organic solvent.
Since the water-based ink composition for ballpoint pens contains a water-soluble organic solvent having a solubility parameter of 8 to 11 and an ionic substance, the anti-drying-up prevention performance is improved by adding another water-soluble organic solvent. Therefore, an effective thickening suppressing function can be exhibited in a system in which no other water-soluble organic solvent is added or a very small amount is added.

The ink composition contains an ionic substance, and the content of the ionic substance in the ink is 1% by mass or more, preferably 2% by mass or more, more preferably 3%, based on the total amount of the ink composition. It is at least mass%.
In a system including a shear thinning agent and a water-soluble organic solvent having a solubility parameter of 8 to 11, by containing the ionic substance, it is possible to maintain the dry-up resistance permanently even after the initial time and after the passage of time. .
The ionic substance is ionized in the ink composition to generate a cation and an anion, but a cation having a valence of 2 or more easily reacts with other components in the ink composition to form an insoluble salt. Therefore, the ionic substance is preferably a substance that is ionized to produce a monovalent cation, and is excellent in the effect of maintaining the dry-up resistance after aging while maintaining the writing performance.
Monovalent cations include alkali metal ions such as lithium ions, sodium ions, and potassium ions, ammonium ions, and aliphatic ammonium ions such as monoalkyl ammonium ions, dialkyl ammonium ions, trialkyl ammonium ions, and tetraalkyl ammonium ions. Aromatic ammonium ions such as ions, pyridinium ions, and anilinium ions are exemplified, and alkali metal ions are preferred.
The ionic substances are shown below.
Examples of inorganic salts include halides, sulfates, nitrates, phosphates, carbonates, etc., specifically sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, potassium iodide. , Lithium sulfate, sodium sulfate, ammonium sulfate, sodium nitrate, potassium nitrate, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, metaphosphoric acid Examples thereof include sodium, sodium polyphosphate, potassium polyphosphate, potassium silicate, sodium silicate, sodium carbonate, potassium carbonate, and ammonium carbonate. Among the inorganic salts, neutral inorganic salts that do not affect the pH of the ink composition are suitable, and examples thereof include alkali halides.
Examples of organic salts include salts of various low molecular weight organic acids, surfactants, water-soluble resins, water-soluble dyes, and the like.
Examples of the salts of low molecular weight organic acids include carboxylate, sulfonate, sulfate ester salt, phosphate ester salt and the like.
Examples of the carboxylate include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, benzoic acid, p-butylbenzoic acid, p-phenylbenzoic acid and the like. Substituted benzoic acids, α-naphthalene acetic acid, oxalic acid, succinic acid, butane-1,2,3,4-tetracarboxylic acid, terephthalic acid, naphthalenedicarboxylic acid, trimesic acid, lactic acid, malic acid, glycolic acid, glyceric acid And carboxylate obtained from hydroxybutyric acid, hydroxyisobutyric acid, tartaric acid, mevalonic acid, citric acid, isocitric acid, sorbic acid and the like.
Examples of the sulfonate include aliphatic sulfonic acids such as pentane sulfonic acid, hexane sulfonic acid, heptane sulfonic acid, octane sulfonic acid, and dodecane sulfonic acid, and alkylbenzene sulfones such as benzene sulfonic acid, benzene disulfonic acid, and p-toluene sulfonic acid. Acid, 1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid, naphthalene disulfonic acid such as 1,5-naphthalenesulfonic acid disulfonic acid, naphtholsulfonic acid such as 1-naphthol-3-sulfonic acid, 1-naphthol-2,5 Examples thereof include sulfonates obtained from aromatic sulfonic acids such as naphthol disulfonic acid such as disulfonic acid and aminonaphthol sulfonic acid such as 4-amino-5-hydroxy-2,7-naphthalenesulfonic acid.
Examples of the sulfate salt include salts obtained from monohexyl sulfate, monooctyl sulfate, monodecyl sulfate, monododecyl sulfate and the like.
Examples of the phosphoric acid ester salts include salts obtained from monolauryl phosphoric acid, monostearyl phosphoric acid, monodecyl phosphoric acid, monoisodecyl phosphoric acid and the like.
These salts can be added to the ink as a salt, but when preparing the ink, the organic acid such as carboxylic acid, sulfonic acid, sulfuric acid ester, phosphoric acid ester, alkali hydroxide, aqueous ammonia, various amines, etc. May be neutralized to form a salt directly in the ink.
The surfactant includes a nonionic surfactant and an ionic surfactant, and the ionic surfactant is effective as the ionic substance of the present invention. Examples of the ionic surfactant include anionic surfactants, cationic surfactants, and amphoteric surfactants. Anionic surfactants and amphoteric surfactants are preferable, and an ink composition is more preferably alkaline. Anionic surfactants are used because they are often adjusted to a variety of types and are diverse.
Examples of the anionic surfactant include a carboxylate, a sulfonate, a sulfate ester salt, and a phosphate ester salt. Examples of the carboxylate include a fatty acid soap, an N-acyl amino acid salt, and a polyoxyethylene alkyl ether carboxylic acid. Examples thereof include salts, acylated peptides, and polymer polycarboxylates.
Examples of sulfonates include alkylbenzene sulfonate, alkyl naphthalene sulfonate, formalin condensate of naphthalene sulfonate, formalin condensate of melamine sulfonate, dialkyl sulfosuccinate ester salt, alkyl disulphate sulfosuccinate, polyoxyethylene alkyl Examples thereof include sulfosuccinic acid di-salt, alkyl sulfoacetate, α-olefin sulfonate, N-acyl-N-methyl taurate, dimethyl-5-sulfoisophthalate sodium salt, and the like.
Sulfate esters include sulfated oils, higher alcohol sulfates, secondary higher alcohol sulfates, polyoxyethylene alkyl ether sulfates, secondary higher alcohol ethoxy sulfates, polyoxyethylene fatty acid alkanolamide sulfates, poly Examples thereof include oxyethylene alkylphenyl ether sulfates, monoglyculates, and sulfate esters of fatty acid alkylol amides.
Examples of phosphoric acid ester salts include polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, and alkyl phosphates.
Examples of the cationic surfactant include aliphatic amine salts, aliphatic quaternary ammonium salts, benzalkonium chloride salts, benzethonium chloride, imidazolinium salts, and the like.
Examples of amphoteric surfactants include carboxybetaine-type amphoteric surfactants, aminocarboxylates, imidazolium betaines, lecithins, and alkylamine oxides.
As the water-soluble resin, those having an ionic group in the molecule are effective. Salts of cellulose derivatives having a carboxyl group such as carboxymethylcellulose, alginates, polyacrylates, styrene-acrylic acid copolymer resins and sulfonic acids -Salts of acrylic acid copolymer resins such as acrylic acid copolymer resins, and salts of maleic acid copolymer resins such as ethylene-maleic acid copolymer resins.
If the water-soluble dye also has an ionic group, it is effective as the ionic substance of the present invention, and specifically includes an acid dye, a direct dye, and a basic dye, but the ink composition is adjusted to be alkaline. Acid dyes and direct dyes are more preferred in view of the fact that they are often used and the variety of types.
The ionic substance exhibits a thickening suppression effect when added to a water-based ink composition for ballpoint pens together with a water-soluble organic solvent having a solubility parameter of 8 to 11, and the content of the ionic substance in the ink is It must be 1% by mass or more with respect to the total amount of the ink composition, and a practical range is 2 to 15% by mass, preferably 3 to 10% by mass with respect to the total amount of the ink composition.
If it exceeds 15% by mass, the initial ink viscosity is not sufficient (not showing high ink viscosity). Therefore, there is a problem that the dispersion stability of the pigment is impaired, the handwriting is smeared or the sag is liable to occur. Arise.
Two or more kinds of ionic substances can be used in combination.

A pigment is used as the colorant.
As the pigment, in addition to inorganic pigments such as carbon black and ultramarine blue, organic pigments such as copper phthalocyanine blue and benzidine yellow, surfactants and water-soluble resins have already been used to finely and stably disperse in an aqueous medium. Water-dispersed pigment products and the like are used, for example, as a water-dispersed pigment using a surfactant,
C. I. Pigment Blue 15: 3B [trade name: Sandye Super Blue GLL, pigment content 22%, manufactured by Sanyo Dye Co., Ltd.]
C. I. Pigment Red 146 [trade name: Sandye Super Pink FBL, pigment content 24%, manufactured by Sanyo Dye Co., Ltd.]
C. I. Pigment Yellow 81 [trade name: TC Yellow FG, pigment content about 30%, manufactured by Dainichi Seika Kogyo Co., Ltd.]
C. I. Pigment Red 220/166 [trade name: TC Red FG, pigment content: about 35%, manufactured by Dainichi Seika Kogyo Co., Ltd.].
In addition, as a water-dispersed pigment using a water-soluble resin,
C. I. Pigment Black 7 [Product name: WA color Black
A250, 15% pigment content, manufactured by Dainichi Seika Kogyo Co., Ltd.]
C. I. Pigment Green 7 [trade name: WA-S color Green, pigment content 8%, manufactured by Dainichi Seika Kogyo Co., Ltd.]
C. I. Pigment Violet 23 [trade name: Micropigmo WMVT-5, pigment content 20%, manufactured by Orient Chemical Co., Ltd.]
C. I. Pigment Yellow 83 [trade name: Emacol NS Yellow 4618, pigment content 30%, manufactured by Sanyo Color Co., Ltd.].

  As fluorescent pigments, synthetic resin fine particle fluorescent pigments in which various fluorescent dyes are formed into a solid solution in a resin matrix can be used.

Moreover, a thermochromic pigment can also be used as the pigment.
Examples of the thermochromic pigment include (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reversible thermochromic property comprising a reaction medium that determines the temperature at which the color reaction occurs. A reversible thermochromic microcapsule pigment encapsulating the composition is preferably used.
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 while the heat or cold necessary to develop the state is applied, but when the heat or cold is not applied, the hysteresis width returns to the state exhibited in the normal temperature range. A heat decolorable microcapsule pigment in which a reversible thermochromic composition having relatively small characteristics (ΔH = 1 to 7 ° C.) is encapsulated in a microcapsule can be applied (see FIG. 1).

In addition, large hysteresis characteristics (ΔH _B = 8 to 50 ° C.) described in JP- _B -4-17154, JP-A-7-179777, JP-A-7-33997, JP-A-8-39936, and the like. ), That is, when the shape of the curve plotting the change in color density due to temperature change is lower than the color change temperature range, the temperature rises from the lower temperature side than the color change temperature range. In the specific temperature range, the color changes in a low temperature range below the complete color development temperature (t ₁ ) or the color erase state in the high temperature range above the complete color erase temperature (t ₄ ). A heat-erasable microcapsule pigment in which a reversible thermochromic composition having color memory in a temperature range between t _{2 and} t ₃ (substantially two-phase holding temperature range) is encapsulated in microcapsules Applicable (Fig. 2 Irradiation).

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 color erasing temperature) reaching a complete color erasing state, and B is a temperature t ₃ (hereinafter referred to as a color erasing 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 the density at the coloring temperature).
Discoloration temperature region is a temperature range between the t ₁ and t _4, both states of the colored state and the decolored state can coexist, a 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.

Specifically, as the reversible thermochromic composition having color memory, a complete color development temperature t ₁ is a temperature that can be obtained only in a freezing room, a cold region, etc., that is, −50 to 0 ° C., preferably −40 to − 5 ° C., more preferably −30 to −10 ° C., and a temperature at which a complete decoloring temperature t ₄ is obtained from a frictional heat generated by a friction body, a heating body such as a hair dryer, that is, 50 to 95 ° C., preferably 50 to 90
By specifying the temperature in the range of 60 ° C., more preferably in the range of 60 to 80 ° C., and specifying the ΔH value in the range of 40 to 100 ° C., it is possible to effectively function to maintain the color exhibited in the normal state (daily life temperature range).

Hereinafter, the components (A), (B), and (C) will be described.
(B) As an electron-donating color-forming organic compound of the component, diphenylmethane phthalides, phenyl indolyl phthalides, indolyl phthalides, diphenyl methane azaphthalides, phenyl indolyl azaphthalides, fluorans , Styrinoquinolines, 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-diethylamino) Phenyl) -3- (1-ethyl-2-methylindol-3-yl) -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, -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-d) pyrimidine-5,1 '(3'H) isobenzofuran] -3'-one, 2 -(Di-n-butylamino) -8- (di-n-butylamino) -4-methyl-, spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5,1 '(3' H) Isobenzofuran] -3'-one, 2- (di-n-butylamino) -8- (diethylamino) -4-methyl-, spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5,1 '( 3'H) isobenzofuran] -3'-one, 2- (di-n-butylamino) -8- (N-ethyl-Ni-amylamino) -4-methyl-, spiro [5H- (1) Benzopyrano (2,3-d) pyrimidine-5,1 '(3'H) isobenzofuran] -3'-one, 2- (di-n-butylamino) -8- (di-n-butylamino)- 4-phenyl, 3- (2-methoxy-4-dimethylaminophenyl) -3- (1-butyl-2-methylindol-3-yl) -4,5,6,7-tetrachlorophthalide, 3- (2-Ethoxy-4-diethylaminophenyl) -3- (1-ethyl- -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.
Furthermore, pyridine-based, quinazoline-based, bisquinazoline-based compounds and the like effective for developing fluorescent yellow to red color development can also be used.

(B) Component electron-accepting compounds include active proton-containing compound groups, pseudo-acidic compound groups [not acid, but compounds that act as acids in the composition and 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.

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 esters, ketones, ethers, alcohols, and acid amides.
As the component (c), the color density-temperature curve has a large hysteresis characteristic (the curve plotting the change in the color density due to the 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 exhibiting a ΔT value (melting point-cloud point) of 5 ° C. or more and less than 50 ° C., which can form a reversible thermochromic composition exhibiting color memory, which changes color when changing to Carboxylic acid ester having a substituted aromatic ring in the molecule, carboxylic acid ester having an unsubstituted aromatic ring and an aliphatic alcohol ester having 10 or more carbon atoms, carboxylic acid ester having a cyclohexyl group in the molecule, 6 or more 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 aroma Ester of alcohol or branched aliphatic alcohol, dibenzyl cinnamate, heptyl stearate, didecyl adipate, dilauryl adipate, dimyristyl adipate, dicetyl adipate, distearyl adipate, trilaurin, trimyristin, tristearin, dimyristin, Distearin or the like is 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, 5-undecanone, 2 -Dodecanone, 3-dodecanone, 4-dodecanone, 5-dodecanone, 2-tridecanone, 3-tridecanone, 2-tetradecanone, 2-pentadecanone, 8-pentadecanone, 2-hexadecanone, 3-hexadecanone, 9-heptadecanone, 2-pentadecanone 2-octadecanone, 2-nonadecanone, 10-nonadacanone, 2-eicosanone, 11-eicosanone, 2-heneicosanone, 2-docosanone, laurone, stearone and the like.
Further, arylalkyl ketones having 12 to 24 carbon atoms in total, 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 include dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, dinonyl ether, didecyl ether, diundecyl ether, didodecyl ether, ditrityl ether. Decyl ether, ditetradecyl ether, dipentadecyl ether, dihexadecyl ether, dioctadecyl ether, decane diol dimethyl ether, undecane diol dimethyl ether, dodecane diol dimethyl ether, tridecane diol dimethyl ether, decane diol diethyl ether, undecane diol diethyl ether, etc. Can be mentioned.
As the alcohols, aliphatic monovalent saturated alcohols having 10 or more carbon atoms are effective. Decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, heptadecyl Alcohol, octadecyl alcohol, eicosyl alcohol, docosyl alcohol, etc. can be mentioned.
Acid amides include hexanoic acid amide, heptanoic acid amide, octanoic acid amide, nonanoic acid amide, decanoic acid amide, undecanoic acid amide, lauric acid amide, tridecanoic acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, Examples thereof include docosanoic acid amide.

〔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。 Further, as the component (c), a compound represented by the following general formula (1) described in JP-A No. 2006-137886 is preferably used.

[Wherein, R ₁ represents a hydrogen atom or a methyl group, 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, the compound shown by following General formula (3) described in Unexamined-Japanese-Patent No. 2006-188660 can also be used as said (c) component.

(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−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、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、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- [4- (3-Methylbenzyloxy) phenyl)] diester with ethanol, diester of glutaric acid with 2- (4-benzyloxyphenyl) ethanol, glutaric acid with 2- (4-benzyloxyphenyl) ethanol Diester, diester of glutaric acid and 2- (4-benzyloxyphenyl) ethanol, diester of glutaric acid and 2- [4- (4-chlorobenzyloxy) phenyl)] ethanol, adipic acid and 2- (4- Diester with benzyloxyphenyl) ethanol, adipic acid and 2- (4-benzylo) Diester with ciphenyl) ethanol, diester with adipic acid and 2- (4-benzyloxyphenyl) ethanol, diester with pimelic acid and 2- (4-benzyloxyphenyl) ethanol, suberic acid and 2- (4-benzyl) Diester of oxyphenyl) ethanol, diester of suberic acid and 2- [4- (3-methylbenzyloxy) phenyl)] ethanol, suberic acid and 2- [4- (4-chlorobenzyloxy) phenyl)] ethanol Diester of suberic acid and 2- [4- (2,4-dichlorobenzyloxy) phenyl)] ethanol, diester of azelaic acid and 2- (4-benzyloxyphenyl) ethanol, sebacic acid and 2 -Diester with (4-benzyloxyphenyl) ethanol Diester of 1,10-decanedicarboxylic acid and 2- (4-benzyloxyphenyl) ethanol, diester of 1,18-octadecanedicarboxylic acid and 2- (4-benzyloxyphenyl) ethanol, 1,18-octadecanedicarboxylic A diester of an acid and 2- [4- (2-methylbenzyloxy) phenyl)] ethanol can be exemplified.

  Further, as the component (b), a specific alkoxyphenol compound having a linear or side chain alkyl group having 3 to 18 carbon atoms (Japanese Patent Laid-Open No. 11-129623), a specific hydroxybenzoic acid ester (Japanese Patent Laid-Open No. 2001-105732). Gazette), gallic acid esters (Japanese Patent Laid-Open No. 2003-253149), and the like, a heat-colorable microcapsule pigment encapsulating a reversible thermochromic composition 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).
Here, in the reversible thermochromic microcapsule pigment or the ink, a colorant such as a non-thermochromic dye or pigment is blended to change the color from color (1) to color (2). Changes can also be exhibited.

  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. Further, a secondary resin film may be provided on the surface of the microcapsule according to the purpose to impart durability, or the surface characteristics may be modified for practical use.

The form of the microcapsule pigment does not refuse application of a circular cross-section, but a non-circular cross-section is effective.
The handwriting formed by writing, the microcapsule pigment is closely oriented and fixed in close contact with the writing surface on the long diameter side (maximum outer diameter side), and exhibits a high concentration of color development. The microcapsule pigment is slightly elastically deformed into a shape that relieves the external force against the external force caused by friction by a friction body such as rubber, and the destruction of the wall film of the microcapsule is suppressed and the thermal discoloration function is not impaired. It can be expressed effectively.
Here, the non-circular cross-sectional shape microcapsule pigment has an average value of the maximum outer diameter of 0.5 to 5.0 μm, preferably 1 to 4 μm, more preferably 1 to 3 μm, and reversible heat. Color-changing composition: wall film = 7: 1 to 1: 1 (mass ratio), preferably 6: 1 to 1: 1.
If the average value of the maximum outer diameter of the microcapsule pigment (including those having a circular cross-sectional shape) exceeds 5.0 μm, the outflow from the capillary gap tends to be reduced, and the average value of the maximum outer diameter is less than 0.5 μm. In this case, it becomes difficult to show high color density.
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.

Other examples include metallic luster pigments, phosphorescent pigments, white pigments such as titanium dioxide, silica, and calcium carbonate, and capsule pigments containing fragrances and fragrances.
The metallic luster pigment is a metallic luster pigment such as aluminum or brass, and a metallic luster pigment in which the surface of natural mica, synthetic mica, glass piece, alumina, or transparent film piece is coated with a metal oxide such as titanium oxide as a core substance. (Pearl pigment), a metallic luster pigment in which a metal vapor deposition film is formed on a transparent or colored transparent film, and a metallic luster pigment having an iris property obtained by finely cutting an iris film in which a plurality of transparent resin layers are laminated.
The pigment can be used singly or in combination of two or more, and is used in the range of 1 to 40% by mass, preferably 2 to 30% by mass, more preferably 3 to 30% by mass in the ink composition.
Moreover, a pigment dispersant can be added as needed. As the pigment dispersant, surfactants such as anions and nonions, anionic polymers such as polyacrylic acid and styreneacrylic acid, and nonionic polymers such as polyvinylpyrrolidone and polyvinyl alcohol are used.
Since an ink composition using a pigment as a colorant has a higher solid content than an ink composition using a dye, when the water in the ink evaporates, the ink viscosity increases and the handwriting tends to be blurred. The ink composition applied to the invention of the present application can maintain dry-up resistance even when a pigment is used, and is less likely to cause fading. It is excellent in usefulness as a product.

The shear thinning agent will be described.
The shear thinning of the ink composition is a rheological characteristic that has a property of being extremely high viscosity and difficult to flow in a static state or when the stress is low, and showing a good fluidity by decreasing the viscosity when the stress increases. It means liquidity also called thixotropic property or pseudoplasticity. Therefore, the ink composition is temporarily destroyed in the three-dimensional structure under high shear stress at the time of writing and the viscosity of the ink is lowered, and the ink at the tip of the writing becomes a low-viscosity ink suitable for writing and transferred to the paper surface. The When not writing, the viscosity of the ink becomes high, so that leakage of the ink can be prevented, and separation and backflow of the ink can be prevented. Also, the ink physical properties can be kept stable over time.
In particular, a ballpoint pen with a ball held at the tip of the writing has a low viscosity suitable for writing under high shear stress during writing, and the gap between the ball and the ball house moves by capillary force to move the paper surface. It is necessary to have ink characteristics that can be transferred to, and when not writing, the viscosity of all inks, including the vicinity of the ball, must be increased to prevent ink leakage, ink separation, and backflow. An ink composition having an ink viscosity at 100 rpm by an E-type rotational viscometer of 20 to 200 mPa · s (25 ° C.) and a shear thinning index of 0.1 to 0.8 is suitable.
The shear thinning index n can be obtained by assigning a numerical value to the empirical formula T = Kj ⁿ (T: shear stress value, j: shear rate, K is a calculated constant).

As the shear thinning agent, a water-soluble or dispersible substance is effective, and xanthan gum, welan gum, and succinoglycan whose constituent monosaccharide is an organic acid-modified heteropolysaccharide of glucose and galactose (average molecular weight) The main component is gum, guar gum, locust bean gum and its derivatives, hydroxyethyl cellulose, alginic acid alkyl esters, methacrylic acid alkyl ester, which are composed of glucose, glucuronic acid, fucose and rhamnose. A polymer having a molecular weight of 100,000 to 150,000, a thickening polysaccharide having gelling ability extracted from seaweed such as glucomannan, agar and carrageenan, benzylidene sorbitol and benzylidene xylitol or their derivatives, crosslinkable acrylic acid heavy Coalescence, inorganic fine particles, Nonionic interfaces having an HLB value of 8 to 12, such as liglycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl ether, fatty acid amide Examples include activators, salts of dialkyl or dialkenyl sulfosuccinic acid, and the like, which can be used alone or in combination.
The shear thinning agent can be used in the range of 0.1 to 20% by mass in the ink composition.
By using the shear thinning agent, a water-soluble organic solvent having a solubility parameter of 8 to 11 and an ionic substance, when the moisture in the ink is reduced, the shear thinning agent is in a semi-swelled state, As a result, the ink viscosity hardly increases.
As the shear thinning agent, xanthan gum, welan gum, succinoglycan is preferably used, and the ink stability is excellent.
In the ink composition containing the shear thinning agent, the water-soluble organic solvent, and the ionic substance, the viscosity when water is evaporated by 40% by mass from the total amount of the ink / initial ink viscosity (E-type rotational viscometer (Measured at 1 rpm and 20 ° C.) is 2 or less, preferably 0.01 to 1.5, more preferably 0.01 to 1.
When the numerical value (x) is 2 or less, it is excellent in dry-up resistance when written and put into practical use in a composite ballpoint pen refill. Can be made.
If the value exceeds 2, the change in the viscosity when the water in the ink is evaporated by 40% by mass and the initial viscosity of the ink is large.

In addition to the above components, 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 and its derivatives, tolyltriazole, dicyclohexylammonium as necessary Rust inhibitor such as nitrite, diisopropylammonium nitrite, sodium thiosulfate, saponin, coalic acid, sodium salt of 1,2-benzthiazolin-3-one, sodium benzoate, sodium dehydroacetate, potassium sorbate, paraoxybenzoic acid Preservatives or antifungal agents such as propyl, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, metal soap, fatty acid ester, ethylene oxide addition type cationic activator, phosphoric acid based activator, thiocarbamine Acid salt, dimethyldithio Lubricants such as carbamate, ascorbic acid, ascorbic acid derivative, α-tocopherol, catechin, catechin derivative, synthetic polyphenol, phosphonate, phosphinate, sulfite, sulfoxylate, dithionate, thiosulfate Antioxidants such as thiourea dioxide, formamidinesulfinic acid, glutathione, urea, nonionic surfactants, sorbitol, mannitol, sucrose, glucose, reduced starch hydrolysate, wetting agent such as sodium pyrophosphate, ink Fluorine-based surfactants and nonionic, anionic and cationic surfactants that improve the permeability of dimethylpolysiloxane, antifoaming agents such as dimethylpolysiloxane, acrylic resins, styrene-maleic acid copolymers, polyvinylpyrrolidone, polyvinyl alcohol, Water-soluble resins such as dextrin, dispersants, etc. May be used.
Furthermore, as a sulfur type extreme pressure agent, 2-amino-5-mercapto-1,3,4-thiadiazole, 2-mercapto-5-methyl-1,3,4-thiadiazole, 1,4-dithiane, 2,5 -Dihydroxy-1,4-dithiane, 2,5-dihydroxy-2,5-dimethyl-1,4-dithiane, 1,4-thiazan, thiazolidine, 2,4-thiazolidinedione, rhodanine, thioamide as thioacetamide By adding thiopropionamide, 2,5-dimercapto-1,3,4-thiadiazole, etc., good and stable ink ejection properties can be maintained even at the initial stage and after the passage of time.
These compounds contain an ionic substance, and a compound that exhibits a thickening suppression effect when used in combination with a water-soluble organic solvent having a solubility parameter of 8 to 11 can also be used as an ionic substance. It can be used in combination with the aforementioned ionic substance.

The ink composition is filled in a composite ballpoint pen refill having a ballpoint tip attached to the writing tip.
The structure and shape of the refill for the ballpoint pen are not particularly limited. An example is a refill for a ballpoint pen that is communicated via a connecting member (holder) and in which the ink backflow preventer composition is in close contact with the end face of the ink composition.
For the structure of the ballpoint pen tip, a general-purpose mechanism is effective, a mechanism for 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 drill of a metal material, etc. A mechanism that forms a chip part by cutting with a ball holding part, a mechanism that urges the ball forward by a spring body, or a resin ball inside a metal or plastic chip A mechanism provided with a receiving seat can be exemplified.
The ball may be about 0.3 to 1.5 mm in diameter, such as cemented carbide, stainless steel, ruby, ceramic, resin, rubber, etc., preferably 0.3 to 0.7 mm, more preferably 0. 3 to 0.5 mm are 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 and nylon is used in addition to metal.

The back end of the ink stored in the ink storage tube can 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 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.

A reversible thermochromic composition comprising (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reaction medium that determines the temperature at which the color reaction occurs between the two ink compositions. In the case of including a reversible thermochromic microcapsule pigment encapsulating the 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. A molded body made of resin 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.
Furthermore, both the ink storage tube and the shaft tube can be formed of a material having a light shielding property.

The ball-point pen refill is used in a composite ball-point pen in which a plurality of ball-point refills are housed in a shaft cylinder, and the writing tip of one of the ball-point pen refills protrudes and retracts from the front end opening of the shaft cylinder by the operation of a retracting mechanism.
Examples of the operation method of the retracting mechanism include a knock type, a rotary type, and a slide type.
The knock type has a knock portion at the rear end portion of the shaft tube or the side surface of the shaft tube, and can be exemplified by a configuration in which the ball-point pen tip is projected and retracted from the front end opening portion of the shaft tube by pressing the knock portion.
The rotary type has a rotating part at the rear part of the shaft cylinder, and a configuration in which the ball-point pen tip is projected and retracted from the front end opening part of the shaft cylinder by rotating the rotating part can be exemplified.
The slide type can be exemplified by a configuration in which a slide part is provided on the side surface of the shaft cylinder, and the ballpoint pen tip is projected and retracted from the front end opening of the shaft cylinder by operating the slide.
Examples of the shaft that constitutes the refill for the ballpoint pen include resin, metal, and ceramic.
In the composite ball-point pen, the diameter of the shaft tube is 12.5 mm or less, preferably 11.5 mm or less, more preferably 10.5 mm or less, so that it can be easily accommodated in a notebook or a pen case. If a refill for a ballpoint pen having a ball of less than 5 mm is accommodated and used, small letters can be written, so that it is easy to fill in a notebook, and more practicality can be satisfied.

A reversible thermochromic composition comprising (i) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reaction medium that determines a temperature at which the color reaction of the two occurs. When the encapsulated reversible thermochromic microcapsule pigment is included, the handwriting formed from the composite ballpoint pen containing the ink composition can be changed in color 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.
As the friction member and the friction body, an elastic body such as an elastomer or plastic foam which is rich in elasticity and can generate appropriate friction during friction to generate frictional heat is preferable. Wood, metal, and fabric may be used.
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 at the time of friction.
As the material of the friction member or friction body, silicone resin or SEBS resin (styrene ethylene butadiene styrene block copolymer) is preferably used. However, the silicone resin easily adheres to the portion erased by friction, and repeated writing. SEBS resin is more preferably used because the handwriting tends to be repelled.
The friction member may be an arbitrary-shaped member (friction body) that is separate from the writing instrument, but is excellent in portability by being fixed to the writing instrument.
Examples of the location where the friction member is fixed include a shaft cylinder front end opening or a shaft cylinder rear end.
Further, a friction member having the same shape as the refill for the ballpoint pen can be accommodated in the composite ballpoint pen and used.
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.
Moreover, a writing instrument set can be obtained by combining the composite ballpoint pen and a friction body.

The following table shows the formulation of the water-based ink composition for ballpoint pens.
In addition, the numerical value in a table | surface shows the mass%, and the numerical value in the parenthesis described after the solvent name is a solubility parameter (SP value).

The contents of the raw materials in the table are explained according to the note numbers.
(1) C.I. I. Pigment Black 7
(2) C.I. I. Pigment Red 254
(3) C.I. I. Pigment Blue 15: 3
(4) BASF, trade name: Rubytec K-30
(5) Made by Sanki Co., Ltd., trade name: Kelzan (6) Made by Kao Corporation, trade name: Demol N
(7) Product name: DEMAL EP (active ingredient 25%), manufactured by Kao Corporation
(8) Made by The Dow Chemical Company, trade name: Dowfax2A1 (active ingredient 47%)
(9) Made by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Prisurf AL, polyoxyethylene distyrenated phenyl ether phosphate monoester and diester mixture

The reversible thermochromic pigments in the table were prepared by the following method.
Preparation of reversible thermochromic pigment a (a) 3- (4-Diethylamino-2-hexyloxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) as an electron-donating color-forming organic compound -4-azaphthalide 2.0 parts, (b) 2,2-bis (4-hydroxyphenyl) hexafluoropropane 5.0 parts as an electron accepting compound, 1,1-bis (4-hydroxyphenyl) n-decane 3.0 parts, (c) A reversible thermochromic composition comprising 50.0 parts of 4-benzyloxyphenylethyl caprate as a reaction medium for controlling the color reaction of (i) and (b) above is uniformly added. Dissolve in a warm solution and emulsify a solution of 30.0 parts of aromatic isocyanate prepolymer and 40 parts of ethyl acetate as a wall film material into microdroplets in an 8% aqueous polyvinyl alcohol solution. After stirring at 70 ° C. for about 1 hour, 2.5 parts of a water-soluble aliphatic modified amine was gradually added with stirring, and the liquid temperature was kept at 90 ° C. and stirring was continued for about 6 hours. A reversible thermochromic pigment suspension was obtained.
A reversible thermochromic pigment was isolated from the suspension by centrifugation to obtain a reversible thermochromic pigment a (coloring from blue to colorless) (solid content: 60%, average particle size: 3 μm).
When the reversible thermochromic pigment a is cooled from a colorless state, it begins to develop a blue color from -6 ° C, and becomes a complete blue colored state at -14 ° C. The discoloration behavior that became colorless and completely decolored was shown. The discoloration behavior could be reproduced repeatedly.
The reversible thermochromic pigment a was previously cooled to −14 ° C. or lower to completely develop color and used as a colorant.

Preparation of reversible thermochromic pigment b The component (a) of the reversible thermochromic composition is 4.5 parts of 2- (2-chloroanilino) -6-di-n-butylaminofluorane, and the component (b) is 2, 7.5 parts of 2-bis (4-hydroxyphenyl) hexafluoropropane, 4.5 parts of 1,1-bis (4-hydroxyphenyl) n-decane, and (c) component are 4-benzyloxyphenylethyl caprate 50 A reversible thermochromic pigment b was obtained in the same manner as the reversible thermochromic pigment a except that the amount was changed to 0.0 parts (solid content: 60%, average particle size: 2 μm).
When the reversible thermochromic pigment b is cooled from a colorless state, it begins to develop a black color from -9 ° C. and becomes a completely colored state at −20 ° C. When it is heated from this state, it starts to lose its color from 40 ° C. at 57 ° C. It showed a discoloration behavior that resulted in a colorless and completely decolored state. The discoloration behavior could be reproduced repeatedly.
The reversible thermochromic pigment b was cooled in advance to −20 ° C. or less and completely developed to be used as a colorant.

Preparation of reversible thermochromic pigment c The component (a) of the reversible thermochromic composition was changed to 2- (dibutylamino) -8- (dipentylamino) -4-methyl-spiro [5H- [1] -benzopyrano [2, 3-g] pyrimidine-5,1 ′ (3′H) -isobenzofuran] -3-one (2.0 parts) and (b) component as 2,2-bis (4-hydroxyphenyl) hexafluoropropane 5.0 Parts, 1,1-bis (4-hydroxyphenyl) n-decane 3.0 parts, (c) reversible thermochromic pigment a, except that component (c) was changed to capric acid 4-benzyloxyphenylethyl 50.0 parts A reversible thermochromic pigment c that changes from pink to colorless was obtained by the same method (solid content: 60%, average particle size: 2 μm).
When the reversible thermochromic pigment c is cooled from a colorless state, it begins to develop a color from -6 ° C to pink, and at -14 ° C it turns into a complete pink color. When heated from this state, it begins to lose its color from 48 ° C and 58 It showed a discoloration behavior that became colorless and completely decolored at ℃. The discoloration behavior could be reproduced repeatedly.
The reversible thermochromic pigment c was previously cooled to −14 ° C. or less to completely develop a color and used as a colorant.

Preparation of reversible thermochromic pigment d (i) component of reversible thermochromic composition 2.5 parts of 1,3-dimethyl-6-diethylaminofluorane and (b) component 2,2-bis (4-hydroxy) Phenyl) hexafluoropropane 5.0 parts, 1,1-bis (4-hydroxyphenyl) n-decane 3.0 parts, (ha) component was changed to capric acid 4-benzyloxyphenylethyl 50.0 parts Obtained reversible thermochromic pigment d which changes from orange to colorless in the same manner as reversible thermochromic pigment a (solid content: 60%, average particle size: 2 μm).
When the reversible thermochromic pigment d is cooled from a colorless state, it begins to develop an orange color from -9 ° C., and becomes a full colored state of orange at −18 ° C. When heated from this state, it starts to lose its color from 45 ° C. at 64 ° C. It showed a discoloration behavior that resulted in a colorless and completely decolored state. The discoloration behavior could be reproduced repeatedly.
The reversible thermochromic pigment d was cooled in advance to −18 ° C. or less and completely developed to be used as a colorant.

Preparation of reversible thermochromic pigment e The component (a) of the reversible thermochromic composition was changed to 4- [2,6-bis (2-ethoxyphenyl) -4-pyridinyl] -N, N-dimethylbenzenamine 3.0. Reversible heat, except that the component (b) was changed to 10.0 parts 2,2-bis (4-hydroxyphenyl) hexafluoropropane and the component (c) was changed to 50.0 parts 4-benzyloxyphenylethyl caprate. A reversible thermochromic pigment e which changes from yellow to colorless was obtained in the same manner as the color-changing pigment a (solid content: 60%, average particle size: 2 μm).
When the reversible thermochromic face e is cooled from a colorless state, it begins to develop a color from -15 ° C. to yellow, and at −25 ° C., it becomes a complete yellow colored state. It showed a discoloration behavior that resulted in a colorless and completely decolored state. The discoloration behavior could be reproduced repeatedly.
The reversible thermochromic pigment e was cooled in advance to −25 ° C. or less and completely developed to be used as a colorant.

  A water-based ink composition for ballpoint pens is obtained by mixing the respective formulations in the table and stirring for 1 hour.

Measurement of x value Each x value of the ink composition [viscosity when water in ink is evaporated by 40% by mass with respect to the total amount of ink / initial ink viscosity (measured at E-type rotational viscometer, 1 rpm, 20 ° C.) ] Was measured.
Dry-up resistance test The ink composition is filled in an ink containing tube fitted with one end of a polypropylene pipe with a stainless steel chip holding a ball having a diameter of 0.5 mm, and is further brought into close contact with the rear end surface of the ink. Then, a refill for a composite ballpoint pen was obtained by filling the ink backflow prevention body.
The composite ballpoint pen refill was left standing at 50 ° C. for 30 days in an inverted state (the writing tip was downward), then writing was performed, and the state of the handwriting was visually observed.
Each x value of the ink composition and the dry-up resistance test results are shown in the following table.

The determination results in the table are as follows.
Dry-up resistance test A: A good handwriting that is uniform and not blurred is obtained.
○: Handwriting without blur is obtained.
X: A blur is seen in a handwriting.

Example 1
Fabrication of composite ballpoint pen refill (see Fig. 4)
Filling the ink composition A, B, and C into a transparent ink containing tube 4 made of polypropylene with a stainless steel ballpoint pen tip 2 holding a ball having a diameter of 0.3 mm fitted through a connecting member 3 Further, the ink backflow prevention body 5 was filled in close contact with the rear end surface of the ink to obtain a composite ballpoint pen refill 1.

Fabrication of compound ballpoint pen (see Fig. 5)
The three composite ballpoint pen refills obtained as described above are incorporated into a transparent shaft 7 (diameter: 10.5 mm), and the writing tip of one of the ballpoint pen refills is activated by the operation body 8 of the retracting mechanism. Was obtained from the front end opening of the shaft cylinder.
When the above-described dry-up resistance test was performed using the composite ballpoint pen, the handwriting formed using any of the refills for the ballpoint pen was uniform and was not blurred, and a good handwriting could be formed.

Example 2
Preparation of refill for compound ballpoint pen (see Fig. 6)
The ink compositions A and B are filled in a transparent ink containing tube 4 made of polypropylene, in which a stainless steel ballpoint pen tip 2 holding a ball having a diameter of 0.4 mm is fitted via a connecting member 3, Further, the ink backflow prevention body 5 was filled in close contact with the rear end surface of the ink.
Next, an operation body 8 having the same color as that of each ink composition was fitted to the rear part of the ink containing tube to obtain a composite ballpoint pen refill 1.

Fabrication of compound ballpoint pen (see Fig. 7)
The two composite ballpoint pen refills obtained as described above are incorporated in a transparent shaft cylinder 7 (diameter: 10.5 mm) having a lid 9 that can be freely opened and closed at the rear, and after the lid is closed, a retracting mechanism The composite ball-point pen 6 in which the writing tip portion of any of the refills for ball-point pens appears and disappears from the front end opening portion of the shaft cylinder is obtained by the operation of the operation body 8.
When the above-described dry-up resistance test was performed using the composite ballpoint pen, the handwriting formed using any of the refills for the ballpoint pen was uniform and was not blurred, and a good handwriting could be formed.

Example 3
Preparation of refill for composite ballpoint pen Transparent ink containing tube made of polypropylene in which the ink compositions D and G are fitted with stainless steel ballpoint pen tips each holding a ball having a diameter of 0.4 mm via a connecting member In addition, the ink backflow preventer was filled in close contact with the rear end surface of the ink to obtain a composite ballpoint pen refill.

Fabrication of compound ballpoint pen (see Fig. 8)
Two composite ballpoint pen refills obtained as described above are incorporated into a light shielding (opaque) shaft cylinder 7 (diameter 11 mm), and writing of one of the ballpoint pen refills is performed by operating the operation body 8 of the retracting mechanism. A composite ball-point pen 6 having a tip portion protruding from the front end opening portion of the shaft cylinder was obtained.
A friction member 10 made of SEBS resin is provided at the rear end of the shaft of the composite ballpoint pen.
When the above-described dry-up resistance test was performed using the composite ballpoint pen, the handwriting formed using any of the refills for the ballpoint pen was uniform and was not blurred, and a good handwriting could be formed.
Furthermore, the handwriting could be decolored by rubbing with a friction member.

Example 4
Preparation of refill for composite ballpoint pen Light shielding property made of polypropylene in which a stainless steel ballpoint pen tip that holds a ball having a diameter of 0.4 mm for each of the ink compositions D, F, and G is fitted via a connecting member An (opaque) ink containing tube was filled, and further, an ink backflow prevention body was filled in close contact with the rear end surface of the ink.
Next, an operation body having the same color as that of each ink composition was fitted to the rear part of the ink containing tube to obtain a composite ballpoint pen refill.

Fabrication of compound ballpoint pen (see Fig. 9)
The three composite ballpoint pen refills obtained as described above were incorporated into a transparent shaft cylinder 7 (diameter 11 mm) having a lid 9 that can be opened and closed at the rear, and after closing the lid, the operation of the retracting mechanism was performed. The composite ball-point pen 6 in which the writing tip portion of any of the refills for ball-point pens appears and disappears from the front end opening portion of the shaft cylinder by the operation of the body 8 was obtained.
A friction member 10 made of SEBS resin is provided in the vicinity of the opening at the tip of the shaft cylinder.
When the above-described dry-up resistance test was performed using the composite ballpoint pen, the handwriting formed using any of the refills for the ballpoint pen was uniform and was not blurred, and a good handwriting could be formed.
Furthermore, the handwriting could be decolored by rubbing with a friction member.

Example 5
Production of a composite ballpoint pen refill Polypropylene light shielding (opaque) with a stainless steel ballpoint pen tip that holds the ink compositions E and H each having a diameter of 0.4 mm through a connecting member The ink containing tube was filled, and further, an ink backflow prevention body was filled in close contact with the rear end surface of the ink.
Next, an operation body having the same color as that of each ink composition was fitted to the rear part of the ink containing tube to obtain a composite ballpoint pen refill.

Fabrication of friction member (see FIG. 10)
A SEBS resin molded product is provided at the front end of the ink containing tube 4 used for the composite ballpoint pen refill, and the operating body 8 (transparent) used for the composite ballpoint pen refill is fitted to the rear end of the friction member. 10 was obtained.

Fabrication of compound ballpoint pen (see Fig. 11)
The two composite ball-point pen refills and the friction member 10 obtained as described above are incorporated into a light-shielding (opaque) shaft cylinder 7 (diameter 11 mm) having a lid portion 9 that can be freely opened and closed at the rear portion. After closing, the ballpoint pen refill or the composite ball-point pen 6 in which the writing tip portion of the friction member appears and disappears from the front end opening portion of the shaft cylinder is obtained by the operation of the operation body 8 of the appearance mechanism.
When the above-described dry-up resistance test was performed using the composite ballpoint pen, the handwriting formed using any of the refills for the ballpoint pen was uniform and was not blurred, and a good handwriting could be formed.
Furthermore, the handwriting could be decolored by rubbing with a friction member.

Example 6
Preparation of a refill for a composite ballpoint pen Filling the transparent ink containing tube made of polypropylene with a stainless steel ballpoint pen chip that holds a ball having a diameter of 0.3 mm with a connecting member through the ink composition A, Further, a refill for a composite ballpoint pen was obtained by being in close contact with the rear end surface of the ink and filled with an ink backflow prevention body.
Using the ink composition A, a refill for a composite ballpoint pen was obtained in the same manner as described above except that a ball having a diameter of 0.4 mm was used.
Using the ink composition A, a refill for a composite ballpoint pen was obtained in the same manner as described above except that a ball having a diameter of 0.5 mm was used.

Production of composite ballpoint pens The three composite ballpoint pen refills obtained as described above are incorporated into a transparent shaft (diameter 10 mm), and the writing tip of one of the ballpoint pen refills is activated by the operation of the retracting mechanism. A composite ball-point pen whose part protrudes and emerges from the front end opening of the shaft cylinder was obtained.
When the above-described dry-up resistance test was performed using the composite ballpoint pen, the handwriting formed using any of the refills for the ballpoint pen was uniform and was not blurred, and a good handwriting could be formed.

Example 7
Preparation of a refill for a composite ballpoint pen Filled with a transparent ink containing tube made of polypropylene, with a stainless steel ballpoint pen chip that holds a ball having a diameter of 0.5 mm, which is inserted through a connecting member, with the ink composition A, Further, an ink backflow prevention body was filled in close contact with the rear end surface of the ink.
Next, an operation body having the same color as that of each ink composition was fitted to the rear part of the ink containing tube to obtain a composite ballpoint pen refill.
The ink composition F is filled with a light-shielding (opaque) ink containing tube fitted with one end of a polypropylene pipe with a stainless steel chip holding a ball having a diameter of 0.5 mm. The ink backflow preventer was filled in close contact with the ink.
Next, an operation body having the same color as that of each ink composition was fitted to the rear part of the ink containing tube to obtain a composite ballpoint pen refill.

Fabrication of friction member SEBS resin molding is provided at the front end of the light shielding (opaque) ink containing tube used in the composite ballpoint pen refill, and the operating body used for the composite ballpoint pen refill (white) To obtain a friction member.

Production of composite ballpoint pen The two composite ballpoint pen refills and friction members obtained as described above were incorporated in a transparent shaft cylinder (diameter 11 mm) having a lid that can be opened and closed at the rear, and the lid was closed. Thereafter, either a ballpoint pen refill or a composite ballpoint pen in which the writing tip portion of the friction member protrudes and retracts from the front end opening portion of the barrel is obtained by the operation of the operation mechanism of the appearance mechanism.
When the above-described dry-up resistance test was performed using the composite ballpoint pen, the handwriting formed using any of the refills for the ballpoint pen was uniform and was not blurred, and a good handwriting could be formed.
Furthermore, one of the handwriting could be decolored by rubbing with a friction member.

Example 8
Preparation of a composite ballpoint pen refill A transparent ink container made of polypropylene in which a stainless steel ballpoint pen tip that holds a ball having a diameter of 0.4 mm is fitted through each of the ink compositions E, F, and H via a connecting member. The tube was filled, and further, an ink backflow prevention body was filled in close contact with the rear end surface of the ink to obtain a composite ballpoint pen refill.

Production of composite ballpoint pens The three composite ballpoint pen refills obtained as described above were incorporated into a transparent shaft (diameter 11 mm), and the writing tip of one of the ballpoint pen refills was activated by operating the operating body of the retracting mechanism. A composite ball-point pen whose part protrudes and emerges from the front end opening of the shaft cylinder was obtained.

Preparation of writing instrument set A writing instrument set was obtained by combining the composite ballpoint pen and a friction body (cubic shape) made of SEBS resin.
When the above-described dry-up resistance test was performed using the composite ballpoint pen, the handwriting formed using any of the refills for the ballpoint pen was uniform and was not blurred, and a good handwriting could be formed.
Furthermore, the handwriting could be decolored by rubbing with a friction body.

Comparative Example 1
Preparation of a refill for a composite ballpoint pen Transparent ink made of polypropylene in which a stainless steel ballpoint pen tip that holds a ball having a diameter of 0.3 mm is fitted to each of the ink compositions I, J, and K via a connecting member The container tube was filled, and the ink backflow prevention member was filled in close contact with the rear end surface of the ink to obtain a composite ballpoint pen refill.

Fabrication of a composite ballpoint pen The three composite ballpoint pen refills obtained as described above were incorporated into a transparent shaft (diameter: 10.5 mm), and either ballpoint pen refill was operated by operating the operating body of the retracting mechanism. A composite ballpoint pen in which the writing tip portion protrudes from the front end opening portion of the shaft cylinder was obtained.
When the above-described dry-up resistance test was performed using the composite ballpoint pen, the handwriting formed from all the refills for the ballpoint pen was faint, and the commercial value was poor.

Comparative Example 2
Preparation of a refill for a composite ballpoint pen Transparent ink containing tube made of polypropylene in which a stainless steel ballpoint pen tip that holds a ball having a diameter of 0.4 mm is fitted to each of the ink compositions L and N via a connecting member In addition, the ink backflow prevention body was filled in close contact with the rear end surface of the ink to obtain a composite ballpoint pen refill.

Production of a composite ballpoint pen The two composite ballpoint pen refills obtained as described above are incorporated into a light-shielding (opaque) shaft cylinder (diameter 11 mm), and either ballpoint pen is operated by operating the operating body of the retracting mechanism. A composite ballpoint pen in which the refill writing tip portion appears and disappears from the front end opening portion of the shaft cylinder was obtained.
A friction member made of SEBS resin is provided at the rear end of the shaft of the composite ballpoint pen.
When the above-described dry-up resistance test was performed using the composite ballpoint pen, the handwriting formed from all the refills for the ballpoint pen was faint, and the commercial value was poor.

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 sectional drawing which shows one Example of the refill for composite type ball-point pens of this invention. FIG. 5 is a cross-sectional view of a composite ballpoint pen containing the composite ballpoint pen refill of FIG. 4. It is sectional drawing which shows the other Example of the refill for composite type ball-point pens of this invention. It is sectional drawing of the composite type ball-point pen which accommodated the refill for composite type ball-point pens of FIG. It is sectional drawing which shows the other Example of the composite type ball-point pen of this invention. It is sectional drawing which shows the other Example of the composite type ball-point pen of this invention. It is sectional drawing which shows one Example of the friction member applied to this invention. It is sectional drawing of the composite type ball-point pen which accommodated the friction member of FIG.

Explanation of symbols

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 and coloring type ΔH Hysteresis width 1 Composite formula Refill for ball-point pen 2 Ball-point pen tip 3 Connection member 4 Ink storage tube 5 Ink backflow prevention body 6 Compound ball-point pen 7 Shaft cylinder 8 Operating body 9 Lid 1 Friction member

Claims (11)

  An ink containing tube equipped with a ballpoint pen tip that rotatably holds a ball directly or via a connecting member is provided with at least a pigment, water, a water-soluble organic solvent, a shear thinning agent, and an ionic substance. The content of the ionic substance in the ink is 1% by mass or more based on the total amount of the ink composition, the water-soluble organic solvent is 1 to 20% by mass in the ink composition, and the total amount of the water-soluble organic solvent A composite ballpoint pen refill filled with a water-based ink composition for ballpoint pens containing 80 to 100% by mass of a water-soluble organic solvent having a solubility parameter of 8 to 11.   The refill for a composite ballpoint pen according to claim 1, comprising 90 to 100% by mass of a water-soluble organic solvent having a solubility parameter of 8 to 11 in the total amount of the water-soluble organic solvent.   The composite ballpoint pen refill according to claim 1 or 2, wherein the cation formed by dissociation of the ionic substance contained in the ink composition in the ink is a monovalent cation.   The refill for a composite ballpoint pen according to claim 3, wherein the monovalent cation is selected from alkali metal ions and ammonium ions.   The refill for a composite ballpoint pen according to any one of claims 1 to 4, wherein the content of the ionic substance in the ink composition is 2 to 15% by mass with respect to the total amount of the ink composition.   The pigment includes (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reversible thermochromic composition comprising a reaction medium that determines the temperature at which the color reaction occurs. The refill for a composite ballpoint pen according to any one of 1 to 5, which is a reversible thermochromic microcapsule pigment. The microcapsule pigment, color density - exhibit photochromic colored state and the colorless state shows a large hysteresis characteristic with respect to temperature curve, the pigment is the process of temperature increase from the colored state, decoloring and reach a temperature t ₃ in is started, become completely colorless state at a temperature t ₄ above temperature range than the temperature t _3, the process of the temperature is lowered from colorless state, it begins to color to reach a temperature t ₂ less than the temperature t _3, the temperature t ₂ In the temperature range lower than the temperature t ₁ or less, the film is completely colored, and in the temperature range between the temperature t ₂ and the temperature t ₃ , it exhibits a hysteresis characteristic in which the colored state or the colorless state is selectively maintained, and the temperature t ₁ Is in the range of -50 to 0 ° C, and the temperature t ₄ is in the range of 50 to 90 ° C.   The composite ballpoint pen refill according to claim 6 or 7, wherein the ink containing tube is light-shielding.   The refill for a composite ballpoint pen according to any one of claims 1 to 8, wherein an ink backflow prevention body that follows the ink consumption is disposed on the rear end surface of the ink composition accommodated in the ballpoint pen refill.   The composite ballpoint pen refill according to any one of claims 1 to 9 is accommodated in a plurality of shaft cylinders, and the writing tip portion of any of the ballpoint pen refills is projected and retracted from the front end opening portion of the shaft cylinder by the operation of the retracting mechanism. Combined ballpoint pen.   The composite ballpoint pen according to claim 10, further comprising a friction member.

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