JP2011080025A - Reversible thermochromic oil ink composition for ballpoint pen and ballpoint pen incorporating the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a reversible thermochromic oil ink composition for ballpoint pen which does not cause ink separation or precipitation of pigment due to long lapse of time even when a microcapsule pigment including a reversible thermochromic composition is used as the colorant, for an oil ink composition applied for a ballpoint pen, hardly dries a pen point even when the cap is detached and is excellent in aging stability and dry-up resistance, and to provide the ballpoint pen incorporating the reversible thermochromic oil ink composition for ballpoint pen. <P>SOLUTION: The reversible thermochromic oil ink composition for ballpoint pen comprises: a reversible thermochromic microcapsule pigment including a reversible thermochromic composition composed of an electron-donating color-developing organic compound (a), an electron-accepting compound (b) and a reaction medium (c) of determining the temperature of causing the color-developing reaction of both (a) and (b); a liquid medium selected from polybutene, fluid paraffin, fluid isoparaffin, ethylene-α-olefine oligomer, α-olefinic oil and refined mineral oil; and a fatty acid amide. The ballpoint pen incorporating the ink composition is also disclosed. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a reversible thermochromic oil-based ink composition for ballpoint pens and a ballpoint pen incorporating the same. Furthermore, the present invention relates to a reversible thermochromic oil-based ink composition for ballpoint pens using a reversible thermochromic microcapsule pigment as a colorant and a ballpoint pen incorporating the same.

Conventionally, an oil-based ink composition using a microcapsule pigment encapsulating a reversible thermochromic composition as a colorant and using a highly volatile organic solvent having a vapor pressure at 20 ° C. of about 5 to 50 mmHg as a main solvent has been disclosed. (See Patent Document 1).
When the microcapsule pigment is applied to an oil-based ink, the solid content in the ink tends to be higher than that of a general-purpose colorant in order to ensure a certain handwriting density.
For this reason, when applied to a ballpoint pen, the ink may be separated over a long period of time, resulting in sedimentation of the microcapsule pigment and accompanying reduction in handwriting density. Moreover, when left in a state where the cap is removed, the organic solvent evaporates and the pen tip dries, and the solid content such as the colorant is dried and cured, resulting in poor writing.

JP 2005-320485 A

  The present invention solves the above problems, and even when a microcapsule pigment encapsulating a reversible thermochromic composition is used as a colorant in an oil-based ink composition applied to a ballpoint pen, a long-term Reversible heat for ball-point pens, which does not cause ink separation or microcapsule pigment settling with the passage of time, is difficult to dry even when the cap is removed, and has excellent aging stability and dry-up resistance Disclosed are a discolorable oil-based ink composition and a ballpoint pen incorporating the same.

The present invention includes 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 of the two occurs. A ballpoint pen comprising a reversible thermochromic microcapsule pigment, one or more liquid media selected from polybutene, liquid paraffin, liquid isoparaffin, ethylene-α-olefin oligomer, α-olefin oil, refined mineral oil, and fatty acid amide A reversible thermochromic oil-based ink composition is required.
Furthermore, it is a requirement that the fatty acid amide is contained in the range of 0.1 to 3% by weight in the total amount of the ink composition.
Furthermore, a ballpoint pen comprising any of the above reversible thermochromic oil-based ink compositions for ballpoint pens is a requirement.

  According to the present invention, even when a microcapsule pigment encapsulating a reversible thermochromic composition is used as a colorant for oil-based inks, ink separation over a long period of time and accompanying sedimentation of the microcapsule pigment are suppressed, and the cap is removed. Therefore, it is possible to maintain the writing performance stable for a long period of time.

It is a graph explaining the hysteresis characteristic in the color density-temperature curve of the reversible thermochromic composition used for this invention.

  The present invention relates to an oil-based ink using a microcapsule pigment encapsulating a reversible thermochromic composition, and a liquid medium serving as a main solvent is polybutene, liquid paraffin, liquid isoparaffin, ethylene-α-olefin oligomer, α-olefin. By applying at least one of oil and refined mineral oil and using fatty acid amide in combination, the stability of the ink over time and the resistance to dry-up are obtained.

The reversible thermochromic microcapsule pigment is a pigment in which a reversible thermochromic composition comprising at least three components (a), (b), and (c) is encapsulated in a microcapsule.
Among the reversible thermochromic compositions, the compositions that can be decolored by heating are described in JP-B-51-44706, JP-B-51-44707, JP-B-1-29398, and the like. The color changes before and after the temperature (discoloration point), shows a decolored state in the temperature range above the high temperature side discoloration point, and develops a color state in the temperature range below the low temperature side discoloration point. There is only one specific state, and the other state is maintained while the heat or cold required to develop that state is applied, but if the heat or cold is no longer applied, The composition which has the characteristic ((DELTA) H = 1-7 degreeC) with a comparatively small hysteresis width | variety which returns to the state exhibited in a region can be illustrated.
In addition, large hysteresis characteristics described in JP-B-4-17154, JP-A-7-179777, JP-A-7-33997, JP-A-8-39936, JP-A-2005-1369, and the like. (ΔH = 8 to 70 ° C.), and the shape of the curve plotting the change in color density due to the temperature change is from the higher temperature side than the color change temperature range, contrary to the case where the temperature is raised from the lower temperature side than the color change temperature range. Use a reversible thermochromic composition that changes color by following a path that differs greatly from that of lowering, and can store and retain the color development state in the low temperature range or the decoloration state in the high temperature range in the specific temperature range. You can also.

The hysteresis characteristic in the color density-temperature curve of the composition will be described in detail.
In FIG. 1, the vertical axis represents color density and the horizontal axis represents temperature. The change in color density due to the temperature change proceeds along the arrow. Here, A is a point indicating the density at the lowest temperature T ₄ (hereinafter referred to as the complete color erasing temperature) reaching the complete color erasing state, and B is the maximum temperature T ₃ (hereinafter referred to as the color erasing) capable of maintaining the complete color development state. C is a point indicating the density at the lowest temperature T ₂ (hereinafter referred to as a color development start temperature) at which a completely decolored state can be maintained, and D reaches a complete color development state. This is a point indicating the density at the maximum temperature T ₁ (hereinafter referred to as a complete color development temperature).
Discoloration temperature region is a temperature region between the T ₁ and T _4, the first hue and can co-exist two phases of the second color, the temperature range between T ₂ and T ₃ is a large area of the difference in color density Is a substantial discoloration temperature range (two-phase holding 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.

Of the above-described compositions, by using a reversible thermochromic composition having color memory, it is possible to easily change the color from colored to colorless, and to make colors different from normal colors interchangeably visible. it can.
Specifically, the complete color development temperature T ₁ is a temperature that can be obtained only in a freezing room, a cold district, etc., that is, −30 to 10 ° C., preferably −30 to 0 ° C., more preferably −30 to −10 ° C., and , complete decoloring temperature _{T 4} frictional heat generated by friction body, the temperature obtained from the hair dryer familiar heating body, i.e. 30 to 80 ° C., preferably 50 to 80 ° C., and more preferably specific in the range of 60-80 ° C. However, by specifying the ΔH value at 40 to 60 ° C., it is possible to effectively function to maintain the color exhibited in the normal state (daily life temperature range).

  As the component (i), that is, the electron-donating color-forming organic compound, conventionally known diphenylmethane phthalides, phenyl indolyl phthalides, indolyl phthalides, diphenyl methane azaphthalides, phenyl indolyl azaphthalides Fluoranes, styrinoquinolines, diazarhodamine lactones, and pyridine, quinazoline, and bisquinazoline compounds that are effective in developing fluorescent yellow to red color.

(B) Component electron-accepting compounds include active proton-containing compounds, pseudo-acidic compounds (compounds that are not acids but act as acids in the composition to cause component (I) to develop color), electrons There is a group of compounds having pores.
Examples of compounds having active protons include monophenols to polyphenols as compounds having phenolic hydroxyl groups, and alkyl groups, aryl groups, acyl groups, alkoxycarbonyl groups, carboxy groups and esters thereof as substituents. Or what has an amide group, a halogen group, etc., phenol-aldehyde condensation resin etc., such as a bis type and a tris type phenol, are mentioned. Moreover, the metal salt of the compound which has the said phenolic hydroxyl group may be sufficient.

Examples of the component (c) include alcohols, esters, ketones, ethers, and acid amides.
The component (c) is preferably a large hysteresis characteristic regarding the color density-temperature curve (a curve plotting a change in color density due to a temperature change changes the temperature from the low temperature side to the high temperature side and the high temperature side to the low temperature side). A carboxylic acid ester compound that exhibits a ΔT value (melting point-cloud point) of 5 ° C. or higher and lower than 50 ° C., which can form a reversible thermochromic composition that exhibits color memory, and changes color when changing to the side) For example, a carboxylic acid ester having a substituted aromatic ring in the molecule, an ester of a carboxylic acid having an unsubstituted aromatic ring and an aliphatic alcohol having 10 or more carbon atoms, a carboxylic acid ester having a cyclohexyl group in the molecule, 6 carbon atoms Fatty acid and unsubstituted aromatic alcohol or phenol ester, fatty acid having 8 or more carbon atoms and branched aliphatic alcohol or ester, dicarboxylic acid And esters of aromatic alcohols or branched aliphatic alcohols, dibenzyl cinnamate, heptyl stearate, didecyl adipate, dilauryl adipate, dimyristyl adipate, dicetyl adipate, distearyl adipate, trilaurin, trimyristin, tristearin, Dimyristin, distearin and the like are used.
Also, fatty acid ester compounds obtained from an odd aliphatic monohydric alcohol having 9 or more carbon atoms and an aliphatic carboxylic acid having an even number of carbon atoms, n-pentyl alcohol or n-heptyl alcohol and an even fat having 10 to 16 carbon atoms. A fatty acid ester compound having a total carbon number of 17 to 23 obtained from a group carboxylic acid is also effective.
More preferably, the compound described in JP-A-2006-137886 or the compound described in JP-A-2006-188660 is used as the component (c).

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. Parts by weight).
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.

  In addition to the heat decoloring type, a specific alkoxyphenol compound having a linear or side chain alkyl group having 3 to 18 carbon atoms as an electron accepting compound (Japanese Patent Laid-Open No. 11-129623), a specific hydroxybenzoic acid A heat-colorable microcapsule pigment using an ester (Japanese Patent Laid-Open No. 2001-105732), a gallic acid ester (Japanese Patent Laid-Open No. 2003-253149), or the like can also be applied.

Although the form of the microcapsule pigment applied to the present invention does not refuse application of a circular cross-sectional form, a non-circular cross-sectional form is effective.
The reversible thermochromic handwriting formed by writing has the above-mentioned microcapsule pigment closely oriented and fixed in close contact with the writing surface on the long diameter side (maximum outer diameter side). In addition, the microcapsule pigment is slightly elastically deformed into a shape that relaxes the external force against the external force caused by rubbing with a friction body such as rubber, and the destruction of the wall film of the microcapsule is suppressed. It can be expressed effectively without impairing the function.
Here, the non-circular cross-sectional shape microcapsule pigment has an average maximum outer diameter in the range of 0.5 to 5.0 μm and a reversible thermochromic composition / wall film = 7/1 to 1. / 1 (weight ratio) is preferably satisfied.
The microcapsule pigments (including those having a circular cross-sectional shape) exhibit a decrease in the ability to flow out from the capillary gap when the average maximum outer diameter exceeds 5.0 μm, while the average maximum outer diameter In a system having a value of 0.5 μm or less, it is difficult to show coloration at a high concentration. Preferably, the average value of the maximum outer diameter is in the range of 1 to 4 μm, the average particle diameter of the microcapsule [(maximum outer diameter + center The minimum outer diameter) / 2] is preferably in the range of 1 to 3 μm.
If the ratio of the reversible thermochromic composition to the wall film is larger than the above range, the wall film becomes too thin, causing a decrease in pressure and heat resistance, and conversely, the reversible thermochromic composition of the wall film. When the ratio to the above is larger than the above range, the color density and sharpness during color development are unavoidable, and preferably the reversible thermochromic composition / wall film = 6/1 to 1/1 (weight ratio). .

  For the microencapsulation of the reversible thermochromic composition, known means such as an interfacial polymerization method, an interfacial polycondensation method, an in situ polymerization method, and a coacervate method can be applied, but the particle size range satisfying the above-described requirements of the present invention. In order to obtain a microcapsule pigment having a non-circular cross-sectional shape, it is effective to apply an interfacial polymerization method or an interfacial polycondensation method that hardly causes aggregation or coalescence.

  The microcapsule pigment can be blended in an amount of 2 to 50% by weight (preferably 3 to 40% by weight, more preferably 4 to 30% by weight) based on the total amount of the ink composition. If it is less than 2% by weight, the color density is insufficient, and if it exceeds 50% by weight, the ink outflow property is lowered and the writing property may be impaired.

As the colorant that can be applied together with the microcapsule pigment, general-purpose dyes and pigments conventionally applied to oil-based inks are appropriately used.
Examples of the dye include organic solvent-soluble dyes classified as solvent dyes in the color index.
Specific examples of the solvent dye include Balifast Black 3806 (CI Solvent Black 29), 3807 (Trimethylbenzylammonium salt of the dye of CI Solvent Black 29), Spirit Black SB (C.I. Solvent Black 5), Spiron Black GMH (CI Solvent Black 43), Bali Fast Red 1308 (Salt Form of Dye of CI Basic Red 1 and Dye of CI Acid Yellow 23), Bali Fast Yellow AUM (Salt of CI Basic Yellow 2 dye and CI Acid Yellow 42 dye), Spiron Yellow C2GH (organic acid salt of CI Basic Yellow 2 dye) Ron Violet CRH (CI Solvent Violet 8-1), Balifu Strioviolet 1701 (salt salt of CI Basic Violet 1 and CI Acid Yellow 42 dyes), Spiron Red CGH (organic acid salt of CI Basic Red 1 dye), Spiron Pink BH (C.I. CI Solvent Red 82), Nigrosine Base EX (CI Solvent Black 7), Oil Blue 613 (CI Solvent Blue 5), Neozapon Blue 808 (CI Solvent Blue 70) and the like. It is done.
Examples of the pigment include inorganic pigments such as carbon black, ultramarine, and titanium dioxide pigment, azo pigments, phthalocyanine pigments, indigo pigments, thioindigo pigments, selenium pigments, quinacridone pigments, anthraquinone pigments, selenium pigments, diketopyrrolo Organic pigments such as pyrrole pigments, dioxazine pigments, perylene pigments, perinone pigments, isoindolinone pigments, aluminum pigments, metal pigments whose surfaces are treated with colored resins, transparent or colored transparent films such as aluminum Metallic pigment, gold, silver, platinum, copper, with a thickness of 0.01 to 0.1 μm, obtained by peeling a metallic vapor deposited film such as aluminum formed on a substrate such as a metallic luster pigment, film, etc. Colloidal particles with an average particle size selected from 5 to 30 nm, fluorescent pigments, luminous pigments, thermal discoloration Pigments, natural mica as a core material, synthetic mica, glass pieces, alumina, pearl pigment and the like to the surface of the transparent film pieces were coated with a metal oxide such as titanium oxide.

As the liquid medium serving as the main solvent, at least one of polybutene, liquid paraffin, liquid isoparaffin, ethylene-α-olefin oligomer, α-olefin oil, and refined mineral oil is applied.
The liquid isoparaffin is a hydrocarbon compound called hydrogenated polyisobutene, and one having a relatively low kinematic viscosity can be applied.
The liquid medium preferably has an average molecular weight of 1000 or less.

Moreover, the drying time of a handwriting can also be adjusted using a general purpose organic solvent with the said main solvent.
As the organic solvent, hydrocarbon solvents such as methylcyclohexane, ethylcyclohexane, normal heptane, normal octane, isooctane and xylene are suitable.
The liquid medium used alone or mixed with one or more organic solvents is used in the range of 40 to 90% by weight in the ink composition.

The fatty acid amide is added to adjust the ink viscosity and increase the stability of the microcapsule pigment. Specifically, lauric acid amide, stearic acid amide, oleic acid amide, erucic acid amide, ricinoleic acid amide, 12-hydroxystearic acid amide, N-isobutyl lauric acid amide, N-isobutyl stearic acid amide, N-oleyl olein Acid amide, N-stearyl stearic acid amide, N-stearyl oleic acid amide, N-oleyl palmitic acid amide, N-stearyl erucic acid amide, N-cyclohexylmethyl lauric acid amide, N-cyclohexylmethyl caproic acid amide, N, N '-Ethylenebislauric acid amide, N, N'-ethylenebisstearic acid amide, N, N'-ethylenebisoleic acid amide, N, N'-ethylenebisbehenic acid amide, N, N'-ethylenebi 12-hydroxystearic acid amide, N, N'- butylene-bis-stearic acid amide, N, N'- hexamethylene bis-stearic acid amide, N, can be mentioned N'- hexamethylene bis oleic acid amide or the like.
The fatty acid amide is preferably applied to ink after being prepared in a paste form.

The fatty acid amide is used in the range of 0.1 to 3% by weight, preferably 0.5 to 3% by weight, based on the total amount of the ink composition.
If the amount is less than 0.1% by weight, it is difficult to achieve the desired effect, and it is possible to add more than 3% by weight. However, if the amount is less than 3% by weight, the desired effect can be sufficiently obtained. do not do.

A general-purpose resin can be used for fixing to the paper surface or imparting viscosity.
Examples of the resin include ketone resins, ketone-formaldehyde resins, amide resins, alkyd resins, rosin-modified resins, rosin-modified phenol resins, phenol resins, xylene resins, polyvinylpyrrolidone, α- and β-pinene / phenol polycondensation resins, and polyvinyl butyral. Examples thereof include resins, acrylic resins, styrene maleic acid copolymers, cellulose derivatives, polyvinyl pyrrolidone, polyvinyl alcohol, and dextrin.

Further, in addition to the above components, an antioxidant, an ultraviolet absorber, a rust inhibitor, a lubricant, a viscosity modifier, a release agent, a pigment dispersant, an antifoaming agent, a shear thinning agent, and a surfactant as necessary. Various additives such as can be used.
The additive is a so-called conventional additive, and can be appropriately used as necessary from known compounds.

As the rust inhibitor, benzotriazole, tolyltriazole, dicyclohexylammonium nitrite, diisopropylammonium nitrite, saponin and the like can be used.
As the antioxidant, dibutylhydroxytoluene, nordihydroxytoluene, flavonoids, butylhydroxyanisole, ascorbic acid derivatives, α-tocopherol, catechins and the like can be used.
As UV absorbers, 2- (2'-hydroxy-3'-t-butyl 5'-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) Benzotriazole, p-benzoic acid-2-hydroxybenzophenone, and the like can be used.
As the antifoaming agent, dimethylpolysiloxane or the like can be used.

  Lubricants include higher fatty acids such as oleic acid, nonionic surfactants having a long chain alkyl group, polyether-modified silicone oil, thiophosphite tri (alkoxycarbonylmethyl ester) and thiophosphite tri (alkoxycarbonylethyl ester). ) And the like can be used. In particular, polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether phosphoric acid monoester, polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether phosphoric acid diester, or metal salts, ammonium salts, amine salts thereof, When an alkanolamine salt or the like is used, the effect of preventing wear of the ball seat is excellent.

  As the shear thinning agent, a conventionally known compound can be used. For example, a crosslinked acrylic resin, an emulsion type of a crosslinked acrylic resin, a crosslinked N-vinylcarboxylic acid amide polymer or copolymer, Non-crosslinked N-vinylcarboxylic acid amide polymer or copolymer Non-crosslinked N-vinylcarboxylic acid amide polymer or copolymer aqueous solution, hydrogenated castor oil, fatty acid amide wax, waxes such as oxidized polyethylene wax, Fatty acid metal salts such as aluminum stearate, aluminum palmitate, aluminum octylate, aluminum laurate, dibenzylidene sorbitol, dextrin fatty acid ester, N-acyl amino acid compound, smectite inorganic compound, montmorillonite inorganic compound, bentonite inorganic compound , Hex Light-based inorganic compounds, silica and the like.

  The ink composition is put to practical use by filling a ballpoint pen with a ballpoint tip attached to the writing tip. The structure and shape of the ballpoint pen itself are not particularly limited. For example, a structure in which ink is impregnated with a fiber bundle housed inside the shaft tube and ink is supplied to the writing tip, and the shaft tube A structure for interposing an ink flow rate adjusting member composed of a comb groove-like ink flow rate adjusting member or a fiber bundle, containing an ink directly, and having an ink containing tube filled with an ink composition. Further, there can be exemplified a structure in which a ballpoint pen refill in which an ink follower such as a liquid stopper or a solid stopper is in close contact with the end face of the ink and is in close contact with the end face of the ink is contained in the shaft cylinder.

The ballpoint pen can be applied to either a cap type or a retractable type. As a retractable ballpoint pen, the writing tip provided on the ballpoint pen refill is housed in the shaft cylinder in a state exposed to the outside air, and the writing tip is projected from the opening of the shaft tube by the operation of the retracting mechanism. Anything can be used.
Examples of the operation method of the retracting mechanism include a knock type, a rotary type, and a slide type.
The knock type has a knock portion on the rear end portion of the shaft cylinder and the side surface of the shaft tube, and the writing tip portion of the ball pen refill is projected and retracted from the front end opening portion of the outer shaft by pressing the knock portion. The structure which makes the writing tip part of a ball-point pen refill appear and disappear from the axial cylinder front-end opening part by pressing the provided clip part can be illustrated.
The rotary type can be exemplified by a configuration in which the shaft cylinder has a rotating portion (rear shaft or the like), and the writing tip of the ballpoint pen refill is caused to appear and disappear from the front end opening of the shaft cylinder by rotating the rotating portion.
The slide type has a slide part on the side surface of the shaft cylinder, and the sliding tip of the writing point of the ballpoint pen refill is projected and retracted from the front end opening of the shaft cylinder by operating the slide, or the clip part provided on the shaft cylinder is slid. By doing so, it is possible to exemplify a configuration in which the writing tip portion of the ballpoint pen refill is projected and retracted from the opening at the front end of the shaft cylinder.
The retractable ballpoint pen may be a composite retractable ballpoint pen that accommodates a plurality of ballpoint pen refills in addition to the one that accommodates one ballpoint refill in the shaft cylinder.

The ball-point pen tip will be described in detail. A tip formed by holding a ball in a ball holding portion in which the vicinity of the tip of a metal pipe is pressed and deformed inward from the outer surface, or a metal material is cut by a drill or the like. A tip formed by holding the ball in the formed ball holding portion, a tip provided with a resin ball receiving seat inside a metal or plastic tip, or a ball held by the tip is attached to the front by a spring body. You can apply what you have
The ball is 0.2 to 3.0 mm, preferably 0.3 to 1.5 mm, more preferably 0.4 to 1.2 mm, such as cemented carbide, stainless steel, ruby, ceramic, resin, and rubber. A thing of a diameter is applicable.

The ink compositions of Examples and Comparative Examples are shown in the following table.
In addition, the numerical value of a composition in a table | surface shows a weight part.

The contents of the raw materials in the table will be described along the note numbers.
(1) 2.0 parts of 3- (4-diethylamino-2-hexyloxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide as component (a), (b) Ingredients include bis (3-methyl-4-hydroxyphenyl) sulfide 8.0 parts, 2,2-bis (4'-hydroxyphenyl) hexafluoropropane 5.0 parts, (ha) capric acid 4-benzyloxy A microcapsule pigment encapsulating a reversible thermochromic composition comprising 50.0 parts of phenylethyl (T ₁ : −14 ° C., T ₂ : −6 ° C., T ₃ : 48 ° C., T ₄ : 60 ° C., ΔH: 64 (° C., average particle size: 2.5 μm, reversible thermochromic composition / wall film = 2.6 / 1.0, color change from blue to colorless)
(2) 4.5 parts of 2- (2-chloroanilino) -6-di-n-butylaminofluorane as component (a) and 1,1-bis (4'-hydroxyphenyl) n- as component (b) Reversible thermochromic composition comprising 4.5 parts of decane, 7.5 parts of 2,2-bis (4'-hydroxyphenyl) hexafluoropropane, and 50.0 parts of 4-benzyloxyphenylethyl caprate as the component (c) Microcapsule pigment encapsulating a product (T ₁ : −20 ° C., T ₂ : −9 ° C., T ₃ : 40 ° C., T ₄ : 57 ° C., ΔH: 63 ° C., average particle size: 2.5 μm, reversible thermal discoloration Composition / wall film = 2.6 / 1.0, color changes from black to colorless)
(3) Fatty acid amide paste obtained by uniformly stirring 15 parts of ethyl alcohol, 65 parts of xylol and 20 parts of N-stearyl erucic acid amide at 105 ° C. and then allowing to cool at room temperature (4) 90 parts of mineral spirits, N -Fatty acid amide paste obtained by uniformly stirring 10 parts of isobutyl lauric acid amide at 120 ° C and then allowing to cool at room temperature. (5) Terpene phenol resin, manufactured by Yashara Chemical Co., Ltd.
(6) Product name: Prisurf A208B, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
(7) NOF Corporation, trade name: New Glide M
(8) Product name: Pearl Ream 4 manufactured by NOF Corporation
(9) High call K-140N, manufactured by Kaneda Corporation

Preparation of ink In the compositions of the above examples and comparative examples, the respective components were mixed and each ink was prepared by stirring with a disper at 25 ° C for 3 hours.

Preparation of ink backflow prevention body 47 parts of polybutene, 47 parts of mineral oil, and 6 parts of fatty acid dextrin were kneaded in a three-roll mill to obtain an ink backflow prevention body.

Preparation of Ballpoint Pen The ink compositions of the above examples and comparative examples were filled into a ballpoint pen refill in which a stainless steel tip holding a carbide ball having a diameter of 0.7 mm was fitted to one end of a polypropylene pipe. After the ink backflow preventive body was disposed on, the ballpoint pen refill was incorporated into an outer shaft (cap type) to produce a sample ballpoint pen. The rear end portion of the outer shaft is provided with SEBS resin as a friction member.

The following tests were performed using the obtained ballpoint pen.
Drying resistance test Each ballpoint pen cap is removed and held in a horizontal position, left at a temperature of 25 ° C. for 10 days, and then handwritten on the old JIS P3201 writing paper A. The state of was observed visually.
Ink stability test Each ballpoint pen is held upwards, left in a constant temperature bath at 40 ° C for 30 days, and then allowed to cool at room temperature. The ink is spirally handwritten on the old JIS P3201 writing paper A. The state of the handwriting (colored state) when continuously writing the circle was visually observed and compared with the initial ink and handwriting.

The test results are shown in the following table.

In addition, the evaluation regarding the symbol in a table | surface is as follows.
Drying resistance test ◯: A handwriting with no blur is obtained.
X: Scratch occurs in the handwriting or writing is impossible.
Ink stability test ○: Ink separation does not occur, and handwriting with the same density as the initial stage is obtained.
X: The ink is separated and the handwriting is lightened.

T ₁ complete color development temperature T ₂ color development start temperature T ₃ color erase start temperature T ₄ complete color erase temperature ΔH hysteresis width

Claims (3)

  (B) Reversible heat encapsulating a reversible thermochromic composition comprising a reaction medium that determines the temperature at which the color reaction of both occurs (b) an electron-donating color-forming organic compound; Reversible thermochromic properties for ballpoint pens comprising a discolorable microcapsule pigment, one or more liquid media selected from polybutene, liquid paraffin, liquid isoparaffin, ethylene-α-olefin oligomer, α-olefin oil, refined mineral oil, and fatty acid amide. Oil-based ink composition.   The reversibly thermochromic oil-based ink composition for ballpoint pens according to claim 1, wherein the fatty acid amide is contained in the total amount of the ink composition in an amount of 0.1 to 3% by weight.   A ballpoint pen comprising the reversible thermochromic oil-based ink composition for ballpoint pens according to claim 1 or 2.

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