JP6903429B2 - Bright ink composition for ballpoint pens and ballpoint pens containing them - Google Patents

Description

The present invention relates to a brilliant ink composition for a ballpoint pen. Further, the present invention relates to a brilliant ink composition for a ballpoint pen capable of forming a handwriting with high color development on a paper surface, and a ballpoint pen having excellent writing performance.

Conventionally, various reflective pigments such as metal powder are added to the ink in order to obtain a metallic glossy brush stroke, but due to the high brightness of the obtained brush stroke, a plate-shaped (scaly) metal powder or pearl pigment is used. An aqueous ink composition using a plate-like bright pigment such as the above has been proposed.
In the brilliant ink using the plate-shaped brilliant pigment, in order to adjust the hue of the ink, a general-purpose dye or pigment may be added to the ink, or the surface of the plate-shaped brilliant pigment may be colored. (See, for example, Patent Documents 1 and 2).
As described in Patent Document 1, when a general-purpose colorant (dye or pigment) is added to the ink, the paper surface has permeability, so that only a plate-shaped bright pigment having a large particle size at the time of writing is used. Is laminated on the surface of the paper, and the colorant component permeates the paper surface, so that it becomes difficult to obtain a stroke of a desired hue. Further, when a plate-shaped bright pigment whose surface is colored is used, it is not necessary to consider the penetration of the above-mentioned coloring component, but in order to color the entire ink, the plate-shaped bright pigment used is used. Since it is necessary to increase the particle size of the ink and to increase the amount of the ink added, ink ejection failure is likely to occur during writing, and sedimentation or the like is likely to occur during storage.

Further, when the ink using the plate-shaped bright pigment is built in the ballpoint pen, the plate-shaped bright pigment may aggregate to hinder the rotation of the ball during writing. Therefore, there arises a problem that ink ejection becomes unstable during writing and causes writing defects such as handwriting blurring.
In order to solve the above problems, attempts have been made to improve the dispersibility of the plate-shaped bright pigment by adding hollow resin particles to the ink composition using the plate-shaped bright pigment (for example, Patent Documents). 3).
The hollow resin particles are added in an emulsion or dispersion state to the ink to inhibit the adsorption action between the bright pigments and maintain the dispersed state, but a thickener such as xanthan gum or the like. When used in combination with (shear thinning agent), the hollow resin particles aggregate with each other, which deteriorates the writing performance.

Japanese Unexamined Patent Publication No. 11-29734 Japanese Unexamined Patent Publication No. 2003-12973 Japanese Patent No. 3992493

According to the present invention, even when a high-brightness water-based ink using a plate-shaped bright pigment is incorporated in a ballpoint pen, it is possible to form a vivid handwriting that gives off a colorful and high-brightness shine on paper surfaces of various hues. At the same time, the present invention provides a brilliant ink composition for a ballpoint pen capable of maintaining stable ink characteristics for a long period of time without causing aggregation or the like even when a shear-degrading agent is used, and a ballpoint pen incorporating the same. ..

The bright ink composition for a ball pen of the present invention comprises a plate-shaped bright pigment, a coloring pigment, microcapsule particles containing an oily solvent, water, a salt of an acrylic acid-based polymer, or an olefin-based polymer. It contains one or more salts or emulsions selected from urethane-based polymers and emulsions of acrylic acid-based polymers, and the salts of the acrylic acid-based polymers are polyacrylic acid, polycarboxylic acid, acrylic acid / maleine. One or more selected from acid copolymers, acrylic acid / sulfonic acid-based monomer copolymers, acrylic acid / unsaturated carboxylic acid copolymers, and salts of styrene / acrylic acid copolymers, and the above-mentioned olefin-based The polymer is selected from polyethylene, polypropylene, ethylene-vinyl acetate copolymer or ethylene-ethyl acrylate copolymer having an anionic functional group as the main skeleton, and ethylene- (meth) acrylic acid copolymer. One or more of the above, and the urethane-based polymer is selected from polymers having an anionic functional group having a reaction product of polyisocyanate and polyether polyol, polyester polyol or polycarbonate polyol as the main skeleton. Alternatively, there are two or more of them , and the emulsion of the acrylic acid-based polymer is an acrylic acid / maleic acid copolymer, an acrylic acid / sulfonic acid-based monomer copolymer, an acrylic acid / unsaturated carboxylic acid copolymer or styrene /. It is required that the amount is one or more selected from the emulsion of the acrylic acid copolymer.
Further, it is required that the oily solvent has a specific gravity of 1.0 or less.
Further, it is required that the plate-shaped bright pigment is at least one selected from pearl pigments, aluminum pigments, metals or metal oxide-coated glass flakes.
Further, the solvent contained in the microcapsule particles is one or more selected from esters, aromatic hydrocarbons, higher alcohols, ketones and ethers, and contains a shear thinning agent. Is a requirement.
Further, a ballpoint pen incorporating the brilliant ink composition for a ballpoint pen is required.

According to the present invention, even when a high-brightness water-based ink using a brilliant plate-like pigment is built in a ballpoint pen, writing can be performed without causing ink ejection failure due to precipitation or the like, and coloring components do not permeate the paper surface. A handwriting of a desired hue can be formed. Further, a brilliant ink composition for a ballpoint pen capable of maintaining stable ink characteristics for a long period of time without causing aggregation or the like even when a shear thinning agent is used, and a ballpoint pen incorporating the same.

In the present invention, in a colorful bright water-based ink composition using a plate-shaped (including scaly) bright pigment together with a coloring pigment, a salt of an acrylic acid-based polymer or a salt of an acrylic acid-based polymer is used together with microcapsule particles containing an oily solvent. , Olefin-based polymer, urethane-based polymer, and acrylic acid-based polymer emulsion are blended to prevent the plate-like bright pigment and the coloring pigment from adsorbing and aggregating, and at the time of writing, the coloring pigment. By suppressing the penetration of the ink from the paper surface into the inside, it is possible to form a stable brush stroke for a long period of time with a vivid color tone having a high color-developing property that expresses brilliance.
The average particle size of the plate-shaped pigment in the present invention is a value calculated by assuming that the minimum value of the particle size axis in the particle size distribution map is 0.5 μm when measured by a laser diffraction method (volume basis). The average particle size of the microcapsule particles is an arithmetic mean diameter obtained by measurement by a laser diffraction method (volume basis).

The plate-shaped brilliant pigment may be a plate-shaped or scaly pigment that reflects light in a brush stroke state, and in particular, a pearl pigment, an aluminum pigment, a metal or a metal oxide-coated glass flake, or the like. Can be mentioned. These are selected one or more and blended in the ink.

Specifically, the pearl pigment includes a natural product such as fish scale foil and a synthetic product in which the surface of natural mica, synthetic mica, silica or the like is coated with a metal oxide, and the latter is generally used in many cases. .. The pearl pigment exhibits various color tones depending on the type of metal oxide coated on the surface of mica and the coating film thickness. Examples of commercially available pearl pigments include Iriodin 100 (silver), 111 (silver), 151 (silver), 153 (silver), 201 (gold), 217 (bronze), and 289. (Blue), 302 (gold), 504 (wine red), Iriodin 530 (copper) [above, manufactured by Merck Japan Co., Ltd.], Ultimate SB-100 (silver) [above, Topy Industry Co., Ltd. Made] etc. Further, there are HELICONE HCS and HCXS [all manufactured by Wacker Chemie Co., Ltd.], which are called cholesteric liquid crystal type brilliant pigments.

The aluminum pigment can be obtained as a paste of aluminum fine particles on very thin scales by pulverizing and polishing aluminum pieces with a petroleum solvent such as higher fatty acid or mineral spirit with a ball mill or the like. Commercially available products include Alpaste WXM-0630, EMERAL EMR-D5660, and WJC-U75C [all manufactured by Toyo Aluminum K.K.].
In addition, thin-film aluminum obtained by vacuum deposition may be finely crushed, and commercially available products include METALURE W-52012 IL, Ultravario Aqua PG-24001 [above, manufactured by ECKART], and Elgi neo Silver. There are # 500 (silver), Gold # 500 (gold) [above, manufactured by Oike Kogyo Co., Ltd.] and the like.

The metal-coated glass flakes are obtained by coating the glass flakes with silver and nickel on the glass surface by an electroless plating method, and the metal oxide-coated glass flakes are obtained by coating the glass flakes with titanium dioxide by a liquid phase method. .. By changing the thickness of this titanium oxide film, colors such as silver, yellow, red, blue, and green can be obtained. Commercially available metal or metal oxide coated glass flakes include Metashine 2040PS, 2020PS, 5090NS, 5090RC [above, manufactured by Nippon Sheet Glass Co., Ltd.] and the like.

These plate-shaped bright pigments may be used alone or in combination of two or more according to a desired hue and light brightness. The amount of the plate-shaped bright pigment used is 1.0 to 20% by weight, preferably 3.0 to 12% by weight, based on the total amount of the ink composition.

Further, in the plate-shaped bright pigment used in the ink composition of the present invention, the particle size is not particularly limited, but writing cannot be performed with the ballpoint pen used, or the pigment is discharged during writing (ink outflow hole). A particle size is selected that does not prevent writing from being blocked. If the particle size is too small, it becomes difficult to obtain a brilliant feeling in the handwriting state, and if it is too large, there is a strong tendency to hinder ink ejection and promote seat wear. Therefore, a particularly preferable average particle size is 3 to 25 μm. Is the range of.

The microcapsule particles used in the present invention contain an oily solvent, and can be used in combination with an emulsion of a polyacrylate, an olefin polymer, a urethane polymer, or an acrylic acid polymer to disperse each pigment. Writing can be performed while maintaining the properties, and the colored pigments of the brush strokes are suppressed from penetrating into the inside from the paper surface. In particular, since the microcapsule particles have high self-dispersion, they have an effect of suppressing adsorption between plate-shaped bright pigments, and can effectively suppress the aggregation of pigments.
Further, by including an oily solvent, the dispersed state can be maintained for a long period of time in an aqueous medium.

The microcapsule particles are obtained by encapsulating the dispersion in a shell made of a wall film-forming substance by a conventionally known microencapsulation method, and examples of the wall film-forming substance include gelatin, shellac, and the like. Arabic gum, rosin, rosin ester, ethyl cellulose, carboxymethyl cellulose, paraffin, tristeare, polyvinyl alcohol, polyethylene, polypropylene, acrylic resin, vinyl resin, polyisobutene, polyurethane, polybutadiene, polyester, polyamide, epoxy resin, phenol resin, silicone Resin, polystyrene, melamine resin and the like can be used alone or in combination.
Examples of the microencapsulation method include an interfacial polymerization method, an interfacial polycondensation method, an insitu polymerization method, a coacervation method, an in-liquid curing coating method, a phase separation method from an aqueous solution, a phase separation method from an organic solvent, and melting. The dispersion cooling method, the air suspension coating method, the spray drying method and the like can be mentioned and can be appropriately selected.

As the solvent contained in the microcapsule particles, an oily solvent is applied because the physical properties are unlikely to change even under high temperature conditions and the release to the outside of the microcapsules is unlikely to occur, and esters, aromatic hydrocarbons, and higher grades are used. One or a mixture of two or more selected from alcohols, ketones, and ethers can be used.
By using a solvent having a specific gravity of 1.0 or less, the specific gravity of the microcapsule particles can be reduced and the difference in specific gravity from the water-based ink medium can be easily adjusted to be small. It becomes easier for the particles to maintain the dispersed state in the ink.

The microcapsule particles are microencapsulated so that the average particle size is in the range of 0.2 to 5 μm, preferably 0.5 to 3 μm (the average particle size is based on laser diffraction or volume).
If the average particle size is less than 0.2 μm, a large amount of addition is required to suppress the aggregation of the plate-like bright pigment, and if it exceeds 5 μm, the writing ejection property of the microcapsule particles may decrease, which is preferable. Absent.

The content of the microcapsule particles is preferably 0.5 to 20% by weight, preferably 1 to 10% by weight, based on the total amount of the ink composition. If the content is less than 0.5%, it may be difficult to obtain the adsorption suppressing effect of each pigment, and if it exceeds 20% by weight, the effect is not improved, so no further addition is required.

The salt of the acrylic acid-based polymer, the emulsion of the olefin-based polymer, the emulsion of the urethane-based polymer, and the emulsion of the acrylic acid-based polymer can be used in combination with the microcapsule particles containing an oily solvent to obtain each pigment. It is possible to write while maintaining the dispersibility, and it suppresses the permeation of the colored pigment of the brush stroke from the paper surface to the inside. In particular, in the salts and emulsions of the acrylic acid-based polymers, carboxyl groups and sulfo groups are adsorbed on the coloring pigments and act on them, and the coloring pigments can be suppressed from penetrating into the paper surface. It becomes possible to form the handwriting of. Further, in the storage state, the aggregation of the pigment adsorbed by the three-dimensional and electrical repulsion can be suppressed, so that the stability with time is excellent.
In particular, the salts and emulsions of the acrylic acid-based polymer are not only adsorbed on the coloring pigment but also easily adsorbed on the plate-like bright pigment, and the salts and emulsions of the acrylic acid-based polymer adsorbed on the coloring pigment It also adsorbs to the plate-shaped bright pigment and binds the three components, and as a result, it works to fix the colored pigment to the plate-shaped bright pigment. Therefore, the colored pigment permeates the inside of the paper surface and aggregates with time. It becomes possible to suppress.

Examples of the salt or emulsion of the acrylic acid-based polymer include polyacrylic acid, polycarboxylic acid, acrylic acid / maleic acid copolymer, acrylic acid / sulfonic acid-based monomer copolymer, and acrylic acid / unsaturated carboxylic acid copolymer. A water-soluble salt obtained by neutralizing a coalescence, a styrene / acrylic acid copolymer or the like with an alkaline substance such as sodium hydroxide, ammonia or alkanolamine, or the polymer or copolymer is dispersed in a medium to form an emulsion. Things are used. Among them, those having a sulfo group in the molecule are more useful because they exhibit a high effect regardless of the pH of the ink.

Specifically, the salts include Aron A-6001, A-6012, A-6330, A-30L [above, manufactured by Toa Synthetic Co., Ltd.], John Krill 60J, 61J, 63J [above, BASF Japan], Aquaric GL, LS [above, manufactured by Nippon Catalyst Co., Ltd.], etc., and the emulsions include John Krill PDX-7182, PDX-7630A, PDX-7692, 711 [above]. , BASF Japan], Boncoat 5400EF [above, DIC Corporation], Movinyl 7525 [above, Nippon Synthetic Chemical Co., Ltd.], Neokrill A-640 [above, Kusumoto Kasei Co., Ltd.], etc. , One type or two or more types are used.

The type of urethane polymer is not particularly limited, and examples thereof include reaction products of polyisocyanate and polyols such as polyether, polyester, and polycarbonate, and these are dispersed in a medium to form an emulsion. Used.
In the urethane-based polymer, since the amorphous portion existing in the molecule and the crystalline urethane bond interact with the coloring pigment and the plate-like bright pigment, only the coloring pigment is absorbed on the paper surface at the time of writing. This can be suppressed, and it becomes possible to form a brush stroke with a vivid color tone having high color development. In particular, a self-emulsifying emulsion having an anionic functional group in the molecule is more useful because it exhibits a high effect regardless of the pH of the ink.
Specifically, NeoRez R-972, R-2170, R-966, R-967, R-986, R-9603, R-9404 [all manufactured by Kusumoto Kasei Co., Ltd.], U-Court UX-485, UWS-145, Upren UXA-307 [above, Sanyo Kasei Co., Ltd.], Hydran AP-40N, APX-101H [above, DIC Co., Ltd.], Superflex 150, 460 , 470, 820 [above, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.] and the like, and one kind or two or more kinds are used.

The type of the olefin polymer is not particularly limited, and examples thereof include polyethylene, polypropylene, ethylene- (meth) acrylic acid copolymer, ethylene-vinyl acetate copolymer, and ethylene-ethyl acrylate copolymer. , These are dispersed in a medium to form an emulsion, which is used. In particular, a self-emulsifying emulsion having an anionic functional group in the molecule is more useful because it exhibits a high effect regardless of the pH of the ink.
Specifically, Zyxen L, A, A-GH [above, manufactured by Sumitomo Seika Chemical Co., Ltd.], HYTEC E-4A, E-5403, E-9460 [above, Toho Chemical Industry Co., Ltd.] Manufactured], etc., and one or more types are used.

The pigments include inorganic pigments such as carbon black and ultramarine blue, organic pigments such as copper phthalocyanine blue and benzidine yellow, and water-dispersed pigments finely and stably dispersed in an aqueous medium using a surfactant or the like in advance. Products and the like are used, for example, C.I. I. Pigment Blue 15: 3B [Product name: S.I. S. Blue GLL, pigment content 22%, manufactured by Sanyo Dye Co., Ltd.], C.I. I. Pigment Red 146 [Product name: S.I. S. Pink FBL, pigment content 21.5%, manufactured by Sanyo Dye Co., Ltd.], C.I. I. Pigment Yellow 81 [Product name: TC Yellow FG, pigment content about 30%, manufactured by Dainichiseika Kogyo Co., Ltd.], C.I. I. Pigment Red 220/166 [Product name: TC Red FG, pigment content of about 35%, manufactured by Dainichiseika Kogyo Co., Ltd.] and the like can be mentioned.
As the fluorescent pigment, a synthetic resin fine particulate fluorescent pigment in which various fluorescent dyes are solid-solved in a resin matrix can be used.
In addition, phosphorescent pigments, white pigments such as titanium dioxide, and further examples include heat-discoloring compositions, photo-discoloring compositions, capsule pigments in which fragrances and the like are directly or microencapsulated.

The thermochromic composition includes (a) an electron-donating color-developing organic compound, (b) an electron-accepting compound, and (c) a reversible thermochromic composition comprising a reaction medium that determines the occurrence temperature of both of the color reactions. A sexual composition is suitable, which is encapsulated in microcapsules and applied as a reversible thermochromic microcapsule pigment.
The reversible thermochromic composition is described in Japanese Patent Publication No. 51-44706, Japanese Patent Publication No. 51-44707, Japanese Patent Publication No. 1-2398, and the like with a predetermined temperature (discoloration point) as a boundary. The color changes before and after, the color is decolorized in the temperature range above the high temperature side discoloration point, and the color is developed in the temperature range below the low temperature side discoloration point. The other state is maintained as long as the heat or cold required for the state to develop is applied, but returns to the state exhibited in the normal temperature range when the heat or cold is not applied, and the hysteresis width is A heat-decoloring type microcapsule pigment in which a reversible thermochromic composition having a relatively small property (ΔH = 1 to 7 ° C.) is encapsulated in a microcapsule can be applied.
Further, relatively large hysteresis characteristics (ΔH = 8 to 50) described in JP-A-4-17154, JP-A-7-179777, JP-A-7-33997, JP-A-8-39936 and the like. It exhibits a large hysteresis characteristic described in JP-A-2006-137886, JP-A-2006-188660, JP-A-2008-45062, JP-A-2008-280523, and the like. That is, the shape of the curve plotting the change in coloring density due to the temperature change is significantly different between the case where the temperature is raised from the lower temperature side than the discoloration temperature range and the case where the temperature is lowered from the higher temperature side than the discoloration temperature range. A reversible thermochromic composition that discolors by following a path and has color memory in a specific temperature range when the color is developed in a low temperature range below the complete color development temperature or in a high temperature range above the complete decolorization temperature. A heat-decoloring type microcapsule pigment can also be applied.
Specifically, as the reversible thermochromic composition having color memory, the complete color development temperature can be obtained only in a freezer, a cold region, or the like, that is, −50 to 0 ° C., preferably -40 to −. 5 ° C, more preferably -30 to -10 ° C, and the complete decoloring temperature is the frictional heat of the friction body, the temperature obtained from a familiar heating body such as a hair dryer, that is, 50 to 95 ° C, preferably 50 to 90 ° C. , More preferably, it is specified in the range of 60 to 80 ° C., and the ΔH value is specified in the range of 40 to 100 ° C., so that it can effectively function to maintain the color exhibited in the normal state (daily living temperature range).

Further, if necessary, a dye that is soluble in an aqueous medium can be used in combination.
As the dye, an acid dye, a basic dye, a direct dye and the like can be used, and as the acid dye, eosin (CI 16255), tartrazine (CI 19140), acid blue black and the like can be used. 10B (CI 20470), Guinea Green (CI 42085), Brilliant Blue FCF (CI 42090), Acid Violet 6B (CI 42640), Solve Blue (CI 42755) ), Naphthalene Green (CI 44025), Eosin (CI 45380), Floxin (CI 45410), Erythrosin (CI 45430), Niglosin (CI 50420), Acid Flavin (CI56205) and the like are used.
As basic dyes, chrysoidin (CI 11270), methyl violet FN (CI 42535), crystal violet (CI 42555), malachite green (CI 42000), Victoria blue FB ( CI 44045), Rhodamine B (CI 45170), Acridine Orange NS (CI 46005), Methylene Blue B (CI 52015) and the like are used.
As direct dyes, Congo Red (CI 22120), Direct Sky Blue 5B (CI 24400), Violet BB (CI 27905), Direct Deep Black EX (CI 30235), Kaya Las black G conc (CI 35225), direct fast black G (CI 35255), phthalocyanine blue (CI 74180) and the like are used.

The colorant containing the pigment may be used alone or in admixture of two or more, and is used in the range of 1 to 35% by weight, preferably 2 to 30% by weight in the ink composition.

Further, a general-purpose pigment dispersant can also be used. As the pigment dispersant, a water-soluble resin, a surfactant, or the like can be applied. Examples of the water-soluble resin include water-soluble maleic acid resin, water-soluble styrene resin, water-soluble styrene maleic acid resin, polyvinylpyrrolidone, polyvinyl alcohol, and water-soluble urethane resin. Further, as the surfactant, any one of anionic, cationic, nonionic and amphoteric surfactants is selected and used.

Further, by adding a shear thinning agent, it is possible to improve the sedimentation stability of the particle components (plate-like bright pigment, coloring pigment, microcapsule particles) during storage and suppress handwriting bleeding.
As the shear-reducing agent, a substance soluble or dispersible in water is effective, and xanthan gum, welan gum, and succinoglycan (average molecular weight) in which the constituent monosaccharides are organic acid-modified heteropolysaccharides of glucose and galactose. Approximately 1-8 million), guar gum, locust bean gum and its derivatives, hydroxyethyl cellulose, alginate alkyl esters, polymers with a molecular weight of 100,000 to 150,000 containing alkyl esters of methacrylic acid as main components, glucomannan, agar and caragenin. Carbohydrates with gelling ability extracted from seaweeds such as benzylidene sorbitol and benziliden xylitol or derivatives thereof, crosslinkable acrylic acid polymers, polyN-vinylcarboxylic acid amides, inorganic fine particles, nonions having an HLB value of 8 to 12. Examples of based surfactants, metal salts and amine salts of dialkylsulfosuccinic acid can be exemplified, and further, it is stable even when N-alkyl-2-pyrrolidone and anionic surfactants are added in combination in the ink composition. It is possible to impart shear de-viscosity.

Further, if necessary, a conventional general-purpose water-soluble organic solvent compatible with water can be used. Specifically, ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, ethylene glycol monomethyl ether, ethylene glycol mono. Examples thereof include ethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone and the like.
The water-soluble organic solvent may be used alone or in combination of two or more, and is used in the range of 2 to 60% by weight, preferably 5 to 35% by weight.

Further, a water-soluble resin can be added to impart stickiness and viscosity to the paper surface. Examples of the water-soluble resin include alkyd resins, styrene-maleic acid copolymers, cellulose derivatives, polyvinylpyrrolidone, polyvinyl alcohol, dextrin and the like. The water-soluble resin may be used alone or in combination of two or more, and is used in the range of 1 to 30% by weight in the ink composition.

In addition, if necessary, inorganic salts such as sodium carbonate, sodium phosphate, sodium acetate, pH adjusters such as organic basic compounds such as water-soluble amine compounds, benzotriazole, tolyltriazole, 2,5-dimercapto- Anti-corrosive agents such as 1,3,4-thiasiazole, saponin, coal acid, sodium salt of 1,2-benzthiazolin 3-one, sodium benzoate, sodium dehydroacetate, potassium sorbate, propyl paraoxybenzoate, 2,3 , 5,6-Tetrachloro-4- (methylsulfonyl) pyridine and other preservatives or anticorrosives, urea, nonionic surfactants, sorbit, mannit, sucrose, glucose, reduced starch hydrolyzate, pyrophosphate Wetting agents such as sodium, defoaming agents, fluorine-based surfactants and nonionic surfactants that improve the permeability of ink may be used.
In addition, ascorbic acids, erythorbic acids, α-tocopherols, catechins, synthetic polyphenols, kodiic acid, alkylhydroxylamines, oxime derivatives, α-glucosylrutin, α-lipoic acid, phosphonates, phosphinates, sulfites, sulfoxyls Bubbles can also be chemically removed by adding acid salt, sulfite, thiosulfate, thiourea dioxide and the like.
In addition, N-vinyl-2-pyrrolidone oligomer, N-vinyl-2-piperidone oligomer, N-vinyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, ε-caprolactam, N-vinyl-ε-caprolactam By adding a thickening inhibitor such as an oligomer, the function in the infested form can be enhanced.
Further, lubricants can be used, for example, metal soaps, polyalkylene glycol fatty acid esters, ethylene oxide-added cationic activators, phosphate ester-based surfactants, β-alanine surfactants, N-acylamino acids, etc. N-acylmethyltaurine, 2,5-dimercapto-1,3,4-thiazazole and its salts and oligomers, 3-amino-5-mercapto-1,2,4-triazole, thiocarbamate, dimethyldithiocarbamate , Α-Lipoic acid, a condensate of N-acyl-L-glutamic acid and L-lysine, a salt thereof, or the like is used.

Further, an ink backflow preventive body (liquid plug) can be arranged at the rear end of the ink composition filled in the ink containing tube.
As the ink backflow preventive body, either a liquid or a solid can be used, and examples of the liquid ink backflow preventive body include non-volatile media such as polybutene, α-olefin oligomer, silicone oil, and refined mineral oil. If desired, silica, aluminum silicate, swellable mica, fatty acid amide and the like can be added to the medium. Further, as a solid ink backflow preventive body, a resin molded product can be mentioned. The liquid and solid ink backflow preventers can also be used in combination.

A conventional general-purpose mechanism is effective for the structure of the writing tip of the ballpoint pen filled with the glittering ink composition for the ballpoint pen, and the ball is deformed by pressing the vicinity of the tip of the metal pipe inward from the outer surface. A tip that holds a ball in the holding part, or a tip that holds a ball in a ball holding part formed by cutting a metal material with a drill or the like, or a metal pipe or metal material. A ball held by a chip formed by cutting and urged forward by a spring body or the like can be applied.
Further, as the ball, a general-purpose ball made of cemented carbide, stainless steel, ruby, ceramic or the like can be applied, and a ball having a diameter in the range of 0.1 mm to 2.0 mm, preferably 0.2 mm to 1.0 mm is preferable. Used for. In particular, when the ball diameter is as small as 0.5 mm or less, the number of rotations of the ball with respect to the writing distance increases, so that the conventional ink using the plate-shaped bright pigment tends to cause spot wear. However, in the ink of the present invention, it is considered that the microcapsule particles act as rollers, but since writing can be performed without causing spot wear even when the small diameter ball is used, the ink of the present invention is more suitable for the small diameter ballpoint pen. Works well. Therefore, even small-diameter ballpoint pens such as 0.5 mm, 0.4 mm, 0.38 mm, 0.35 mm, 0.3 mm, 0.28 mm, and 0.25 mm can exhibit excellent writing performance.
Further, among the materials of the balls, the cemented carbide balls having high hardness are liable to cause spot wear, so that the brilliant ink composition of the present invention is particularly useful.

As the shaft cylinder containing the brilliant ink composition, for example, a molded product made of a thermoplastic resin such as polyethylene, polypropylene, or polyethylene terephthalate is preferably used in terms of low evaporation property and productivity of the ink.
In addition to directly connecting the chip to the shaft cylinder, the shaft cylinder and the chip may be connected via a connecting member.
When the ink composition has a low viscosity, the ink composition accommodated in the barrel includes a method of mounting an ink holding member on the front portion of the barrel and accommodating the ink composition directly in the barrel, and porosity. Examples thereof include a method of impregnating a material or a processed fiber with the ink composition and accommodating the ink composition.

Further, by using a transparent, colored transparent, or translucent molded body as the shaft cylinder, the ink color, the remaining amount of ink, and the like can be confirmed.
The shaft cylinder may be a ballpoint pen refill in which the refill is housed in the outer shaft, or the shaft cylinder itself with the tip mounted on the tip portion is used as an ink container and is directly inside the shaft cylinder. Ink may be filled.

The ballpoint pen using the barrel can be applied in either a cap type or a haunting type. As a withdrawal type ballpoint pen, the writing tip provided in the ballpoint pen refill is housed in the outer shaft in a state of being exposed to the outside air, and the writing tip protrudes from the opening of the outer shaft by the operation of the withdrawal mechanism. If there is, all can be used.
Examples of the operation method of the haunting 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 outer shaft and the side surface of the outer shaft, and by pressing the knock portion, the writing tip portion of the ballpoint pen refill is made to appear and disappear from the opening at the front end end of the outer shaft, or on the outer shaft. By pressing the provided clip portion, a configuration in which the writing tip portion of the ballpoint pen refill is made to appear and disappear from the opening at the front end end of the outer shaft can be exemplified.
In the rotary type, a configuration in which a rotating portion (rear shaft or the like) is provided on the outer shaft and the writing tip portion of the ballpoint pen refill is retracted from the front end opening of the outer shaft by rotating the rotating portion can be exemplified.
The slide type has a slide portion on the side surface of the barrel, and by operating the slide, the writing tip portion of the ballpoint pen refill is made to appear and disappear from the front end opening of the outer shaft, or the clip portion provided on the outer shaft is slid. By doing so, it is possible to exemplify a configuration in which the writing tip portion of the ballpoint pen refill is made to appear and disappear from the opening at the front end end of the outer shaft.
The infestation type ballpoint pen may be a composite type infestation type ballpoint pen in which a plurality of ballpoint pen refills are housed in addition to the one in which one ballpoint pen refill is housed in the outer shaft.

Examples will be described below, but the present invention is not limited to these examples.
The table below shows the compositions of the glitter inks for ballpoint pens of Examples and Comparative Examples. The numerical values of the compositions in the table indicate parts by weight.
The average particle size is a value measured using a laser particle size distribution measuring machine LA-300 (volume standard) manufactured by HORIBA, Ltd., and the median diameter thereof is used as the average particle size. At that time, as the particle size of the plate-shaped bright pigment, the value calculated by assuming that the minimum value of the particle size axis in the particle size distribution map is 0.5 μm is used.

The contents of the raw materials in the table will be explained according to the note numbers.
(1) Aluminum powder paste, manufactured by Toyo Aluminum Co., Ltd., trade name: Alpaste WXM-0630 (average particle size: 7 μm)
(2) Aluminum powder paste, manufactured by Toyo Aluminum Co., Ltd., trade name: Alpaste EMERAL EMR-D5660 (average particle size: 10 μm)
(3) Pearl pigment, manufactured by Merck Japan, trade name: Iriodin 221 (average particle size: 15 μm)
(4) Blue pigment dispersion liquid with an average particle size of 0.2 μm (solid content: 20%)
(5) Magenta pigment dispersion liquid with an average particle size of 0.2 μm (solid content: 20%)
(6) Manufactured by Hodogaya Chemical Industry Co., Ltd., trade name: phloxine (7) Microcapsule particles containing cetyl ethylhexanoate (specific gravity: 0.85) (average particle size: 2 μm)
(8) Microcapsule particles containing cetyl ethylcaproate (specific gravity: 0.85) (average particle size: 4 μm)
(9) Microcapsule particles containing isosetyl myristate (specific gravity: 0.86) (average particle size: 0.5 μm)
(10) Sodium salt of acrylic acid / sulfonic acid monomer copolymer, manufactured by Toa Synthetic Co., Ltd., trade name: A-6012
(11) Sodium salt of acrylic acid / unsaturated carboxylic acid copolymer, manufactured by Toagosei Co., Ltd., trade name: A-6001
(12) Ammonium polyacrylate, manufactured by Toagosei Co., Ltd., trade name: A-30SL
(13) Daiichi Kogyo Seiyaku Co., Ltd., trade name: Prysurf M208F
(14) Sansho Co., Ltd., trade name: Leozan (15) Carboxyl group-containing polyolefin emulsion, Sumitomo Seika Chemical Co., Ltd., trade name: Zyxen L
(16) Carboxyl group-containing polyolefin emulsion, manufactured by Sumitomo Seika Chemical Co., Ltd., trade name: Zyxen A-GH
(17) Urethane resin emulsion, manufactured by Sanyo Chemical Industries, Ltd., trade name: U-coat UX-485
(18) Aqueous urethane resin emulsion, manufactured by Kusumoto Kasei Co., Ltd., trade name: NeoRezR-2170
(19) Acrylic resin emulsion, manufactured by BASF, trade name: John Krill PDX-7630A
(20) Acrylic resin emulsion, manufactured by BASF, trade name: John Krill 711

Preparation of Inks Each component was added to water and stirred at 20 ° C. at 2000 rpm for 1 hour, then a shear thinning agent was added and the mixture was further stirred for 1 hour to prepare each ink.

Preparation of Ink Backflow Prevention Body After adding 1.5 parts of fatty acid amide as a thickener to 98.5 parts of polybutene as a base oil, the mixture was kneaded with three rolls to obtain an ink backflow prevention body.

Preparation of Ballpoint Pen 1.0 g of the ink compositions of the above Examples and Comparative Examples was applied to a ballpoint pen refill in which a stainless steel cutting tip holding a cemented carbide ball having a diameter of 0.4 mm was fitted to one end of a polypropylene pipe. After filling and disposing the ink backflow prevention body at the rear end of the ink, the ballpoint pen refill was incorporated into the outer shaft, and a cap was attached to prepare a sample ballpoint pen.

The following tests were performed using the sample ballpoint pen and the ink composition.
Writing test A sample ballpoint pen confirmed to be writable is continuously written on JIS P3201 writing paper A with an automatic writing tester, and the writing conditions and the ink to be filled can be completely consumed. It was confirmed whether or not (5 each was tested). The testing machine was used under the conditions of a writing load of 100 g, a writing angle of 70 °, and a writing speed of 4 m / min.
Handwriting confirmation test The handwriting of 10 consecutive spiral circles written on black paper by hand was visually confirmed, and the hue was sensory-evaluated.
Ink stability test 10 g of each of the prepared inks was transferred to a sample bottle, covered with a lid, and then left to stand in an environment of 50 ° C. for 30 days. After leaving for each period, the state of the ink inside was visually confirmed at room temperature.
The results of each of the above tests are shown in the table below.

The evaluation of the test results is as follows.
Written test ○: Good handwriting was formed, and all the built-in ink could be written out.
Δ: Some samples could not be written on the way, and ink remained.
X: In all the samples, line skipping and blurring occurred in the handwriting, and it became impossible to write in the middle, and ink remained.
Handwriting confirmation test ○: It has a clear brilliance and a clear hue can be obtained.
Δ: There is a part where the hue is light.
X: The hue is light and the desired hue cannot be obtained.
Ink stability test ○: No abnormality.
Δ: Aggregation is observed in the ink.
X: Sedimentation of granules is observed.

Claims (6)

Plate-shaped bright pigment, coloring pigment, microcapsule particles containing an oily solvent, water, salt of acrylic acid-based polymer, or emulsion of olefin-based polymer, urethane-based polymer, acrylic acid-based polymer The salt of the acrylic acid-based polymer contains one or more salts or emulsions selected from the above, and the salt of the acrylic acid-based polymer is polyacrylic acid, polycarboxylic acid, acrylic acid / maleic acid copolymer, acrylic acid / sulfonic acid-based monomer. One or more selected from copolymers, acrylic acid / unsaturated carboxylic acid copolymers, or salts of styrene / acrylic acid copolymers.
The olefin-based polymer has a polyethylene, polypropylene, ethylene-vinyl acetate copolymer or ethylene-ethyl acrylate copolymer as a main skeleton and has an anionic functional group, and an ethylene- (meth) acrylic acid copolymer. One or more selected from things,
The urethane-based polymer is one or more selected from polymers having an anionic functional group having a reaction product of a polyisocyanate and a polyether polyol, a polyester polyol or a polycarbonate polyol as a main skeleton .
The emulsion of the acrylic acid-based polymer is an emulsion of an acrylic acid / maleic acid copolymer, an acrylic acid / sulfonic acid-based monomer copolymer, an acrylic acid / unsaturated carboxylic acid copolymer, or a styrene / acrylic acid copolymer. A brilliant water-based ink composition for ball pens, which is one or more selected from. The glittering ink composition for a ballpoint pen according to claim 1, wherein the oil-based solvent has a specific gravity of 1.0 or less. The glittering ink composition for a ballpoint pen according to claim 1 or 2, wherein the plate-shaped glittering pigment is one or more selected from pearl pigments, aluminum pigments, metals or metal oxide-coated glass flakes. The method according to any one of claims 1 to 3, wherein the solvent contained in the microcapsule particles is one or more selected from esters, aromatic hydrocarbons, higher alcohols, ketones, and ethers. Bright ink composition for ballpoint pens. The glittering ink composition for a ballpoint pen according to any one of claims 1 to 4, which contains a shear thinning agent. A ballpoint pen containing the glitter ink composition for a ballpoint pen according to any one of claims 1 to 5.