WO2021152779A1 - 水性ボールペン用インク組成物 - Google Patents
水性ボールペン用インク組成物 Download PDFInfo
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- WO2021152779A1 WO2021152779A1 PCT/JP2020/003464 JP2020003464W WO2021152779A1 WO 2021152779 A1 WO2021152779 A1 WO 2021152779A1 JP 2020003464 W JP2020003464 W JP 2020003464W WO 2021152779 A1 WO2021152779 A1 WO 2021152779A1
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- water
- ballpoint pen
- particles
- ink composition
- urethane
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/16—Writing inks
- C09D11/18—Writing inks specially adapted for ball-point writing instruments
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
- B43K—IMPLEMENTS FOR WRITING OR DRAWING
- B43K1/00—Nibs; Writing-points
- B43K1/08—Nibs; Writing-points with ball points; Balls or ball beds
- B43K1/086—Nibs; Writing-points with ball points; Balls or ball beds with resilient supporting means for the ball, e.g. springs
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
- B43K—IMPLEMENTS FOR WRITING OR DRAWING
- B43K7/00—Ball-point pens
- B43K7/02—Ink reservoirs; Ink cartridges
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/16—Writing inks
- C09D11/17—Writing inks characterised by colouring agents
Definitions
- the present invention relates to an ink composition for a water-based ballpoint pen containing an aluminum pigment.
- a water-based ballpoint pen using aluminum powder as a pigment can obtain brilliant lines, but its performance depends on the size of the aluminum powder.
- a large aluminum pigment gives a strong brilliant feeling, but tends to cause a problem that it is easily clogged in a gap in the chip.
- the gap becomes smaller, so that the above-mentioned problems are more likely to occur.
- the fine-character ballpoint pen has a problem that it is difficult to obtain a brilliant feeling because the amount of ink ejected is small.
- spherical resin particles such as acrylic resin, styrene / acrylic copolymer, and polyolefin are used to suppress aggregation of metal particles.
- Writing tools such as ballpoint pens that have been blended (see, for example, Patent Document 1), 2) A brilliant ink composition for ballpoint pens that contains microcapsule particles to prevent bearing wear, and a ballpoint pen that incorporates it (for example, a ballpoint pen that contains microcapsule particles).
- Patent Documents 4 there are known ballpoint pens (see, for example, Patent Documents 4), which are movable and rotatably held within a predetermined range of the ball-point pen clearance of the ballpoint pen tip (see, for example, Patent Documents 2 and 3). ing.
- Patent Documents 1 to 4 Even if the technical contents (inventions) of Patent Documents 1 to 4 are known, in the case of a so-called fine ballpoint pen having a ball diameter of ⁇ 0.5 mm or less, a sufficient effect has not yet been obtained.
- the ball holding force is smaller than that of a ballpoint pen having a ball diameter of more than ⁇ 0.5 mm, and the ball tends to fall off depending on the usage conditions.
- there may be adverse effects such as a decrease in writing quality and a decrease in ink ejection property.
- the holding of the ball is expressed by crimping the tip of the holder in which the ball is stored, but the crimped portion is worn by writing and a solid substance is fitted between the inner surface of the crimped portion and the ball.
- the holding force is lowered due to the local stress strain caused by the ball, and the ball may fall off due to an impact, making writing impossible.
- Japanese Unexamined Patent Publication No. 2010-125841 (Claims, Examples, etc.) Japanese Unexamined Patent Publication No. 2014-129440 (Claims, Examples, etc.) Japanese Unexamined Patent Publication No. 2017-119862 (Claims, Examples, etc.) Japanese Patent Application Laid-Open No. 11-28887 (Claims, Examples, FIG. 1, etc.)
- the present invention has been made in view of the above-mentioned problems of the prior art, and is intended to solve the problem. Even a so-called fine ballpoint pen has stable ink ejection property, excellent drawing line brilliance, and ball dropout. It is an object of the present invention to provide an ink composition for a water-based ballpoint pen and a water-based ballpoint pen.
- the present inventors have achieved the above object by containing at least a specific amount of an aluminum pigment and particles having specific physical properties having an average particle size within a predetermined range. They have found that an ink composition for a water-based ballpoint pen and the like can be obtained, and have completed the present invention.
- the ink composition for a water-based ballpoint pen of the present invention is characterized by containing at least an aluminum pigment and 8 to 25% by mass of solid urethane-based particles having an average particle diameter of 0.3 to 10 ⁇ m. Further, the water-based ballpoint pen of the present invention is characterized in that it is equipped with an ink composition for a water-based ballpoint pen having the above configuration.
- the lower limit value xx to the upper limit value zz which is a numerical range, includes xx and zz.
- an ink composition for a water-based ballpoint pen and a water-based ballpoint pen which have stable ink ejection properties even for a so-called fine-character ballpoint pen, have an excellent brilliance of drawn lines, and do not cause ball dropout.
- FIG. 2 It is an enlarged vertical sectional view which shows an example of the ballpoint pen tip of the water-based ballpoint pen which carries the ink composition for water-based ballpoint pen of this invention. It is a vertical cross-sectional view which shows the ballpoint pen tip of FIG. It is a vertical sectional view which shows another example of a ballpoint pen tip. It is a vertical cross-sectional view which shows the state which attached the ballpoint pen tip of FIG. 2 to an ink containing tube (refill).
- An example of the embodiment of the water-based ballpoint pen of the present invention is shown, and is a vertical cross-sectional view showing a state in which the ink storage tube (refill) of FIG. 4 is attached to a shaft body to form a water-based ballpoint pen.
- FIG. 4 Another example of the embodiment of the water-based ballpoint pen of the present invention is shown, and is a vertical cross-sectional view showing a knock-type water-based ballpoint pen by attaching the ink storage tube (refill) of FIG. 4 to a knock-type shaft body.
- the ink composition for a water-based ballpoint pen of the present invention is characterized by containing at least an aluminum pigment and 8 to 25% by mass of solid urethane-based particles having an average particle diameter of 0.3 to 10 ⁇ m.
- the aluminum pigment that can be used in the present invention is generally produced by pulverizing and grinding aluminum in a ball mill or an attritor mill in the presence of a pulverizing medium solution using a pulverizing aid, and is used as a pigment for water-based inks and the like. If it is used, its manufacturing method, properties (powder, paste, etc.), particle size (average particle size, thickness), etc. are not particularly limited, and for example, for water-based inks. Commercially available products can be used. Preferably, the average particle size is 20 ⁇ m or less, more preferably 5 to 16 ⁇ m, from the viewpoint of further exerting the effect of the present invention.
- Examples of commercially available aluminum pigments include the WXM series in which the aluminum surface is rust-proofed with a phosphorus compound, the WL series in which the aluminum surface is rust-proofed with a molybdenum compound, and the surface of aluminum flakes has a high density.
- Examples thereof include the EMR series coated with silica [above, manufactured by Toyo Aluminum Co., Ltd.], SW-120PM [above, manufactured by Asahi Kasei Chemicals Co., Ltd.], and these can be used alone or in combination of two or more.
- the content of these aluminum pigments is preferably 0.1 to 20% by mass (hereinafter, simply “mass%”) with respect to the total amount of the water-based ink composition for writing instruments (hereinafter, simply referred to as “total amount of ink composition”). Is referred to as “%"), more preferably 2 to 10%. If the content of the aluminum pigment is less than 0.1%, a brilliant feeling cannot be obtained, while if it exceeds 20%, the writing feeling is lowered and the stability of the ink may be impaired.
- the urethane-based particles used in the present invention are dense and have an average particle diameter of 0.3 to 10 ⁇ m.
- the term "fine” means that there are no voids (including single-empty, multi-empty, and porous) in particles such as hollow particles and microcapsule particles, and there are no voids in the particles. It means something that is jammed.
- the average particle size of the urethane-based particles used is 0.3 to 10 ⁇ m, and the lower limit is preferably 0.5 ⁇ m or more, more preferably 0.9 ⁇ m or more, and particularly preferably 1.0 ⁇ m or more.
- the upper limit is preferably 8 ⁇ m or less, more preferably 6 ⁇ m or less.
- the average particle size is a value of D50 calculated on a volume basis in the laser diffraction method.
- the average particle size can be measured by the laser diffraction method using, for example, the particle size distribution analyzer HRA9320-X100 manufactured by Nikkiso Co., Ltd.
- the urethane-based particles used are solid particles having a constant size (range of the average particle size).
- the urethane-based particles used preferably have a 10% strength of 30 MPa or less as measured by a microcompression test.
- the urethane-based particles can be made into soft particles even if they are dense, and because they are soft, they have the property of not causing the balls to fall off even if they are sandwiched between the caulking and the balls.
- the 10% strength is 5 MPa or more, the ink can flow out more stably.
- the "microcompression test” can be performed using, for example, MCT-510 manufactured by Shimadzu Corporation. In this case, it can be the average value of 5 particles.
- the urethane-based particles to be used may be solid and have the above-mentioned average particle size, and are particularly preferable as long as the 10% strength measured by the microcompression test has the above-mentioned characteristics. , It may be a commercially available product or a product manufactured by a production method described later, and the urethane-based particles may be colored as long as they have the above-mentioned characteristics.
- the urethane-based particles of the present invention are colored and used as a coloring material (coloring agent), the amount of addition can be reduced because the coloring property is higher than that of the microcapsule particles.
- the amount of coloring material that can be contained in the microcapsule particles is limited, and there are problems such as the shell inhibiting color development.
- the colored urethane particles function as a colorant to improve the degree of freedom in ink blending. Further, in the present invention, when the urethane-based particles are not colored and the ink composition does not contain other colorants, the hue of the ink composition is aluminum pigment + uncolored urethane-based particles. , Silver color (aluminum pigment + uncolored urethane particles).
- the urethane-based particles used are polymers and copolymers having a urethane bond, and are obtained by reacting an isocyanate component (including a diisocyanate component) with a polyol component (including a diol component).
- a polyol component including a diol component
- urethane At least one kind of particles (polyol type urethane particles, polycarbonate type urethane particles, polyether type urethane particles, etc.), urethane / urea particles, and the like can be mentioned.
- the urethane-based particles used are those obtained by the following production method.
- the method for producing urethane particles is as follows: 1) Preparation of an oil phase containing an organic solvent and an isocyanate monomer or isocyanate prepolymer, and a water-insoluble dye when coloring, and 2) Preparation of an aqueous phase by mixing water and a dispersant. Preparation 3) It can be carried out by a step of mixing the oil phase and the aqueous phase, emulsifying the components of the oil phase, and then polymerizing the components.
- the oil phase contains an organic solvent and an isocyanate monomer or isocyanate prepolymer, and if colored, a water-insoluble dye.
- a plurality of types of this organic solvent may be contained.
- a water-insoluble dye is added and stirred when coloring, then the above-mentioned monomer or prepolymer is added, and another organic solvent is added as necessary. By adding, it can be produced.
- the organic solvent for example, phenyl glycol, benzyl alcohol, ethylene glycol monobenzyl ether, ethyl acetate and the like can be used.
- phenyl ester alkylsulfonate ethylhexyl phthalate, tridecyl phthalate, ethylhexyl trimellitic acid, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, liquid xylene resin and the like can also be used.
- isocyanate monomer or prepolymer for example, hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, isophorone diisocyanate, isocyanate prepolymer and the like can be used.
- isocyanate prepolymer it is preferable to use a trimer such as the above-mentioned triol adduct of isocyanate and isocyanurate-modified product from the viewpoint of good curing by polymerization.
- a dimer such as the above-mentioned allophanate modified isocyanate can be used as an auxiliary prepolymer.
- the above-mentioned adjustment of 10% strength can be performed by selecting the isocyanate component (monomer or prepolymer, auxiliary monomer, auxiliary prepolymer) to be used, adjusting the content, and the like. Further, the average particle size can be adjusted by controlling the stirring conditions during the polymerization.
- the water-insoluble dye used for coloring is a dye that is insoluble in water at room temperature.
- a salt-forming dye, a dispersion dye, an oil-soluble dye, or the like can be used. Is preferably used.
- salt-forming dyes include dyes having an azo-based, metal complex salt-azo-based, anthracinone-based, and metal phthalocyanine-based chemical structures. Registered Trademarks) Blue 2620, Varifast® Brown 2402, Varifast® Green 1501, Varifast® Orange 2210, Varifast® Pink 2310, Valifast® Registered Trademarks Red ) VIOLET 1701, Varifast® Yellow 1101 and the like can be used.
- disperse dye examples include C.I. I. Disperse Yellow 198, C.I. I. Disperse Yellow 42, C.I. I. Disperse Red 92, C.I. I. Disperse Violet 26, C.I. I. Disperse Violet 35, C.I. I. Disperse Blue 60, and C.I. I. At least one dye selected from Disperse Blue 87 can be used.
- oil-soluble dyes include Oil Black 860, Oil Blue 613, Oil Brown BB, Oil Green 530, Oil Orange 201, Oil Pink 312, Oil Red 5B, Oil Small 105, etc. of Orient Chemical Industry Co., Ltd. Can be used.
- the aqueous phase can be prepared by mixing water and a dispersant.
- a dispersant for example, polyvinyl alcohol can be used, but the dispersant is not limited to this.
- the components of the oil phase are emulsified, and in the step of further polymerization, the oil phase is added to the aqueous phase, and the colored urethane is emulsified and mixed while being heated to a predetermined temperature using a homogenizer or the like. System particles and uncolored urethane particles can be obtained.
- urethane-based particles may be produced by a phase separation method.
- this production method comprises preparing a dye-containing solution, preparing a protective colloidal agent-containing solution, and polymerizing an isocyanate monomer or isocyanate.
- the dye-containing solution can be prepared by heating and dissolving a water-insoluble dye in an organic solvent.
- the organic solvent used in the above emulsion polymerization can be used.
- the protective colloidal agent-containing solution can be prepared by dissolving the protective colloidal agent in water.
- the protective colloidal agent for example, a methyl vinyl ether-maleic anhydride copolymer or the like can be used.
- a dye-containing solution is added to a protective colloid agent-containing solution heated to a predetermined temperature and dispersed in the form of oil droplets, and the above-mentioned isocyanate monomer or isocyanate is here. It can be produced by adding a prepolymer and stirring while maintaining the temperature.
- These solid urethane particles can be used alone or in combination of two or more, and the content thereof is 8 to 25%, preferably 10 to 18% of the total amount of the ink composition. % Is desirable. If the content of the solid urethane particles is less than 8%, the effect of the present invention cannot be exhibited, while if it exceeds 25%, the stability of the ink may be impaired, which is not preferable. ..
- the ink composition for a water-based ballpoint pen of the present invention contains at least the above-mentioned aluminum pigment and 8 to 25% by mass of solid urethane-based particles having an average particle diameter of 0.3 to 10 ⁇ m, and other than these components.
- coloring materials such as other pigments and dyes, water-soluble organic solvents, water as a solvent (tap water, purified water, distilled water, ion-exchanged water, pure water, etc.), and if necessary.
- Writing tools Each component usually used in water-based ink compositions, such as thickeners, lubricants, rust inhibitors, preservatives or antibacterial agents, pH adjusters, etc., is appropriately contained as long as the effects of the present invention are not impaired. be able to.
- coloring materials such as pigments and dyes can be used in combination as complementary color components, if necessary.
- Coloring materials include dyes that dissolve or disperse in water, conventionally known inorganic and organic pigments such as titanium oxide, and silica or mica as a base material, and the surface layer is coated with iron oxide, titanium oxide, or the like in multiple layers. Appropriate amounts of pigments and the like can be used as long as the effects of the present invention are not impaired.
- dyes examples include acid dyes such as eosin, phoxin, water yellow # 6-C, acid red, water blue # 105, brilliant blue FCF, and nigrosin NB; direct black 154, direct sky blue 5B, violet B00B, and the like.
- Acid dyes such as eosin, phoxin, water yellow # 6-C, acid red, water blue # 105, brilliant blue FCF, and nigrosin NB
- direct black 154 direct sky blue 5B, violet B00B, and the like.
- Basic dyes such as rhodamine and methyl violet can be mentioned.
- organic pigments include azo lakes, insoluble azo pigments, chelate azo pigments, phthalocyanine pigments, perylene and perinone pigments, and nitroso pigments. More specifically, carbon black, titanium black, zinc chromate, bengara, chromium oxide, iron black, cobalt blue, iron oxide yellow, viridian, zinc sulfide, lithopone, cadmium yellow, vermilion, cadmium red, chrome yellow, molybdade.
- Inorganic pigments such as orange, zinc chromate, strontium chromate, white carbon, clay, talc, ultramarine, precipitated barium sulfate, barite powder, calcium carbonate, lead white, dark blue, dark blue, manganese violet, brass powder, C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 17, C.I. I. Pigment Blue 27, C.I. I. Pigment Red 5, C.I. I. Pigment Red 22, C.I. I. Pigment Red 38, C.I. I. Pigment Red 48, C.I. I. Pigment Red 49, C.I. I. Pigment Red 53, C.I. I. Pigment Red 57, C.I. I. Pigment Red 81, C.I.
- Pigment Orange 16 C.I. I. Pigment Violet 1, C.I. I. Pigment Violet 3, C.I. I. Pigment Violet 19, C.I. I. Pigment Violet 23, C.I. I. Pigment Violet 50, C.I. I.
- Examples thereof include organic pigments such as Pigment Green 7. These coloring materials can be used alone or in combination of two or more.
- water-soluble organic solvent examples include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, 3-butylene glycol, thiodiethylene glycol, and glycerin, and ethylene glycol monomethyl ether and diethylene glycol monomethyl.
- glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, 3-butylene glycol, thiodiethylene glycol, and glycerin
- ethylene glycol monomethyl ether and diethylene glycol monomethyl examples thereof include ether, and these can be used alone or in admixture of two or more.
- the content of these water-soluble organic solvents is appropriately adjusted for each application of the water-based ink composition for writing tools, and is in the range of 1% to 30% with respect to the total amount of the ink composition.
- the thickener that can be used, for example, at least one selected from the group consisting of synthetic polymers, cellulose and polysaccharides is desirable.
- nonionic fatty acid esters such as polyhydric alcohol fatty acid esters, sugar higher fatty acid esters, and polyoxyalkylene higher fatty acid esters, which are also used as surface treatment agents for pigments, phosphoric acid esters, and alkyl sulfonic acids of higher fatty acid amides.
- examples thereof include salts, anionic compounds such as alkylallyl sulfonates, derivatives of polyalkylene glycols, fluorine-based surfactants, and polyether-modified silicones.
- rust preventives include benzotriazole, triltriazole, dicyclohexylammonium nitrate, saponins, etc.
- preservatives or antibacterial agents include phenol, sodium omadin, sodium benzoate, benzoisothiazolin, benzimidazole.
- examples include compounds.
- Examples of the pH adjuster include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, amine compounds such as triethanolamine, diethanolamine, monoethanolamine, dimethylethanolamine, morpholine and triethylamine, and ammonia and the like. Can be mentioned.
- the ink composition for a water-based ballpoint pen of the present invention contains at least the above aluminum pigment and 8 to 25% by mass of solid urethane particles having an average particle diameter of 0.3 to 10 ⁇ m, and other components are added to a ballpoint pen structure or the like.
- a stirrer such as a homomixer, homogenizer, or disper, and if necessary, removing coarse particles in the ink composition by filtration or centrifugation.
- Ink compositions can be prepared.
- the obtained ink composition for a water-based ballpoint pen of the present invention is mounted on a ballpoint pen provided with a ballpoint pen tip and used.
- the ink composition for a water-based ballpoint pen of the present invention configured as described above has stable ink ejection property even in a so-called fine ballpoint pen having a ball diameter of ⁇ 0.5 mm or less, is excellent in the brilliance of drawn lines, and is a ball. It is presumed that the ink composition for a water-based ballpoint pen that does not fall off is as follows.
- the ink composition for a water-based ballpoint pen of the present invention contains at least an aluminum pigment and 8 to 25% of urethane-based particles having an average particle size of 0.3 to 10 ⁇ m.
- the water-based ballpoint pen ink composition having the above composition is contained in a ballpoint pen ink container (refill), and the water-based ink composition contained in the ink container is compatible with the water-based ink composition.
- examples thereof include substances that are not present and have a small specific gravity with respect to the water-based ink composition, for example, those in which at least one of polybutene, silicone oil, mineral oil, and the like is contained as an ink follower.
- the structure of the ballpoint pen is not particularly limited, and for example, a direct liquid type having a collector structure (ink holding mechanism) in which the shaft cylinder itself is used as an ink container and the shaft cylinder is filled with the ink composition for a water-based ballpoint pen having the above configuration. It may be a ballpoint pen.
- the value of X represented by the following formula (I) is 27 to 27 to It is preferably 37, and more preferably 28 to 36.
- X (L / D) ⁇ 100 .
- D Ball diameter
- L Maximum ball ejection dimension
- L (Ball ejection dimension l + clearance m)
- FIG. 2 shows an example of a ballpoint pen tip having a ball with a ball diameter ( ⁇ ) of 0.5 mm or less, more preferably 0.3 mm or less, particularly preferably 0.29 mm or less
- FIG. 3 shows the ballpoint pen tip of FIG. Another example is shown.
- FIG. 4 is a drawing showing a state in which the ballpoint pen tip of FIG. 2 is attached to an ink containing tube (refill)
- FIG. 5 is a drawing showing an ink containing tube (refill) having the ballpoint pen tip of FIG. ) Is attached to the shaft body to form a water-based ballpoint pen
- FIG. 6 is a drawing showing another example (knock-type water-based ballpoint pen body) of the water-based ballpoint pen of FIG.
- FIG. 2 shows a cannonball-shaped ballpoint pen tip A having a tapered tip side and a hollow holder 11 rotatably holding a ball 10 having a ball diameter of, for example, 0.29 mm or less at the tip.
- the water-based ballpoint pen C having the ballpoint pen tip A attaches the rear end side of the ballpoint pen tip A to the ink storage tube 25 via (or directly) the joint member 20 having a backflow prevention mechanism, for example, as shown in FIG. It is obtained by connecting to form a refill 30 and storing the refill 30 in a shaft body 33 having a non-slip member 32, for example, as shown in FIG. A mouthpiece 31 is fixed to the tip of the shaft body 33.
- the ink composition 26 for a water-based ballpoint pen of the present invention filled in the ink storage tube 25 is supplied to the ball 10 through an ink flow path 12 that is sequentially tapered.
- FIG. 3 is a needle-type ball tip B in which the tip of a thin tube 15 made of metal or the like is caulked inward to rotatably hold a ball 16 having a diameter (ball diameter) of 0.29 mm or less. ..
- the ballpoint pen tip B also has a water-based ballpoint pen whose rear end side is connected to an ink accommodating tube and a shaft body (not shown).
- FIG. 6 is a vertical cross-sectional view showing an example of a knock-type water-based ballpoint pen body in which the ink storage tube (refill) having the ballpoint pen tip of FIG. 2 is attached to the knock-type shaft body.
- This knock-type water-based ballpoint pen body E has the ballpoint pen tip 40 of FIG.
- Reference numeral 41 in the drawing is a coil spring member housed in a chip and having a fine wire-shaped tip, and the tip portion urges the ball outward by the elastic force of the coil spring.
- reference numeral 42 is an ink composition for a water-based ballpoint pen of the present invention
- 43 is an ink follower having the above characteristics
- 51 is a knock portion
- 52 is a coating member that protects a tip tip portion.
- the ball material is not particularly limited as long as the ball diameter ( ⁇ ) is 0.5 mm or less, more preferably 0.3 mm or less, and particularly preferably 0.29 mm or less, and is not particularly limited, such as cemented carbide. Examples thereof include those made of metal members and ceramic members, and those having a thin film covering member on the surface thereof in order to improve durability, corrosion resistance and the like.
- the lower limit of the ball diameter is about 0.1 mm from the viewpoint of manufacturing technology and the like.
- the holder material include nickel silver, brass, stainless metal, synthetic resin, and the like.
- the ink storage tube may be made of a transparent or semi-transparent synthetic resin that allows the remaining amount of ink to be confirmed, but may be made of metal.
- the water-based ballpoint pen of the present invention is not limited to the structure of the ballpoint pen tips shown in FIGS. 2 and 3, and has a ball diameter ( ⁇ ) of 0.5 mm or less, more preferably 0.3 mm or less, particularly preferably.
- the structure of the water-based ballpoint pen body including the ballpoint pen tip is not particularly limited as long as it uses a ballpoint pen tip having a ball of 0.29 mm or less, and for example, a water-based ballpoint pen having various structures including a knock type. It can be applied to. Further, the material, size (inner diameter, length) and the like of the ball holder, the ink accommodating pipe, and the joint member (front shaft) are appropriately set according to the chip structure, the ball diameter, the ink follower, and the like.
- a ballpoint pen tip having a ball having a ball diameter ( ⁇ ) of 0.5 mm or less, more preferably 0.3 mm or less, particularly preferably 0.29 mm or less is mounted.
- the ink composition for a water-based ballpoint pen of the present invention by using the ink composition for a water-based ballpoint pen of the present invention, the ink ejection property is stable, the drawing line is excellent in brilliance, and the ball-point pen does not fall off.
- the value of X represented by the above formula (I) is 27 to 37.
- the ink ejection property is stable, the drawing line is excellent in brilliance, the ball does not fall off, and the resistance is further. It is possible to obtain a water-based ballpoint pen that exhibits ball-flying performance and a further writing feeling.
- the oil phase solution was added to the aqueous phase solution at 60 ° C., and the mixture was emulsified and mixed by stirring with a homogenizer for 6 hours to complete the polymerization.
- Urethane-based particles (without coloring) A were obtained by centrifuging the obtained dispersion.
- the oil phase solution was added to the aqueous phase solution at 60 ° C., and the mixture was emulsified and mixed by stirring with a homogenizer for 6 hours to complete the polymerization.
- Urethane-based particles (red particles) B were obtained by centrifuging the obtained dispersion.
- Urethane-based particles (without coloring) D were obtained in the same manner as urethane-based particles A, except that 8 parts by mass of isocyanurate-modified product of hexamethylene diisocyanate (TLA-100, Asahi Kasei Chemicals Co., Ltd.) was changed to 15 parts by mass. rice field.
- TLA-100 isocyanurate-modified product of hexamethylene diisocyanate
- the 10% strength (MPa) and average particle diameter ( ⁇ m) of the obtained urethane particles A to F and the melamine particles G were measured by the following methods. These results are shown in Table 1 below. (Measuring method of 10% strength) It was calculated by the above formula using MCT-510 manufactured by Shimadzu Corporation. (Measuring method of average particle size) The measurement was performed using a particle size distribution analyzer HRA9320-X100 manufactured by Nikkiso Co., Ltd.
- Examples 1 to 8 and Comparative Examples 1 to 3 An ink composition for a water-based ballpoint pen was prepared by a conventional method according to the compounding composition (total amount 100% by mass) shown in Table 2 below. Each of the obtained water-based ink compositions for writing tools (total amount 100% by mass) was evaluated for ink ejection property (drawing line evaluation, ink flow rate) and ball retention by the following evaluation methods using a water-based ballpoint pen having the following configuration. These results are shown in Table 2 below.
- ⁇ Making a water-based ballpoint pen> From a polypropylene ink storage tube (inner diameter 4 mm, length 113 mm), a stainless steel chip (cemented carbide ball, ball diameter 0.38 mm) conforming to FIGS. 1 and 2, and a joint connecting the storage tube and the chip.
- the refill was filled with the ink compositions for water-based ballpoint pens of Examples 1 to 8 and Comparative Examples 1 to 3.
- an ink follower composed of mineral oil, polybutene, and an olefin-based elastomer was loaded on the rear end of the ink. This refill was loaded onto the shaft of a ballpoint pen (UM-151, manufactured by Mitsubishi Pencil Co., Ltd.) to prepare each water-based ballpoint pen.
- 1 to 5 in Table 2 above are as follows. 1: J-4PM, average particle size 2.4 ⁇ m, 10% strength 33 MPa, PMMA, manufactured by Negami Kogyo Co., Ltd. 2: EMERAL EMR-D7675, average particle size 16 ⁇ m, silica coating, manufactured by Toyo Aluminum K.K. 3: EMERAL EMR-D5680, Average particle size 8 ⁇ m, silica coating, manufactured by Toyo Aluminum K.K. 4: RD-510Y, manufactured by Toho Chemical Industry Co., Ltd. 5: KELSAN AR, manufactured by Sansho Co., Ltd.
- Examples 1 to 8 which are within the scope of the present invention have better ink ejection properties (drawing line evaluation, ink flow rate) and ball retention than Comparative Examples 1 to 3 which are outside the scope of the present invention. It turned out to be excellent. Specifically, Examples 1, 4 to 6 use non-colored urethane particles together with the aluminum pigment, and only the aluminum pigments of Comparative Examples 1 to 3 are compared with the aluminum pigment + melamine particles and acrylic particles. It was confirmed that the ink ejection property (line drawing evaluation, ink flow rate) and ball retention were excellent.
- those using colored urethane particles (blue, red) together with the aluminum pigments of Examples 2, 3, 7 and 8 also have excellent color development, ink ejection property (drawing line evaluation, ink flow rate), and balls. It was confirmed that it was excellent in retention.
- An ink composition for a water-based ballpoint pen suitable for a ballpoint pen can be obtained.
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Abstract
Description
大きいアルミニウム顔料は、光輝感が強く出るが、チップ内の間隙で詰まりやすくなるという不具合が生じやすくなる。
特に、ボール径がφ0.5mm以下のいわゆる細字ボールペンの場合、間隙がより小さくなるため、前記のような不具合がより生じやすくなる。また、細字ボールペンは、インク吐出量が少ないので光輝感が得られにくいという課題も生ずる。
更に、ボールの保持は、ボールが収納されるホルダーの先端をカシメることによって発現するものであるが、筆記によるカシメ部分の摩耗や、カシメ部内面とボールとの間に固形物が嵌りこむことによる局部的な応力歪によって保持力が低下し、衝撃を受けるなどしてボールが脱落して筆記不能となることがあるなどの課題がある。
また、本発明の水性ボールペンは、上記構成の水性ボールペン用インク組成物を搭載したことを特徴とする。
本発明において、数値範囲である、下限値xx~上限値zzは、xxとzzを含むものである。
本発明の水性ボールペン用インク組成物は、少なくとも、アルミニウム顔料と、平均粒子径0.3~10μmの密実ウレタン系粒子8~25質量%を含有することを特徴とするものである。
好ましくは、本発明の効果を更に発揮せしめる点から、平均粒子径が20μm以下のものが望ましく、更に好ましくは、5~16μmが望ましい。
このアルミニウム顔料の含有量が0.1%未満であると、光輝感が得られず、一方、20%を越えると、筆記感が低下し、また、インクの安定性が損なわれる場合がある。
本発明において、「密実」とは、中空粒子やマイクロカプセル粒子などの粒子中に空隙(単空、多空、多孔質状を含む)がないものであり、粒子の中には空隙がなく詰まったものをいう。
用いるウレタン系粒子の平均粒子径は、0.3~10μmであり、下限は好ましくは、0.5μm以上、更に好ましくは、0.9μm以上、特に好ましくは、1.0μm以上のものが望ましい。一方、上限は、好ましくは8μm以下、更に好ましくは6μm以下であるものが望ましい。
この平均粒子径が0.3μm未満では、筆記描線においてアルミニウム顔料表面を粒子が覆ってしまうので光輝感が損なわれることがあり、一方、10μm超では、粒子の分散安定化が難しく、チップ内部で詰まりやすくなり、好ましくない。
本発明において、「平均粒子径」とは、レーザー回折法において体積基準により算出されたD50の値である。ここで、レーザー回折法による平均粒子径の測定は、例えば、日機装株式会社の粒子径分布解析装置HRA9320-X100を用いて行うことができる。
本発明において、密実粒子となるものを用いることにより、マイクロカプセル等の粒子と比較して粒子の強度がコントロールしやすいものとなる。
用いるウレタン系粒子は、好ましくは、微小圧縮試験により測定した10%強度が30MPa以下であることが望ましい。これにより、ウレタン系粒子は密実であっても柔らかい粒子とすることができ、柔らかいのでカシメとボールの間に挟まってもボール脱落を引き起こさない特性を有することとなる。また、10%強度を5MPa以上であると、インクが更に安定して流出できるものとなる。
すなわち、上記10%強度を5~30MPaであることにより、良好なインクの流出安定性及びボール脱落を引き起こさない特性を高度に両立させることができるものとなる。
本発明において、「微小圧縮試験」は、例えば、島津製作所社のMCT-510を用いて行うことができる。この場合、5個の粒子の平均値とすることができる。
この10%強度は、次式により算出することができる。
C(x)=(2.48×P)/(π×d2)
C(x):10%強度/MPa
P:粒子径の10%変位時の試験力/N
d:粒子径/mm
本発明のウレタン系粒子を着色して色材(着色剤)として用いる場合、マイクロカプセル粒子に比較して発色性が高いので添加量を少なくすることができる。マイクロカプセル粒子は内包できる色材の量が限定され、また、シェルが発色を阻害するなどの課題がある。
本発明において、着色されているウレタン系粒子は、着色剤として機能することでインク配合の自由度が向上することとなる。
また、本発明において、ウレタン系粒子は着色されておらず、かつインク組成物中に、他の着色剤を含まない場合は、インク組成物の色相はアルミニウム顔料+無着色ウレタン系粒子となるので、シルバー色(アルミニウム顔料+無着色ウレタン系粒子)となる。
好ましくは、用いるウレタン系粒子は、下記製法により得られたものを用いることが望ましい。
このウレタン系粒子の製法は、1)有機溶剤、及びイソシアネートモノマー又はイソシアネートプレポリマー、着色する場合は水不溶性染料を含有する油相の作製、2)水及び分散剤を混合させることによる水相の作製、3)上記油相と水相とを混合させて油相の成分を乳化した後に重合させる工程により行うことができる。
この油相は、有機溶剤を所定の温度に加温しながら、着色する場合は水不溶性染料を加えて撹拌し、次いで、上記モノマー又はプレポリマーを加え、更に必要に応じて他の有機溶剤を加えることにより、作製することができる。
有機溶剤としては、例えば、フェニルグリコール、ベンジルアルコール、エチレングリコールモノベンジルエーテル、酢酸エチル等を用いることができる。また、アルキルスルフォン酸フェニルエステル、フタル酸エチルヘキシル、フタル酸トリデシル、トリメリット酸エチルヘキシル、ジエチレングリコールジベンゾエート、ジプロピレングリコールジベンゾエート、液状のキシレン樹脂等も用いることができる。
イソシアネートプレポリマーとしては、上記のイソシアネートのトリオール付加物、イソシアヌレート変性体等の三量体を用いることが、重合により良好に硬化させる観点から好ましい。また、上記の三量体とともに、補助プレポリマーとして、上記のイソシアネートのアロファネート変性体等の二量体を用いることができる。
この製法において、上述の10%強度の調整は、用いるイソシアネート成分(モノマー又はプレポリマー、補助モノマー、補助プレポリマー)などの選択並びに含有量などを調整等することなどにより行うことができる。また、平均粒子径の調整は、重合の際、撹拌条件をコントロールすることにより調整することができる。
造塩染料としては、例えばアゾ系、金属錯塩アゾ系、アンスラキノン系及び金属フタロシアニン系の化学構造を有する染料が挙げられ、例えば、オリエント化学工業株式会社のValifast(登録商標) Black 1807、Valifast(登録商標) Blue 2620、Valifast(登録商標) Brown 2402、Valifast(登録商標) Green 1501、Valifast(登録商標) Orange 2210、Valifast(登録商標) Pink 2310、Valifast(登録商標) Red 1355、Valifast(登録商標) VIOLET 1701、Valifast(登録商標) Yellow 1101等を用いることができる。
油溶性染料としては、例えば、オリエント化学工業株式会社のOil Black 860、Oil Blue 613、Oil Brown BB、Oil Green 530、Oil Orange 201、Oil Pink 312、Oil Red 5B、Oil Scarlet 318、Oil Yellow 105等を用いることができる。
染料含有溶液は、水不溶性染料を有機溶剤に加熱溶解することにより作製することができる。水不溶性染料及び有機溶剤としては、上記乳化重合により用いる有機溶剤を用いることができる。
イソシアネートモノマー又はイソシアネートプレポリマーの重合は、着色する場合は染料含有溶液を、所定の温度に加温した保護コロイド剤含有溶液に添加して油滴状に分散させ、ここに上述のイソシアネートモノマー又はイソシアネートプレポリマーを添加し、温度を維持して撹拌することにより、製造することができる。
この密実ウレタン系粒子の含有量が8%未満であると、本発明の効果を発揮することができず、一方、25%を越えると、インクの安定性が損なわれる場合があり、好ましくない。
用いることができる色材としては、水に溶解もしくは分散する染料、酸化チタン等の従来公知の無機系および有機顔料系、シリカや雲母を基材とし表層に酸化鉄や酸化チタンなどを多層コーティングした顔料等を本発明の効果を損なわない範囲で適宜量使用することができる。
染料としては、例えば、エオシン、フオキシン、ウォーターイエロー#6-C、アシッドレッド、ウォーターブルー#105、ブリリアントブルーFCF、ニグロシンNB等の酸性染料;ダイレクトブラック154、ダイレクトスカイブルー5B、バイオレットB00B等の直接染料;ローダミン、メチルバイオレット等の塩基性染料などが挙げられる。
これらの色材は、単独で、又は2種以上を混合して用いることができる。
これらの水溶性有機溶剤の含有量は、筆記具用水性インク組成物の用途毎に適宜調整され、インク組成物全量に対して、1%~30%の範囲である。
pH調整剤としては、水酸化ナトリウム、水酸化カリウム、水酸化リチウム等のアルカリ金属の水酸化物、トリエタノールアミン、ジエタノールアミン、モノエタノールアミン、ジメチルエタノールアミン、モルホリン、トリエチルアミン等のアミン化合物、アンモニア等が挙げられる。
得られた本発明の水性ボールペン用インク組成物は、ボールペンチップを備えたボールペンに搭載されて使用に供される。
本発明の水性ボールペン用インク組成物では、少なくとも、アルミニウム顔料と、平均粒子径が0.3~10μmとなるウレタン系粒子を8~25%含有するものである。このウレタン系粒子を8~25%を含有することにより、推測ではあるが、アルミニウム顔料同士の凝集を抑制するとともに、カシメ部内面とボールとの間にウレタン系粒子が嵌りこんでも局部的な応力歪が発生せず、ボール保持力が低下しないことなどにより、インク吐出性が安定であり、描線の光輝感に優れ、ボール脱落が生じることのない水性ボールペン用インク組成物が得られることとなる。
ボールペンの構造は、特に限定されず、例えば、軸筒自体をインク収容体として該軸筒内に上記構成の水性ボールペン用インク組成物を充填したコレクター構造(インク保持機構)を備えた直液式のボールペンであってもよいものである。
X=(L/D)×100 ………(I)
D:ボール径、L:最大ボール出寸法、L=(ボール出寸法l+クリアランスm)
更に好ましくは、上記式(I)で示されるXの値を有し、ボール径(φ)が0.5mm以下、より好ましくは、0.3mm以下、特に好ましくは、0.29mm以下のボールを有するが望ましい。
この構造の水性ボールペンとすることにより、上記特性の水性ボールペン用インク組成物と相俟って、更なる耐ボール飛び性能、更なる優れた筆記感を発揮せしめる水性ボールペンを得ることができる。
図2は、ボール径(φ)が0.5mm以下、より好ましくは、0.3mm以下、特に好ましくは、0.29mm以下のボールを有するボールペンチップの一例、図3は図2のボールペンチップの他例を示すものであり、図4は、図2のボールペンチップをインク収容管(リフィール)に取り付けた状態を示す図面であり、図5は、図4のボールペンチップを有するインク収容管(リフィール)を軸体に取り付けて水性ボールペンとした状態を示す図面であり、図6は、図5の水性ボールペンの他例(ノック式水性ボールペン体)を示す図面である。
この水性ボールペンCでは、インク収容管25に充填される本発明の水性ボールペン用インク組成物26が順次先細状となるインク流路12を通じてボール10に供給されるようになっている。
また、図6は、図2のボールペンチップを有するインク収容管(リフィール)をノック式軸体に取り付けてノック式水性ボールペン体の一例を示す縦断面図である。
このノック式水性ボールペン体Eは、図2のボールペンチップ40を有し、該チップ40を逆流防止機構を有する継手部材45を介してインク収容管46に連結されたリフィール47を滑り止め部材48を有するノック式軸体50に収納したものである。なお、図中の図示符号41は、チップ内に収容され、先端が細線状のコイルスプリング部材であり、該コイルスプリングの弾性力により先端部がボールを外方へ付勢している。図中の図示符号42は、本発明の水性ボールペン用インク組成物、43は、上記特性のインク追従体であり、51はノック部、52はチップ先端部を保護する被膜部材である。
ホルダー材質としては、洋白、真鍮、ステンレスの金属製、合成樹脂等が挙げられる。
また、インク収容管としては、インク残量を確認できる透明性又は半透明性の合成樹脂製等が挙げられるが、金属製であってもよい。
なお、本発明の水性ボールペンでは、上記図2及び図3のボールペンチップの構造に限定されるものではなく、ボール径(φ)が0.5mm以下、より好ましくは、0.3mm以下、特に好ましくは、0.29mm以下のボールを有するボールペンチップを使用したものであれば、ボールペンチップを含む水性ボールペン体の構造は特に限定されるものではなく、例えば、ノック式を含む種々の構造の水性ボールペンに適用できるものである。また、ボールホルダー、インク収容管、継手部材(先軸)の材質、大きさ(内径、長さ)等はチップ構造、ボール径、インク追従体などに応じて適宜設定される。
特に、本発明の水性ボールペンにおいて、図1に示すように、水性ボールペンにおけるボール径をD、最大ボール出寸法をLとした場合に、上記式(I)で示されるXの値を27~37とするボールペンチップを用いることにより、本発明の水性ボールペン用インク組成物と相俟って、インク吐出性が安定であり、描線の光輝感に優れ、ボール脱落が生じることのなく、更に、耐ボール飛び性能、更なる筆記感を発揮せしめる水性ボールペンを得ることができる。この水性ボールペンでは、ボール径(φ)が小さいほど、本発明の効果をより発揮できるものであり、ボール径を0.5mm以下、より好ましくは、0.3mm以下、特に好ましくは、0.29mm以下のボールを有する水性ボールペンに好適に用いることができる。
〈ウレタン系粒子A~F、メラミン粒子Gの作製〉
下記表1に示す配合組成、下記方法によりウレタン系粒子A~F、メラミン粒子Gを作製した。
有機溶剤としての酢酸エチル12.5質量部を60℃に加温しながら、ここにプレポリマーとしてのヘキサメチレンジイソシアネートのイソシアヌレート変性体(TLA-100、旭化成ケミカルズ社製)8質量部を加えて、油相溶液を作製した。一方、蒸留水200質量部を60℃に加温しながら、ここに分散剤としてのポリビニルアルコール(PVA-205、クラレ社製)15質量部を溶解して、水相溶液を作製した。次いで、60℃の水相溶液に油相溶液を投入し、ホモジナイザーで6時間撹拌することにより乳化混合して重合を完了した。得られた分散体を遠心処理することでウレタン系粒子(着色なし)Aを得た。
有機溶剤としてのエチレングリコールモノベンジルエーテル11.5質量部を60℃に加温しながら、ここにプレポリマーとしてのジフェニルメタンジイソシアネート(3モル)のトリメチロールプロパン(1モル)付加物(D-109、三井化学社製)7.2質量部を加えて、油相溶液を作製した。一方、蒸留水200質量部を60℃に加温しながら、ここに分散剤としてのポリビニルアルコール(PVA-205、クラレ社製)15質量部を溶解して、水相溶液を作製した。60℃の水相溶液に油相溶液を投入し、ホモジナイザーで6時間撹拌することにより乳化混合して重合を完了した。得られた分散体を遠心処理することでウレタン系粒子(赤色粒子)Bを得た。
水不溶性染料(Valifast Red 1355、オリヱント化学工業社製)2.8質量部を水不溶性染料(Valifast Blue 2620、オリヱント化学工業社)2.4質量部に、エチレングリコールモノベンジルエーテル11.5質量部をベンジルアルコール9.6質量部に、ジフェニルメタンジイソシアネート(3モル)のトリメチロールプロパン(1モル)付加物(D-109、三井化学社製)7.2質量部をヘキサメチレンジイソシアネートのアロファネート変性体(D-178NL、三井化学社製)7質量部に変更したことを除き、ウレタン系粒子Bと同様にして、ウレタン系粒子(青色粒子)を得た。
ヘキサメチレンジイソシアネートのイソシアヌレート変性体(TLA-100、旭化成ケミカルズ社)8質量部を15質量部に変更したことを除き、ウレタン系粒子Aと同様にして、ウレタン系粒子(着色なし)Dを得た。
製造例2において、重合の際の撹拌条件を変更して平均粒子径が相違するウレタン系粒子(赤色粒子)Eを得た。
製造例3において、重合の際の撹拌条件を変更して平均粒子径が相違するウレタン系粒子(青色粒子)Fを得た。
酢酸エチル12.5質量部をベンジルアルコール20質量部とし、ヘキサメチレンジイソシアネートのイソシアヌレート変性体(TLA-100、旭化成ケミカルズ社製)8質量部をメチロールメラミン7質量部に変更したことを除き、ウレタン系粒子Aの製法と同様にして、メラミン粒子(着色なし)Gを得た。
(10%強度の測定方法)
島津製作所社のMCT-510を用いて、上述の式により算出した。
(平均粒子径の測定方法)
日機装株式会社の粒子径分布解析装置HRA9320-X100を用いて測定した。
(実施例1~8及び比較例1~3)
下記表2に示す配合組成(全量100質量%)により常法により水性ボールペン用インク組成物を調製した。
得られた各筆記具用水性インク組成物(全量100質量%)について、下記構成の水性ボールペンを用いて下記評価方法により、インク吐出性(描線評価、インク流量)、ボール保持について評価した。
これらの結果を下記表2に示す。
ポリプロピレン製インク収容管(内径4mm、長さ113mm)、図1、図2等に準拠するステンレス製チップ(超硬合金ボール、ボール径0.38mm)及び該収容管と該チップを連結する継手からなるリフィールに実施例1~8及び比較例1~3の水性ボールペン用インク組成物を充填した。次いで、インク後端に鉱油、ポリブテン、オレフィン系エラストマーからなるインク追従体を装填した。このリフィールを、ボールペン(UM-151、三菱鉛筆社製)の軸に装填して、各水性ボールペンを作製した。
この実施例、比較例に用いた水性ボールペンのボール径D(0.38mm)、最大ボール出寸法Lとした場合の上述の式(I)で示されるXの値は、27~37の範囲であった。
φ0.38mmボールペンでインクが全て消費されるまで筆記(JIS S6061準拠)して、100m毎の描線評価とインク流量の状態を下記評価基準(A~C)で評価した。
<描線評価の評価基準>
A:十分な光輝感を有している
B:光輝感がやや弱い
C:光輝感が不足
<インク流量の評価基準>
A:最後まで一定の流量を保持した。
B:後半にやや流量が低下した。
C:途中で筆記不能、若しくは極端な流量の低下が発生した。
上記同様のボールペンで200mまで筆記後、ペン先を上向きにして1.8mの高さから落下させ、下記評価基準(A、C)で評価した。n=50本
<ボール保持の評価基準>
A:全てボールが保持された。
C:脱落したボールペンが発生した。
1: J-4PM、平均粒子径2.4μm、10%強度33MPa、PMMA、根上工業社製
2:EMERAL EMR-D7675 、平均粒子径16μm、シリカコーティング、東洋アルミニウム社製
3:EMERAL EMR-D5680 、平均粒子径8μm、シリカコーティング、東洋アルミニウム社製
4:RD-510Y、東邦化学工業社製
5:KELSAN AR、三晶社製
具体的に見ると、実施例1、4~6はアルミニウム顔料と共に、着色しないウレタン系粒子を用いたものであり、比較例1~3のアルミニウム顔料のみ、アルミニウム顔料+メラミン粒子やアクリル粒子に較べ、インク吐出性(描線評価、インク流量)、ボール保持に優れていることが確認された。
また、実施例2、3、7及び8のアルミニウム顔料と共に、着色したウレタン系粒子(青色、赤色)を用いたものも、優れた発色性と共に、インク吐出性(描線評価、インク流量)、ボール保持に優れていることが確認された。
C ボールペン
10 ボール
30 リフィール
Claims (2)
- 少なくとも、アルミニウム顔料と、平均粒子径0.3~10μmの密実ウレタン系粒子8~25質量%を含有することを特徴とする水性ボールペン用インク組成物。
- 請求項1に記載の水性ボールペン用インク組成物を搭載したことを特徴とする水性ボールペン。
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CN202080094775.3A CN115023473A (zh) | 2020-01-30 | 2020-01-30 | 水性圆珠笔用墨组合物 |
EP20917032.3A EP4098707A4 (en) | 2020-01-30 | 2020-01-30 | WATER-BASED BALLPOINT PEN INK COMPOSITION |
US17/759,825 US20230073595A1 (en) | 2020-01-30 | 2020-01-30 | Ink composition for water-based ballpoint pen |
KR1020227029876A KR20220130794A (ko) | 2020-01-30 | 2020-01-30 | 수성 볼펜용 잉크 조성물 |
PCT/JP2020/003464 WO2021152779A1 (ja) | 2020-01-30 | 2020-01-30 | 水性ボールペン用インク組成物 |
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EP4098707A1 (en) | 2022-12-07 |
KR20220130794A (ko) | 2022-09-27 |
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