WO2021095685A1 - Ink composition for water-based ballpoint pens - Google Patents

Ink composition for water-based ballpoint pens Download PDF

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Publication number
WO2021095685A1
WO2021095685A1 PCT/JP2020/041726 JP2020041726W WO2021095685A1 WO 2021095685 A1 WO2021095685 A1 WO 2021095685A1 JP 2020041726 W JP2020041726 W JP 2020041726W WO 2021095685 A1 WO2021095685 A1 WO 2021095685A1
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WIPO (PCT)
Prior art keywords
water
ink composition
ballpoint pen
group
based ballpoint
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PCT/JP2020/041726
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French (fr)
Japanese (ja)
Inventor
陽子 佐々木
孝介 小椋
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三菱鉛筆株式会社
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Publication of WO2021095685A1 publication Critical patent/WO2021095685A1/en

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
    • B43K—IMPLEMENTS FOR WRITING OR DRAWING
    • B43K7/00—Ball-point pens
    • B43K7/01—Ball-point pens for low viscosity liquid ink
    • 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

Definitions

  • the present specification relates to an ink composition for a water-based ballpoint pen, which has a small increase in ink viscosity even in a low temperature environment and is less likely to cause writing defects.
  • an ink composition for an aqueous ball pen using colored particles for example, 1) a pigment having a large specific gravity or a pigment having a slight difficulty in dispersibility, and a microcapsule containing a poorly water-soluble medium having specific physical properties.
  • Aqueous ball pen ink composition containing a pigment see, for example, Patent Document 1), 2) a plate-shaped bright pigment, a coloring pigment, microcapsule particles containing an oily solvent, water, and an acrylic acid-based polymer.
  • a brilliant ink composition for a ball pen containing one or more salts or emulsions selected from emulsions of olefin-based polymers, urethane-based polymers, and acrylic acid-based polymers see, for example, Patent Document 2).
  • An ink composition for an aqueous ball pen which comprises styrene-acrylonitrile resin particles, a colorant, an alkyl sulfate, a phosphoric acid ester-based surfactant, and water (for example).
  • Patent Document 3 and the like are known.
  • Patent Document 1 The purpose of Patent Document 1 is to provide an ink composition for a water-based ballpoint pen that facilitates dispersibility of a pigment having a large specific gravity or a pigment having a slight difficulty in dispersibility, and Patent Document 2 is vivid.
  • An object of the present invention is to provide a brilliant ink composition for a ballpoint pen that can maintain handwriting and stability over time.
  • the above-mentioned Patent Document 3 has excellent dispersion stability and an ink composition for a water-based ballpoint pen that can obtain a good handwriting.
  • the purpose is to provide a product, and each of these patent documents does not disclose or suggest writeability in a low temperature environment.
  • JP-A-2017-12168 (Claims, Examples, etc.) Japanese Unexamined Patent Publication No. 2017-119862 (Claims, Examples, etc.) JP-A-2019-116576 (Claims, Examples, etc.)
  • the present disclosure is intended to solve the problems, and the ink composition for a water-based ballpoint pen is less likely to cause writing defects because the ink viscosity does not increase even in a low temperature environment. It is an object of the present invention to provide a thing and a water-based ballpoint pen.
  • the present inventors contain at least specific colored resin particles having an average particle size in a predetermined range and a specific surfactant. As a result, they have found that an ink composition for a water-based ballpoint pen and the like can be obtained for the above purpose, and have completed the present disclosure.
  • the water-based ballpoint pen ink composition of the present disclosure is characterized by containing at least urethane-based colored resin particles having an average particle diameter of 0.5 to 6 ⁇ m and an acetylene-based surfactant.
  • the water-based ballpoint pen ink composition preferably has a contact angle between the polyethylene terephthalate film and the ink of 40 ° or less.
  • the water-based ballpoint pen of the present disclosure is characterized by being equipped with an ink composition for a water-based ballpoint pen having the above configuration.
  • the surface roughness of the ball of the water-based ballpoint pen is preferably less than 10 nm.
  • an ink composition for a water-based ballpoint pen in which an increase in ink viscosity is small even in a low temperature environment and writing defects are unlikely to occur, and a water-based ballpoint pen on which the ink composition is mounted.
  • the ink composition for an aqueous ballpoint pen of the present disclosure is characterized by containing at least urethane-based colored resin particles having an average particle diameter of 0.5 to 6 ⁇ m and an acetylene-based surfactant.
  • the urethane-based colored resin particles used in the present disclosure are not particularly limited as long as they are composed of colored urethane-based resin particles, and for example, 1) urethane-based colored resin particles colored with a dye or pigment, etc. 2) Urethane-based colored resin particles that are thermally discolored using leuco dyes, etc. 3) Photochromic dyes (compounds) that are photo-discolored dyes, urethane-based colored resin particles that are photo-discolored using fluorescent dyes, etc. Can be mentioned.
  • the urethane-based colored resin particles of 1) above are composed of a polymer and a copolymer having at least a urethane bond, and react an isocyanate component (including a diisocyanate component) with a polyol component (including a diol component).
  • an isocyanate component including a diisocyanate component
  • a polyol component including a diol component
  • urethane particles polyyester type urethane particles, polycarbonate type urethane particles, polyether type urethane particles, etc.
  • urethane / urea particles and the like.
  • the urethane-based colored resin particles for example, those obtained by the following production method can be used.
  • the method for producing urethane-based colored resin particles in 1) above is as follows: a) Preparation of an oil phase containing an organic solvent, an isocyanate monomer or an isocyanate prepolymer, and a water-insoluble dye, and b) An aqueous phase by mixing water and a dispersant. C) The above oil phase and aqueous phase are mixed, and the components of the oil phase are emulsified and then polymerized. When the water-insoluble dye is not used, it can be used as white urethane-based colored resin particles.
  • the oil phase contains an organic solvent and an isocyanate monomer or isocyanate prepolymer, and if colored, a water-insoluble dye.
  • This oil phase is prepared by adding a water-insoluble dye and stirring while heating the organic solvent to a predetermined temperature, then adding the above-mentioned monomer or prepolymer, and further adding another organic solvent if necessary.
  • the organic solvent for example, phenyl glycol, benzyl alcohol, ethylene glycol monobenzyl ether, ethyl acetate and the like can be used.
  • alkylsulfonic acid phenyl ester 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 average particle size can be adjusted by controlling the stirring conditions and the like during the polymerization.
  • the water-insoluble dye is a dye that is insoluble in water at room temperature, and for example, salt-forming dyes, disperse dyes, oil-soluble dyes, and the like can be used. It is preferable to use salt-forming dyes having anthraquinone-based and metallic phthalocyanine-based chemical structures.
  • the aqueous phase can be prepared by mixing water and a dispersant.
  • the 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 oil phase is emulsified and mixed while being heated to a predetermined temperature using a homogenizer or the like. Colored resin particles can be obtained.
  • urethane-based colored resin 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.
  • thermochromic urethane-based colored resin particles in 2) above include an electron-donating dye, a leuco dye that functions as a color-developing agent, and a color-developing agent that is a component having the ability to develop the color of the leuco dye.
  • a thermally discolorable composition containing at least a discoloration temperature adjusting agent capable of controlling the discoloration temperature in the color development of the leuco dye and the color developer so as to have a predetermined average particle size. Examples thereof include heat-discolorable urethane-based colored resin particles.
  • microencapsulation method examples include interfacial polymerization method, interfacial polycondensation method, insitu polymerization method, in-liquid curing coating method, phase separation method from aqueous solution, phase separation method from organic solvent, melting dispersion cooling method, and air.
  • examples thereof include a suspension coating method and a spray drying method, which can be appropriately selected depending on the intended use.
  • a leuco pigment, a color developer, and a discoloration temperature adjuster are heated and melted, then put into an emulsifier solution and heated.
  • the mixture is stirred and dispersed in the form of oil droplets, and then the urethane-based resin raw material whose wall film is exemplified in 1) above is gradually added as a capsule film agent, and the reaction is continued to prepare, and then this dispersion is filtered.
  • This makes it possible to produce heat-discolorable urethane-based colored resin particles composed of heat-discolorable microcapsule pigments.
  • the color development temperature and decolorization temperature of each color are set to suitable temperatures by appropriately combining the types and amounts of the leuco dye, the color developer, and the color change temperature adjusting agent. be able to.
  • thermochromic urethane-based colored resin particles preferably have reversible thermochromic properties.
  • Those with reversible thermal discoloration are a heat decolorization type that decolorizes by heating from the color development state, a color memory retention type that alternately stores the color development state or the decolorization state in a specific temperature range, or a decolorization state.
  • Various types such as a heating color-developing type that develops color by heating and returns to a decolorized state by cooling from the color-developed state can be configured alone or in combination.
  • the photochromic urethane-based colored resin particles of 3) above include, for example, at least one selected from at least a photochromic dye (compound), a fluorescent dye, and a resin such as terpenephenol resin. Includes sex urethane-based colored resin particles, at least one selected from at least photochromic dyes (compounds), fluorescent dyes, etc., organic solvents, and additives such as antioxidants, light stabilizers, and sensitizers. Examples thereof include photocolorable urethane-based colored resin particles produced by microencapsulating a photochromic composition so as to have a predetermined average particle size. As the microencapsulation method, it can be prepared in the same manner as in the production of the heat-discolorable resin particles described above.
  • the photochromic urethane-based colored resin particles are selected from, for example, indoor lighting environments (indoor incandescent lamps, fluorescent lamps, lamps, white LEDs, etc.) by preferably using photochromic dyes (compounds), fluorescent dyes, and the like. It is possible that the lighting fixture is colorless and has the property of developing color in an ultraviolet irradiation environment (irradiation with a wavelength of 200 to 400 nm, irradiation environment with sunlight including ultraviolet rays).
  • Each of the urethane-based colored resin particles 1) to 3) above can be used as a normal coloring material for a ball pen, such as a fluorescent pigment, a heat-changing pigment, or a microcapsule pigment of a photo-changing pigment (coloring material). it can.
  • each urethane-based colored resin particle produced by each known production method can be used, and if there is a commercially available product, they may be used. It's a good one.
  • these urethane-based colored resin particles those having an average particle diameter of 0.5 to 6 ⁇ m are used from the viewpoint of coloring power, dispersion stability, etc., and it is preferably used in an amount of 1 to 5 ⁇ m.
  • the "average particle size" is the value of the particle size (D50) when the volume accumulation of the particle size distribution is 50%, which is calculated by the volume standard measured by the laser diffraction method. is there.
  • 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 content of these urethane-based colored resin particles is preferably 3 to 30%, more preferably 10 to 30%, based on the total amount of the ink composition. If the content of the urethane-based colored resin particles is less than 3%, a preferable drawing density cannot be obtained, and if it exceeds 30%, the writing feeling becomes heavy and the drawing lines tend to be blurred, which is not preferable. ..
  • the acetylene-based surfactant used in the present disclosure is contained in order to exert the effects of the present disclosure, and is at least one selected from acetylene glycols, alkylene oxide adducts thereof, and acetylene alcohols (each alone or 2). Mixtures of seeds and above, and so on).
  • Specific examples of the acetylene glycols, alkylene oxide adducts thereof, and acetylene alcohols that can be used include at least one selected from the following formulas (I) to (VI).
  • R1 and R2 in the above formulas (I) to (III) are alkyl groups having linear or branched chains having 1 to 8 carbon atoms, respectively, and m, n, x, and y are numbers of 1 to 100. is there. ]
  • R3, R4, and R5 represent a carbon chain having a hydrogen atom, a straight chain, or a branched chain and having 0 to 10 carbon atoms, and the carbon chain contains an unsaturated bond.
  • R6 represents an alkylene group having 2 to 5 carbon atoms
  • R7 represents an alkylene group having 1 to 5 carbon atoms.
  • acetylene glycols examples include acetylene glycol represented by the above formula (I) and a derivative to which ethylene oxide (EO) of acetylene glycol represented by the above formula (II) is added.
  • Additives ethylene oxide (EO) of acetylene glycol represented by the above formula (III), derivatives (adducts) to which propylene oxide (PO) is added, and the like can be mentioned.
  • Examples of the alkyl group having a linear or branched chain having 1 to 8 carbon atoms represented by R1 and R2 in the above formulas (I) to (III) include a methyl group, an ethyl group, a propyl group, an isopropyl group, and n-. Examples thereof include a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and the like.
  • Examples of the acetylene glycol of the above formula (I) include 2,5,8,11-tetramethyl-6-dodecine-5,8-diol and 5,8-dimethyl-6-dodecine-5,8-diol. 2,4,7,9-Tetramethyl-5-dodecine-4,7-diol, 8-hexadecin-7,10-diol, 7-tetradecine-6,9-diol, 2,3,6,7-tetra Methyl-4-octin-3,6-diol, 3,6-diethyl-4-octin-3,6-diol, 2,5-dimethyl-3-hexin-2,5-diol and the like can be mentioned.
  • Examples of the alkylene oxide (EO, PO) adduct of the acetylene glycol of the formulas (II) and (III) include the alkylene oxide derivative of the acetylene glycol.
  • acetylene alcohols represented by the above formulas (IV) to (VI) have an acetylene group (-C ⁇ C-) and a hydroxyl group (-OH) in the molecular structure.
  • R3, R4, and R5 in the general formulas (IV) to (VI) include a hydrogen atom, an alkyl group having a linear or branched structure, an alkenyl group, an aryl group, an aralkyl group, and the like.
  • the alkyl group and the alkenyl group may be linear, branched or cyclic, and may be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group or an isobutyl group.
  • the aryl group may have a substituent such as a lower alkyl group on the aromatic ring, and examples thereof include a phenyl group, a tolyl group, a xsilyl group and a naphthyl group.
  • the aralkyl group may have a substituent such as a lower alkyl group on the aromatic ring, and examples thereof include a benzyl group, a phenethyl group and a naphthylmethyl group.
  • R6 in the above formula (V) represents an alkylene group having 2 to 5 carbon atoms, and the alkylene group may be linear, branched or cyclic, but is particularly linear. Those are suitable. Examples of the linear alkylene group include an ethylene group, a trimethylene group, a tetramethylene group, and a pentamethylene group.
  • R7 in the general formula (VI) represents an alkylene group having 1 to 5 carbon atoms, the alkylene group is a methylene group (1 carbon number), and the general formula (VI) has 2 or more carbon atoms. It is the same as R6 in V).
  • acetylene alcohols of the above formula (IV) or derivatives thereof include 2-butyne-1-ol, 3-butyne-2-ol, 2-decine-1-ol, and 3,6-dimethyl-.
  • acetylene alcohols of the above formula (V) or derivatives thereof include 3-butyne-1-ol, 3-decine-1-ol, 9-decin-1-ol, and 3-heptin-1-. All, 3-hexin-1-ol, 5-hexin-1-ol, 3-nonyne-1-ol, 3-octyne-1-ol, 3-pentyne-1-ol, 4-pentyne-1-ol, At least one such as 5-phenyl-4-pentyne-1-ol and 10-undecine-1-ol can be mentioned.
  • acetylene alcohols of the above formula (VI) or derivatives thereof include 4-heptin-2-ol, 5-heptin-3-ol, 5-hexyne-3-ol, and 4-pentyne-. At least one such as 2-ol is mentioned.
  • 3-methyl-1-butyne-3- is preferable from the viewpoint of usability, cost, safety, and further exerting the effects of the present disclosure. It is desirable to use all, 3-methyl-1-pentyne-3-ol, 3,5-dimethyl-1-hexin-3-ol.
  • the content (active ingredient amount) of these acetylene-based surfactants is preferably 0.1 to 3.0%, more preferably 0.3 to 2.0%, based on the total amount of the ink composition. It is desirable to set it to%. If the content of this acetylene-based surfactant is less than 0.1%, the effects of the present disclosure may not be fully exerted, while if it exceeds 3.0%, bleeding or bleeding on the paper may occur. It is not preferable because strike-through is likely to occur.
  • the ink composition for an aqueous ballpoint pen of the present disclosure is characterized by containing the above-mentioned urethane-based colored resin particles having an average particle diameter of 0.5 to 6 ⁇ m and an acetylene-based surfactant.
  • a water-soluble solvent can be contained, and a general-purpose colorant can be contained, if necessary, in addition to the urethane-based colored resin particles.
  • water-soluble 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 ether. , Can be used alone or in combination.
  • the content of this water-soluble solvent is preferably 5 to 40% with respect to the total amount of the ink composition.
  • water-soluble dyes and pigments such as inorganic pigments and organic pigments can be used in appropriate amounts as needed without impairing the effects of the present disclosure.
  • any of the direct dye, the acid dye, the edible dye, and the basic dye can be used in an appropriate amount as long as the effects of the present disclosure are not impaired.
  • the water-based ink composition for a water-based ball pen of the present disclosure is characterized by containing at least urethane-based colored resin particles having an average particle diameter of 0.5 to 6 ⁇ m and an acetylene-based surfactant.
  • water-soluble solvents water as a solvent (tap water, purified water, distilled water, ion-exchanged water, pure water, etc.) as the balance, as long as the effects of the present disclosure are not impaired.
  • Dispersants, lubricants, thickeners, pH adjusters, rust preventives, preservatives, antibacterial agents and the like can be appropriately contained.
  • nonionic, anionic surfactant and water-soluble resin are used as the dispersant that can be used.
  • a water-soluble polymer is preferably used.
  • the lubricant that can be used include nonionic compounds such as fatty acid esters of polyhydric alcohols, higher fatty acid esters of sugars, polyoxyalkylene higher fatty acid esters, and alkyl phosphate esters, which are also used as surface treatment agents for pigments, and phosphoric acid esters. , Alkyl sulfonate of higher fatty acid amide, anionic type such as alkyl allyl sulfonate, derivative of polyalkylene glycol, polyether-modified silicone and the like.
  • the thickener that can be used, for example, at least one selected from the group consisting of synthetic polymers, cellulose and polysaccharides is desirable.
  • Acidity regulators include ammonia, urea, monoethanoamine, diethanolamine, triethanolamine, sodium tripolyphosphate, sodium carbonate and other carbonates, alkali metal salts of phosphoric acid, and alkali metal hydrates such as sodium hydroxide. And so on.
  • rust preventives include benzotriazole, triltriazole, dicyclohexylammonium nitrate, saponins, etc.
  • preservatives or antibacterial agents include phenol, sodium omadin, sodium benzoate, thiazolin compounds, benzimidazole. Examples include system compounds. Each component such as the dispersant, lubricant, thickener, pH adjuster, rust inhibitor, preservative or antibacterial agent may be used alone or in combination of two or more. .. Also, if you have these commercial products, you can use them.
  • the water-based ballpoint pen ink composition of the present disclosure contains at least the urethane-based colored resin particles having an average particle diameter of 0.5 to 6 ⁇ m, an acetylene-based surfactant, a water-soluble solvent, and other components as the ballpoint pen ink.
  • a stirrer such as a homomixer, homogenizer or disper, and if necessary, removing coarse particles in the ink composition by filtration or centrifugation, etc.
  • An ink composition for a ballpoint pen can be prepared.
  • the ink composition for a water-based ballpoint pen of the present disclosure can be produced without any particular difference as compared with other methods for producing an water-based ink composition. That is, in the ink composition for a water-based ballpoint pen of the present disclosure, at least the urethane-based colored resin particles having an average particle diameter of 0.5 to 6 ⁇ m, an acetylene-based surfactant, a water-soluble solvent, and other components are mixed. Further, for example, an ink composition for a water-based ballpoint pen is produced by mixing and stirring using a bead mill, a homomixer, a homogenizer, or the like capable of applying strong shearing, setting the stirring conditions to suitable conditions, and the like. be able to.
  • the pH (25 ° C.) of the ink composition for water-based ballpoint pens of the present disclosure is set to 5 to 10 depending on a pH adjuster or the like from the viewpoints of usability, safety, stability of the ink itself, and matching with the ink container. It is preferably adjusted, and more preferably 6 to 9.5.
  • the ink composition for a water-based ballpoint pen of the present disclosure is mounted on a ballpoint pen provided with a pen tip such as a ballpoint pen tip.
  • the water-based ballpoint pen ink composition having the above composition is housed in a ballpoint pen ink container (refill) having a ball having a diameter of 0.18 to 2.0 mm, and the ink is stored.
  • a substance that is incompatible with the water-based ink composition contained in the body and has a small specific gravity with respect to the water-based ink composition for example, a substance containing polybutene, silicone oil, mineral oil, or the like as an ink follower. Can be mentioned.
  • the structure of the water-based ballpoint pen to be used is not particularly limited as long as it includes balls having a diameter in the above range.
  • the water-based ink composition is filled in an ink storage tube of a polypropylene tube, and a stainless steel tip at the tip ( It is desirable that the ball is finished in a refill water-based ballpoint pen having (super steel alloy).
  • it may be a direct liquid type ballpoint pen provided with 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. ..
  • the surface roughness Ra of the ball of the water-based ballpoint pen is less than 10 nm, and particularly preferably, the surface roughness Ra of the ball of the writing ball is 4 nm or less. At this time, if the surface roughness Ra of the writing ball is 10 nm or more, the writing quality is gradually deteriorated.
  • the "surface roughness Ra" in the present disclosure (including the examples described later) is defined by a non-contact surface shape measuring machine (NewView7200 manufactured by Zygo) under the conditions of a lens magnification of 50 times, an evaluation length of 100 ⁇ m, and a Gaussian filter of 25 ⁇ m. Other than that, it shall comply with JIS B0601 (Geometric characteristic specifications of the product-Surface texture).
  • the water-based ballpoint pen of the present disclosure can further exert the effects of the present disclosure without impairing the writing quality, and can apply a ball having a small surface roughness.
  • the contact angle between the polyethylene terephthalate film (PET film surface, writing surface) and the ink is 40 ° or less in the ink composition from the viewpoint of further exerting the effect of the present disclosure.
  • acrylic colored resin particle species, acetylene surfactant species, and their respective contents having an average particle diameter within a predetermined range to be contained are suitable. It can be prepared by combining with.
  • an automatic contact angle measuring machine (DM500 manufactured by Kyowa Interface Science Co., Ltd.) was used for measuring the contact angle.
  • the ink composition for an aqueous ballpoint pen of the present disclosure contains at least the urethane-based colored resin particles having an average particle diameter of 0.5 to 6 ⁇ m and an acetylene-based surfactant.
  • the acetylene-based surfactants represented by the formulas (I) to (VI) and the like are characterized by having a low contact angle and an effect of enhancing wettability.
  • the ink composition for a water-based ballpoint pen and the water-based ballpoint pen of the present disclosure it is possible to apply a ball having a small surface roughness, and it is possible to further achieve both good writing quality and writeability in a low temperature environment. It becomes.
  • a trimethylolpropane adduct of xylylene diisocyanate (Takenate D110N, manufactured by Mitsui Kagaku Co., Ltd.) as a prepolymer was added thereto to prepare an oil phase solution.
  • aqueous phase solution 600 parts by mass of distilled water is heated to 60 ° C., and 15 parts by mass of polyvinyl alcohol (PVA-205, manufactured by Kuraray Co., Ltd.) as a dispersant is dissolved therein to prepare an aqueous phase solution. did.
  • 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. Colored resin particles were obtained by centrifuging the obtained dispersion. The average particle size (D50) of the colored resin particles was 2.1 ⁇ m.
  • Examples 1 to 6 and Comparative Examples 1 to 2 The urethane-based colored resin particles of Production Examples 1 and 2 were used, and each water-based ballpoint pen ink composition was prepared by a conventional method according to the compounding composition shown in Table 1 below. With respect to the ink compositions for water-based ballpoint pens obtained in Examples 1 to 6 and Comparative Examples 1 and 2, the contact angle between the PET film surface and the ink was measured by the above method, and at a low temperature by the following evaluation method. The writeability at (at 5 ° C.) was evaluated. These results are shown in Table 1 below.
  • the ink compositions for water-based ballpoint pens of Examples 1 to 6 which are within the scope of the present disclosure are in a low temperature environment as compared with Comparative Examples 1 and 2 which are outside the scope of the present disclosure.
  • the ink composition for a water-based ballpoint pen which has a small increase in ink viscosity and is less likely to cause writing defects, and a water-based ballpoint pen equipped with the composition.
  • An ink composition suitable for a water-based ballpoint pen can be obtained.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Pens And Brushes (AREA)

Abstract

The present invention provides: an ink composition for water-based ballpoint pens, said ink composition being suppressed in increase of the ink viscosity even in a low temperature environment, while being not susceptible to the occurrence of writing failure; and a water-based ballpoint pen which is loaded with this ink composition for water-based ballpoint pens.　An ink composition for water-based ballpoint pens according to one embodiment of the present invention is characterized by containing at least an acetylene surfactant and urethane-based colored resin particles that have an average particle diameter of from 0.5 μm to 6 μm.　A water-based ballpoint pen according to one embodiment of the present invention is characterized by being loaded with an ink composition for water-based ballpoint pens, said ink composition having the above-described configuration.

Description

水性ボールペン用インク組成物Ink composition for water-based ballpoint pens
　本明細書は、低温環境下であってもインク粘度の上昇が少なく、筆記不良が発生しにくい水性ボールペン用インク組成物に関する。 The present specification relates to an ink composition for a water-based ballpoint pen, which has a small increase in ink viscosity even in a low temperature environment and is less likely to cause writing defects.
　従来より、着色粒子を用いた水性ボールペン用インク組成物として、例えば、１）比重の大きい顔料や分散性にやや難があるなどの顔料と、特定物性となる水難溶性の媒体を内包したマイクロカプセル顔料を含有した水性ボールペン用インク組成物（例えば、特許文献１参照）、２）板状光輝性顔料と、着色顔料と、油性溶媒を内包するマイクロカプセル粒子と、水と、アクリル酸系重合物の塩、若しくはオレフィン系重合物、ウレタン系重合物、アクリル酸系重合物のエマルジョンから選ばれる一種以上の塩又はエマルジョンとを含有してなるボールペン用光輝性インク組成物（例えば、特許文献２参照）、３）スチレン－アクリロニトリル樹脂粒子と、着色剤と、アルキル硫酸塩と、リン酸エステル系界面活性剤と、水と、を含んでなることを特徴とする、水性ボールペン用インク組成物（例えば、特許文献３参照）などが知られている。 Conventionally, as an ink composition for an aqueous ball pen using colored particles, for example, 1) a pigment having a large specific gravity or a pigment having a slight difficulty in dispersibility, and a microcapsule containing a poorly water-soluble medium having specific physical properties. Aqueous ball pen ink composition containing a pigment (see, for example, Patent Document 1), 2) a plate-shaped bright pigment, a coloring pigment, microcapsule particles containing an oily solvent, water, and an acrylic acid-based polymer. A brilliant ink composition for a ball pen containing one or more salts or emulsions selected from emulsions of olefin-based polymers, urethane-based polymers, and acrylic acid-based polymers (see, for example, Patent Document 2). ), 3) An ink composition for an aqueous ball pen, which comprises styrene-acrylonitrile resin particles, a colorant, an alkyl sulfate, a phosphoric acid ester-based surfactant, and water (for example). , Patent Document 3) and the like are known.
　上記特許文献１は、比重の大きい顔料や分散性にやや難がある顔料の分散性を容易にする水性ボールペン用インク組成物の提供を目的とするものであり、上記特許文献２は、鮮やかな筆跡と経時安定性を維持できるボールペン用光輝性インク組成物の提供を目的とするものであり、上記特許文献３は、分散安定性に優れ、良好な筆跡が得ることができる水性ボールペン用インク組成物の提供を目的とするものであり、これらの各特許文献には、低温環境下での筆記性については、開示や示唆等はないものである。 The purpose of Patent Document 1 is to provide an ink composition for a water-based ballpoint pen that facilitates dispersibility of a pigment having a large specific gravity or a pigment having a slight difficulty in dispersibility, and Patent Document 2 is vivid. An object of the present invention is to provide a brilliant ink composition for a ballpoint pen that can maintain handwriting and stability over time. The above-mentioned Patent Document 3 has excellent dispersion stability and an ink composition for a water-based ballpoint pen that can obtain a good handwriting. The purpose is to provide a product, and each of these patent documents does not disclose or suggest writeability in a low temperature environment.
　一般に、低温環境下においてボールペンで筆記すると、正常に筆記できないことがしばしば発生している。この原因として、低温時には、インク粘度が上昇しペン先から吐出されにくくなりインクの転写が不良となることが考えられる。特に、粒子径が大きな材料などを配合した水性ボールペン用インク組成物においては、インクの流動性が乏しいため、よりこの現象が発生しやすいなどの課題があるのが現状である。 In general, when writing with a ballpoint pen in a low temperature environment, it often happens that writing cannot be performed normally. It is considered that the cause of this is that at low temperatures, the viscosity of the ink increases and it becomes difficult for the ink to be ejected from the pen tip, resulting in poor ink transfer. In particular, in an ink composition for a water-based ballpoint pen containing a material having a large particle size or the like, there is a problem that this phenomenon is more likely to occur because the fluidity of the ink is poor.
特開２０１７－１２２１６８号公報（特許請求の範囲、実施例等）JP-A-2017-12168 (Claims, Examples, etc.) 特開２０１７－１１９８６２号公報（特許請求の範囲、実施例等）Japanese Unexamined Patent Publication No. 2017-119862 (Claims, Examples, etc.) 特開２０１９－１１６５７６号公報（特許請求の範囲、実施例等）JP-A-2019-116576 (Claims, Examples, etc.)
　本開示は、上記従来技術の課題及び現状等に鑑み、これを解消しようとするものであり、低温環境下であってもインク粘度の上昇が少なく、筆記不良が発生しにくい水性ボールペン用インク組成物及び水性ボールペンを提供することを目的とする。 In view of the above-mentioned problems of the prior art and the current situation, the present disclosure is intended to solve the problems, and the ink composition for a water-based ballpoint pen is less likely to cause writing defects because the ink viscosity does not increase even in a low temperature environment. It is an object of the present invention to provide a thing and a water-based ballpoint pen.
　本発明者らは、上記従来の課題及び現状等に鑑み、鋭意研究を行った結果、少なくとも、平均粒子径が所定の範囲となる特定の着色樹脂粒子と、特定の界面活性剤とを含有することにより、上記目的の水性ボールペン用インク組成物等が得られることを見出し、本開示を完成するに至ったのである。 As a result of diligent research in view of the above-mentioned conventional problems and the current situation, the present inventors contain at least specific colored resin particles having an average particle size in a predetermined range and a specific surfactant. As a result, they have found that an ink composition for a water-based ballpoint pen and the like can be obtained for the above purpose, and have completed the present disclosure.
　すなわち、本開示の水性ボールペン用インク組成物は、少なくとも、平均粒子径が０．５～６μｍのウレタン系着色樹脂粒子と、アセチレン系界面活性剤とを含有することを特徴とする。
　上記水性ボールペン用インク組成物は、ポリエチレンテレフタレートフィルムとインクとの接触角が４０°以下であることが好ましい。
　本開示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。
　上記水性ボールペンのボールの表面粗さは１０ｎｍ未満であることが好ましい。 That is, the water-based ballpoint pen ink composition of the present disclosure is characterized by containing at least urethane-based colored resin particles having an average particle diameter of 0.5 to 6 μm and an acetylene-based surfactant.
The water-based ballpoint pen ink composition preferably has a contact angle between the polyethylene terephthalate film and the ink of 40 ° or less.
The water-based ballpoint pen of the present disclosure is characterized by being equipped with an ink composition for a water-based ballpoint pen having the above configuration.
The surface roughness of the ball of the water-based ballpoint pen is preferably less than 10 nm.
　本開示によれば、低温環境下であってもインク粘度の上昇が少なく、筆記不良が発生しにくい水性ボールペン用インク組成物及びそれを搭載した水性ボールペンが提供される。
　本明細書において、前述の一般的な説明及び後述の詳細な説明の両方は、例示的及び説明的なものであり、特許請求の範囲に記載されている本開示を制限するものではない。 According to the present disclosure, there is provided an ink composition for a water-based ballpoint pen in which an increase in ink viscosity is small even in a low temperature environment and writing defects are unlikely to occur, and a water-based ballpoint pen on which the ink composition is mounted.
In the present specification, both the general description described above and the detailed description described below are exemplary and descriptive, and do not limit the disclosure described in the claims.
　以下に、本開示の少なくとも幾つかの実施形態について詳しく説明する。但し、本開示の技術的範囲は下記で詳述するそれぞれの実施の形態に限定されず、特許請求の範囲に記載された発明とその均等物に及ぶ点に留意されたい。
　本開示の水性ボールペン用インク組成物は、少なくとも、平均粒子径が０．５～６μｍのウレタン系着色樹脂粒子と、アセチレン系界面活性剤を含有することを特徴とするものである。 At least some embodiments of the present disclosure will be described in detail below. However, it should be noted that the technical scope of the present disclosure is not limited to the respective embodiments described in detail below, but extends to the inventions described in the claims and their equivalents.
The ink composition for an aqueous ballpoint pen of the present disclosure is characterized by containing at least urethane-based colored resin particles having an average particle diameter of 0.5 to 6 μm and an acetylene-based surfactant.
〈ウレタン系着色樹脂粒子〉
　本開示に用いるウレタン系着色樹脂粒子としては、着色されたウレタン系樹脂粒子から構成されるものであれば特に限定されず、例えば、１）染料または顔料などで着色されたウレタン系着色樹脂粒子、２）ロイコ色素等を用いて熱変色性としたウレタン系着色樹脂粒子、３）光変色性色素となるフォトクロミック色素（化合物）、蛍光色素等を用いて光変色性としたウレタン系着色樹脂粒子などが挙げられる。 <Urethane-based colored resin particles>
The urethane-based colored resin particles used in the present disclosure are not particularly limited as long as they are composed of colored urethane-based resin particles, and for example, 1) urethane-based colored resin particles colored with a dye or pigment, etc. 2) Urethane-based colored resin particles that are thermally discolored using leuco dyes, etc. 3) Photochromic dyes (compounds) that are photo-discolored dyes, urethane-based colored resin particles that are photo-discolored using fluorescent dyes, etc. Can be mentioned.
　上記１）のウレタン系着色樹脂粒子は、少なくともウレタン結合を有する重合体、共重合体から構成されるものであり、イソシアネート成分（ジイソシアネート成分を含む）とポリオール成分（ジオール成分含む）などとを反応させることにより得られるものであり、例えば、ウレタン粒子（ポリエステル型ウレタン粒子、ポリカーボネート型ウレタン粒子、ポリエーテル型ウレタン粒子など）、ウレタン・ウレア粒子などの少なくとも１種が挙げられる。
　ウレタン系着色樹脂粒子は、例えば、下記製法により得られたものを用いることができる。
　上記１）のウレタン系着色樹脂粒子の製法は、ａ）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、水不溶性染料を含有する油相の作製、ｂ）水及び分散剤を混合させることによる水相の作製、ｃ）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。なお、水不溶性染料を用いない場合は、白色のウレタン系着色樹脂粒子として用いることができる。 The urethane-based colored resin particles of 1) above are composed of a polymer and a copolymer having at least a urethane bond, and react an isocyanate component (including a diisocyanate component) with a polyol component (including a diol component). For example, at least one kind of urethane particles (polyester type urethane particles, polycarbonate type urethane particles, polyether type urethane particles, etc.), urethane / urea particles, and the like can be mentioned.
As the urethane-based colored resin particles, for example, those obtained by the following production method can be used.
The method for producing urethane-based colored resin particles in 1) above is as follows: a) Preparation of an oil phase containing an organic solvent, an isocyanate monomer or an isocyanate prepolymer, and a water-insoluble dye, and b) An aqueous phase by mixing water and a dispersant. C) The above oil phase and aqueous phase are mixed, and the components of the oil phase are emulsified and then polymerized. When the water-insoluble dye is not used, it can be used as white urethane-based colored resin particles.
　油相は、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している。この有機溶剤は、複数種含有されていてもよい。
　この油相は、有機溶剤を所定の温度に加温しながら、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、アルキルスルホ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。 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.
This oil phase is prepared by adding a water-insoluble dye and stirring while heating the organic solvent to a predetermined temperature, then adding the above-mentioned monomer or prepolymer, and further adding another organic solvent if necessary. Can be made.
As the organic solvent, for example, phenyl glycol, benzyl alcohol, ethylene glycol monobenzyl ether, ethyl acetate and the like can be used. Further, alkylsulfonic acid phenyl ester, ethylhexyl phthalate, tridecyl phthalate, ethylhexyl trimellitic acid, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, liquid xylene resin and the like can also be used.
　イソシアネートモノマー又はプレポリマーとしては、例えば，ヘキサメチレンジイソシアネート、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、キシリレンジイソシアネート、イソホロンジイソシアネート、イソシアネートプレポリマー等を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。
　平均粒子径の調整は、重合の際、撹拌条件等をコントロールすることにより調整することができる。 As the isocyanate monomer or prepolymer, for example, hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, isophorone diisocyanate, isocyanate prepolymer and the like can be used.
As the 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. In addition to the above-mentioned trimer, a dimer such as the above-mentioned allophanate modified isocyanate can be used as an auxiliary prepolymer.
The average particle size can be adjusted by controlling the stirring conditions and the like during the polymerization.
　水不溶性染料としては、常温において水に不溶の染料であり、例えば、造塩染料、分散染料、油溶性染料等を用いることができるが、発色性の観点から、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造塩染料を用いることが好ましい。
　水相は、水及び分散剤を混合させることにより作製することができる。分散剤としては、例えば、ポリビニルアルコールを用いることができるが、これに限定されない。
　乳化及び重合工程は、上記油相の成分を乳化し、さらに重合させる工程は、水相に油相を投入し、ホモジナイザー等を用いて所定の温度に加温しながら乳化混合することによりウレタン系着色樹脂粒子を得ることができる。 The water-insoluble dye is a dye that is insoluble in water at room temperature, and for example, salt-forming dyes, disperse dyes, oil-soluble dyes, and the like can be used. It is preferable to use salt-forming dyes having anthraquinone-based and metallic phthalocyanine-based chemical structures.
The aqueous phase can be prepared by mixing water and a dispersant. As the dispersant, for example, polyvinyl alcohol can be used, but the dispersant is not limited to this.
In the emulsification and polymerization steps, 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 oil phase is emulsified and mixed while being heated to a predetermined temperature using a homogenizer or the like. Colored resin particles can be obtained.
　また、上記乳化重合の他、相分離法によるウレタン系着色樹脂粒子を作製してもよい。この製造法は、染料含有溶液を作製すること、保護コロイド剤含有溶液を作製すること、イソシアネートモノマー又はイソシアネートを重合させることからなる。
　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。
　保護コロイド剤含有溶液は、保護コロイド剤を水に溶解させることにより、作製することができる。保護コロイド剤としては、例えば、メチルビニルエーテル－無水マレイン酸共重合体等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。 In addition to the above emulsion polymerization, urethane-based colored resin 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. As the water-insoluble dye and the 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. As the protective colloidal agent, for example, a methyl vinyl ether-maleic anhydride copolymer or the like can be used.
In the polymerization of the isocyanate monomer or the isocyanate prepolymer, in the case of coloring, 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.
　上記２）の熱変色性のウレタン系着色樹脂粒子としては、電子供与性染料であって、発色剤としての機能するロイコ色素と、該ロイコ色素を発色させる能力を有する成分となる顕色剤及び上記ロイコ色素と顕色剤の呈色において変色温度をコントロールすることができる変色温度調整剤を少なくとも含む熱変色性組成物を、所定の平均粒子径となるように、マイクロカプセル化することにより製造された熱変色性のウレタン系着色樹脂粒子などを挙げることができる。
　マイクロカプセル化法としては、例えば、界面重合法、界面重縮合法、ｉｎｓｉｔｕ重合法、液中硬化被覆法、水溶液からの相分離法、有機溶媒からの相分離法、融解分散冷却法、気中懸濁被覆法、スプレードライニング法などを挙げることができ、用途に応じて適宜選択することができる。例えば、水溶液からの相分離法では、上記１）のウレタン系着色樹脂粒子の相分離法と同様に、ロイコ色素、顕色剤、変色温度調整剤を加熱溶融後、乳化剤溶液に投入し、加熱攪拌して油滴状に分散させ、次いで、カプセル膜剤として、壁膜が上記１）で例示したウレタン系樹脂原料などを徐々に投入し、引き続き反応させて調製後、この分散液を濾過することにより熱変色性のマイクロカプセル顔料からなる熱変色性のウレタン系着色樹脂粒子を製造することができる。この熱変色性のウレタン系着色樹脂粒子では、ロイコ色素、顕色剤及び変色温度調整剤の種類、量などを好適に組み合わせることにより、各色の発色温度、消色温度を好適な温度に設定することができる。
　なお、前記熱変色性のウレタン系着色樹脂粒子は、可逆熱変色性となるものが好ましい。可逆熱変色性となるものは、発色状態から加熱により消色する加熱消色型、発色状態又は消色状態を互変的に特定温度域で記憶保持する色彩記憶保持型、又は、消色状態から加熱により発色し、発色状態からの冷却により消色状態に復する加熱発色型等、種々のタイプを単独又は併用して構成することができる。 The thermochromic urethane-based colored resin particles in 2) above include an electron-donating dye, a leuco dye that functions as a color-developing agent, and a color-developing agent that is a component having the ability to develop the color of the leuco dye. Manufactured by microencapsulating a thermally discolorable composition containing at least a discoloration temperature adjusting agent capable of controlling the discoloration temperature in the color development of the leuco dye and the color developer so as to have a predetermined average particle size. Examples thereof include heat-discolorable urethane-based colored resin particles.
Examples of the microencapsulation method include interfacial polymerization method, interfacial polycondensation method, insitu polymerization method, in-liquid curing coating method, phase separation method from aqueous solution, phase separation method from organic solvent, melting dispersion cooling method, and air. Examples thereof include a suspension coating method and a spray drying method, which can be appropriately selected depending on the intended use. For example, in the phase separation method from an aqueous solution, similarly to the phase separation method of urethane-based colored resin particles in 1) above, a leuco pigment, a color developer, and a discoloration temperature adjuster are heated and melted, then put into an emulsifier solution and heated. The mixture is stirred and dispersed in the form of oil droplets, and then the urethane-based resin raw material whose wall film is exemplified in 1) above is gradually added as a capsule film agent, and the reaction is continued to prepare, and then this dispersion is filtered. This makes it possible to produce heat-discolorable urethane-based colored resin particles composed of heat-discolorable microcapsule pigments. In the heat-discoloring urethane-based colored resin particles, the color development temperature and decolorization temperature of each color are set to suitable temperatures by appropriately combining the types and amounts of the leuco dye, the color developer, and the color change temperature adjusting agent. be able to.
The thermochromic urethane-based colored resin particles preferably have reversible thermochromic properties. Those with reversible thermal discoloration are a heat decolorization type that decolorizes by heating from the color development state, a color memory retention type that alternately stores the color development state or the decolorization state in a specific temperature range, or a decolorization state. Various types such as a heating color-developing type that develops color by heating and returns to a decolorized state by cooling from the color-developed state can be configured alone or in combination.
　上記３）の光変色性のウレタン系着色樹脂粒子としては、例えば、少なくともフォトクロミック色素（化合物）、蛍光色素などから選択される１種以上と、テルペンフェノール樹脂などの樹脂とにより構成される光変色性のウレタン系着色樹脂粒子や、少なくともフォトクロミック色素（化合物）、蛍光色素などから選択される１種以上と、有機溶媒と、酸化防止剤、光安定剤、増感剤などの添加剤とを含む光変色性組成物を、所定の平均粒子径となるように、マイクロカプセル化することにより製造された光変色性のウレタン系着色樹脂粒子などを挙げることができる。マイクロカプセル化法としては、上述の熱変色性の樹脂粒子の製造と同様に調製することができる。
　この光変色性のウレタン系着色樹脂粒子は、フォトクロミック色素（化合物）、蛍光色素などを好適に用いることにより、例えば、室内照明環境（室内での白熱灯、蛍光灯、ランプ、白色ＬＥＤなどから選ばれる照明器具）において無色であり、紫外線照射環境（２００～４００ｎｍ波長の照射、紫外線を含む太陽光での照射環境）で発色する性質を有するものとすることができる。
　上記１）～３）の各ウレタン系着色樹脂粒子は、ボールペン用の通常の色材として、蛍光顔料、熱変色性顔料や光変色性顔料のマイクロカプセル顔料など（色材）として使用することができる。また、上記１）～３）の各ウレタン系着色樹脂粒子は、公知の各製造法により製造した各ウレタン系着色樹脂粒子を使用することができ、市販品があれば、それらを使用してもよいものである。
　これらのウレタン系着色樹脂粒子は、着色力、分散安定性などの点から、平均粒子径が０．５～６μｍとなるものが使用され、好ましくは、１～５μｍの使用が望ましい。
　本開示（後述する実施例を含む）において、「平均粒子径」とは、レーザー回折法で測定される体積基準により算出された粒度分布の体積累積５０％時の粒子径（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。 The photochromic urethane-based colored resin particles of 3) above include, for example, at least one selected from at least a photochromic dye (compound), a fluorescent dye, and a resin such as terpenephenol resin. Includes sex urethane-based colored resin particles, at least one selected from at least photochromic dyes (compounds), fluorescent dyes, etc., organic solvents, and additives such as antioxidants, light stabilizers, and sensitizers. Examples thereof include photocolorable urethane-based colored resin particles produced by microencapsulating a photochromic composition so as to have a predetermined average particle size. As the microencapsulation method, it can be prepared in the same manner as in the production of the heat-discolorable resin particles described above.
The photochromic urethane-based colored resin particles are selected from, for example, indoor lighting environments (indoor incandescent lamps, fluorescent lamps, lamps, white LEDs, etc.) by preferably using photochromic dyes (compounds), fluorescent dyes, and the like. It is possible that the lighting fixture is colorless and has the property of developing color in an ultraviolet irradiation environment (irradiation with a wavelength of 200 to 400 nm, irradiation environment with sunlight including ultraviolet rays).
Each of the urethane-based colored resin particles 1) to 3) above can be used as a normal coloring material for a ball pen, such as a fluorescent pigment, a heat-changing pigment, or a microcapsule pigment of a photo-changing pigment (coloring material). it can. Further, as each of the urethane-based colored resin particles 1) to 3) above, each urethane-based colored resin particle produced by each known production method can be used, and if there is a commercially available product, they may be used. It's a good one.
As these urethane-based colored resin particles, those having an average particle diameter of 0.5 to 6 μm are used from the viewpoint of coloring power, dispersion stability, etc., and it is preferably used in an amount of 1 to 5 μm.
In the present disclosure (including examples described later), the "average particle size" is the value of the particle size (D50) when the volume accumulation of the particle size distribution is 50%, which is calculated by the volume standard measured by the laser diffraction method. is there. Here, 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.
　これらのウレタン系着色樹脂粒子の含有量は、インク組成物全量に対して、３～３０％とすることが好ましく、更に好ましくは、１０～３０％とすることが望ましい。このウレタン系着色樹脂粒子の含有量が３％未満であると、好ましい描線濃度が得られなくなり、また、３０％を越えると、筆記感が重くなったり、描線にカスレが生じやすくなり、好ましくない。 The content of these urethane-based colored resin particles is preferably 3 to 30%, more preferably 10 to 30%, based on the total amount of the ink composition. If the content of the urethane-based colored resin particles is less than 3%, a preferable drawing density cannot be obtained, and if it exceeds 30%, the writing feeling becomes heavy and the drawing lines tend to be blurred, which is not preferable. ..
　本開示に用いるアセチレン系界面活性剤は、本開示の効果を発揮せしめるために含有するものであり、アセチレングリコール類、そのアルキレンオキサイド付加物及びアセチレンアルコール類から選ばれる少なくとも１種（各単独又は２種以上の混合物、以下同様）が挙げられる。
　用いることができるアセチレングリコール類、そのアルキレンオキサイド付加物及びアセチレンアルコール類としては、具体的には、下記式（Ｉ）～（ＶＩ）から選ばれる少なくとも１種が挙げられる。 The acetylene-based surfactant used in the present disclosure is contained in order to exert the effects of the present disclosure, and is at least one selected from acetylene glycols, alkylene oxide adducts thereof, and acetylene alcohols (each alone or 2). Mixtures of seeds and above, and so on).
Specific examples of the acetylene glycols, alkylene oxide adducts thereof, and acetylene alcohols that can be used include at least one selected from the following formulas (I) to (VI).
Figure JPOXMLDOC01-appb-C000001
   
 
〔上記式（Ｉ）～（ＩＩＩ）中のＲ１、Ｒ２は、それぞれ炭素数１～８の直鎖又は分岐鎖を有するアルキル基であり、ｍ、ｎ、ｘ、ｙは１～１００の数である。〕
Figure JPOXMLDOC01-appb-C000002
  
 
 
〔上記式（ＩＶ）～（ＶＩ）中、Ｒ３、Ｒ４、Ｒ５は、水素原子、直鎖又は分岐鎖を有する炭素数０～１０の炭素鎖を表し、該炭素鎖には不飽和結合を含んでもいてもよく、Ｒ６は、炭素数２～５のアルキレン基、Ｒ７は、炭素数１～５のアルキレン基を表す。〕
Figure JPOXMLDOC01-appb-C000001

[R1 and R2 in the above formulas (I) to (III) are alkyl groups having linear or branched chains having 1 to 8 carbon atoms, respectively, and m, n, x, and y are numbers of 1 to 100. is there. ]
Figure JPOXMLDOC01-appb-C000002


[In the above formulas (IV) to (VI), R3, R4, and R5 represent a carbon chain having a hydrogen atom, a straight chain, or a branched chain and having 0 to 10 carbon atoms, and the carbon chain contains an unsaturated bond. R6 represents an alkylene group having 2 to 5 carbon atoms, and R7 represents an alkylene group having 1 to 5 carbon atoms. ]
　用いることができるアセチレングリコール類、そのアルキレンオキサイド付加物としては、例えば、上記式（Ｉ）で示されるアセチレングリコール、上記式（ＩＩ）で示されるアセチレングリコールのエチレンオキサイド（ＥＯ）を付加した誘導体（付加物）、上記式（ＩＩＩ）で示されるアセチレングリコールのエチレンオキサイド（ＥＯ）、プロピレンオキサイド（ＰＯ）を付加した誘導体（付加物）などを挙げることができる。
　上記式（Ｉ）～（ＩＩＩ）中のＲ１、Ｒ２が示す炭素数１～８の直鎖又は分岐鎖を有するアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基等が挙げられる。 Examples of the acetylene glycols that can be used and the alkylene oxide adduct thereof include acetylene glycol represented by the above formula (I) and a derivative to which ethylene oxide (EO) of acetylene glycol represented by the above formula (II) is added. Additives), ethylene oxide (EO) of acetylene glycol represented by the above formula (III), derivatives (adducts) to which propylene oxide (PO) is added, and the like can be mentioned.
Examples of the alkyl group having a linear or branched chain having 1 to 8 carbon atoms represented by R1 and R2 in the above formulas (I) to (III) include a methyl group, an ethyl group, a propyl group, an isopropyl group, and n-. Examples thereof include a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and the like.
　上記式（Ｉ）のアセチレングリコールとしては、例えば、２，５，８，１１－テトラメチル－６－ドデシン－５，８－ジオール、５，８－ジメチル－６－ドデシン－５，８－ジオール、２，４，７，９－テトラメチル－５－ドデシン－４，７－ジオール、８－ヘキサデシン－７、１０－ジオール、７－テトラデシン－６，９－ジオール、２，３，６，７－テトラメチル－４－オクチン－３，６－ジオール、３，６－ジエチル－４－オクチン－３，６－ジオール、２，５－ジメチル－３－ヘキシン－２，５－ジオール等を挙げることでき、上記式（ＩＩ）、式（ＩＩＩ）のアセチレングリコールのアルキレンオキサイド（ＥＯ、ＰＯ）付加物としては、上記アセチレングリコールのアルキレンオキサイド誘導体を挙げることができる。 Examples of the acetylene glycol of the above formula (I) include 2,5,8,11-tetramethyl-6-dodecine-5,8-diol and 5,8-dimethyl-6-dodecine-5,8-diol. 2,4,7,9-Tetramethyl-5-dodecine-4,7-diol, 8-hexadecin-7,10-diol, 7-tetradecine-6,9-diol, 2,3,6,7-tetra Methyl-4-octin-3,6-diol, 3,6-diethyl-4-octin-3,6-diol, 2,5-dimethyl-3-hexin-2,5-diol and the like can be mentioned. Examples of the alkylene oxide (EO, PO) adduct of the acetylene glycol of the formulas (II) and (III) include the alkylene oxide derivative of the acetylene glycol.
　上記式（Ｉ）～（ＩＩＩ）に挙げた各化合物の合成法は、既知であり、種々の製法により得ることができ、また、市販のものを使用してもよい。例えば、アセチレングリコール類、そのアルキレンオキサイド付加物としては、市販のサーフィノール１０４〔２，４，７，９－テトラメチル－５－ドデシン－４，７－ジオール、日信化学工業株式会社製〕、サーフィノール１０４を各種溶剤で希釈したサーフィノール１０４Ｅ（エチレングリコール）、１０４Ｈ（エチレングリコール）、１０４Ａ（２－エチルヘキサノール）等、シリカ粒子を含有した１０４Ｓなどのサーフィノール１０４シリーズ、サーフィノール１０４のＥＯ付加物である４２０、４４０、４６５、４８５、ＤＦ１１０Ｄ、ＤＦ３７、ＤＦ５８、ＤＦ７５、ＤＦ２２０などが挙げられる。 The synthetic methods of the compounds listed in the above formulas (I) to (III) are known and can be obtained by various production methods, or commercially available ones may be used. For example, as acetylene glycols and alkylene oxide adducts thereof, commercially available surfinol 104 [2,4,7,9-tetramethyl-5-dodecine-4,7-diol, manufactured by Nissin Chemical Industry Co., Ltd.], Surfinol 104 series such as 104S containing silica particles such as Surfinol 104E (ethylene glycol), 104H (ethylene glycol), 104A (2-ethylhexanol) obtained by diluting Surfinol 104 with various solvents, EO of Surfinol 104. Additives such as 420, 440, 465, 485, DF110D, DF37, DF58, DF75, DF220 and the like can be mentioned.
　また、上記式（ＩＶ）～（ＶＩ）で示されるアセチレンアルコール類は、分子構造中にアセチレン基（－Ｃ≡Ｃ－）とヒドロキシル基（－ＯＨ）を有するものである。
　上記一般式（ＩＶ）～（ＶＩ）中のＲ３、Ｒ４、Ｒ５としては、それぞれ、水素原子、直鎖又は分岐を有するアルキル基、アルケニル基、アリール基、アラルキル基等が挙げられる。ここで、上記アルキル基及びアルケニル基は、直鎖状、枝分かれ状、環状のいずれであってもよく、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ヘキシル基、オクチル基、デシル基、ドデシル基、シクロペンチル基、シクロヘキシル基、ビニル基、プロぺニル基、アリル基、ヘキセニル基、オクテニル基、シクロペンテニル基、シクロヘキセニル基等が挙げられる。また、上記アリール基は、芳香環上に低級アルキル基等の置換基を有していてもよく、例えば、フェニル基、トリル基、キシリル基、ナフチル基等が挙げられる。更に、上記アラルキル基は、芳香環上に低級アルキル基等の置換基を有していてもよく、例えば、ベンジル基、フェネチル基、ナフチルメチル基等が挙げられる。
　また、上記式（Ｖ）中のＲ６は、炭素数２～５のアルキレン基を表し、該アルキレン基は、直鎖状、枝分かれ状、環状のいずれであってもよいが、特に直鎖状のものが好適である。該直鎖状アルキレン基としては、エチレン基、トリメチレン基、テトラメチレン基、ペンタメチレン基等が挙げられる。
　更に、上記一般式（ＶＩ）中のＲ７は、炭素数１～５のアルキレン基を表し、該アルキレン基としては、メチレン基（炭素数１）であり、炭素数２以上では、上記一般式（Ｖ）中のＲ６と同様である。 Further, the acetylene alcohols represented by the above formulas (IV) to (VI) have an acetylene group (-C≡C-) and a hydroxyl group (-OH) in the molecular structure.
Examples of R3, R4, and R5 in the general formulas (IV) to (VI) include a hydrogen atom, an alkyl group having a linear or branched structure, an alkenyl group, an aryl group, an aralkyl group, and the like. Here, the alkyl group and the alkenyl group may be linear, branched or cyclic, and may be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group or an isobutyl group. , Se-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, cyclopentyl group, cyclohexyl group, vinyl group, propenyl group, allyl group, hexenyl group, octenyl group, cyclo Examples thereof include a pentenyl group and a cyclohexenyl group. Further, the aryl group may have a substituent such as a lower alkyl group on the aromatic ring, and examples thereof include a phenyl group, a tolyl group, a xsilyl group and a naphthyl group. Further, the aralkyl group may have a substituent such as a lower alkyl group on the aromatic ring, and examples thereof include a benzyl group, a phenethyl group and a naphthylmethyl group.
Further, R6 in the above formula (V) represents an alkylene group having 2 to 5 carbon atoms, and the alkylene group may be linear, branched or cyclic, but is particularly linear. Those are suitable. Examples of the linear alkylene group include an ethylene group, a trimethylene group, a tetramethylene group, and a pentamethylene group.
Further, R7 in the general formula (VI) represents an alkylene group having 1 to 5 carbon atoms, the alkylene group is a methylene group (1 carbon number), and the general formula (VI) has 2 or more carbon atoms. It is the same as R6 in V).
　上記式（ＩＶ）のアセチレンアルコール類又はこれらの誘導体として、具体的には、２－ブチン－１－オール、３－ブチン－２－オール、２－デシン－１－オール、３，６－ジメチル－１－ヘプチン－３－オール、３，５－ジメチル－１－ヘキシン－３－オール、３，４－ジメチル－１－ペンチン－３－オール、１，１－ジフェニル－２－プロピン－１－オール、３－エチル－１－ヘプチン－３－オール、４－エチル－１－オクチン－３－オール、３－エチル－１－ペンチン－３－オール、１－エチニル－１－シクロヘキサノール、９－エチニル－９－フルオレノール、１－ヘプチン－３－オール、２－ヘプチン－１－オール、１－ヘキシン－３－オール、２－ヘキシン－１－オール、３－メチル－１－ブチン－３－オール、３－メチル－１－ペンテン－４－イン－３－オール、３－メチル－１－ペンチン－３－オール、２－メチル－４－フェニル－３－ブチン－２－オール、１－オクチン－３－オール、１－ペンチン－３－オール、２－ペンチン－１－オール、１－フェニル－２－プロピン－１－オール、３－フェニル－２－プロピン－１－オール、２－プロピン－１－オール、１，１，３－トリフェニル－２－プロピン－１－オールなどの少なくとも１種が挙げられる。
　上記式（Ｖ）のアセチレンアルコール類又はこれらの誘導体として、具体的には、３－ブチン－１－オール、３－デシン－１－オール、９－デシン－１－オール、３－ヘプチン－１－オール、３－ヘキシン－１－オール、５－ヘキシン－１－オール、３－ノニン－１－オール、３－オクチン－１－オール、３－ペンチン－１－オール、４－ペンチン－１－オール、５－フェニル－４－ペンチン－１－オール、１０－ウンデシン－１－オールなどの少なくとも１種が挙げられる。 Specific examples of the acetylene alcohols of the above formula (IV) or derivatives thereof include 2-butyne-1-ol, 3-butyne-2-ol, 2-decine-1-ol, and 3,6-dimethyl-. 1-Heptin-3-ol, 3,5-dimethyl-1-hexin-3-ol, 3,4-dimethyl-1-pentyne-3-ol, 1,1-diphenyl-2-propin-1-ol, 3-Ethyl-1-heptin-3-ol, 4-ethyl-1-octin-3-ol, 3-ethyl-1-pentyne-3-ol, 1-ethynyl-1-cyclohexanol, 9-ethynyl-9 -Fluorenol, 1-heptin-3-ol, 2-heptin-1-ol, 1-hexin-3-ol, 2-hexin-1-ol, 3-methyl-1-butyne-3-ol, 3-methyl -1-Penten-4-in-3-ol, 3-methyl-1-pentyne-3-ol, 2-methyl-4-phenyl-3-butyne-2-ol, 1-octin-3-ol, 1 -Pentyne-3-ol, 2-pentyne-1-ol, 1-phenyl-2-propin-1-ol, 3-phenyl-2-propin-1-ol, 2-propin-1-ol, 1,1 , 3-Triphenyl-2-propin-1-ol and the like.
Specific examples of the acetylene alcohols of the above formula (V) or derivatives thereof include 3-butyne-1-ol, 3-decine-1-ol, 9-decin-1-ol, and 3-heptin-1-. All, 3-hexin-1-ol, 5-hexin-1-ol, 3-nonyne-1-ol, 3-octyne-1-ol, 3-pentyne-1-ol, 4-pentyne-1-ol, At least one such as 5-phenyl-4-pentyne-1-ol and 10-undecine-1-ol can be mentioned.
　上記式（ＶＩ）のアセチレンアルコール類又はこれらの誘導体として、具体的には、例えば、４－ヘプチン－２－オール、５－ヘプチン－３－オール、５－ヘキシン－３－オール、４－ペンチン－２－オールなどの少なくとも１種が挙げられる。
　上記式（ＩＶ）～（ＶＩ）で具体的に挙げた中で、使用性、コスト、安全性、本開示の効果を更に発揮せしめる点から、好ましくは、３－メチル－１－ブチン－３－オール、３－メチル－１－ペンチン－３－オール、３，５－ジメチル－１－ヘキシン－３－オールの使用が望ましい。
　上記式（ＩＶ）～（ＶＩ）に挙げた各化合物の合成法は、既知であり、種々の製法により得ることができ、また、市販のものを使用してもよい。例えば、アセチレンアルコール類としては、市販の日信化学工業株式会社製のサーフィノール６１（３，５－ジメチル－１－ヘキシン－３－オール）、オルフィンＡ（２，５－ジメチルヘキサン－２，５－ジオール）、オルフィンＢ（３－メチル－１－ブチン－３－オール）、オルフィンＰ（３－メチル－１－ペンチン－３－オール）、オルフィンＰＤ－００２Ｗ、ＥＸＰ．４１２３、ＥＸＰ．４２００、ＷＥ－００３、ＳＰＣ、その他のオルフィン系などが挙げられる。 Specific examples of the acetylene alcohols of the above formula (VI) or derivatives thereof include 4-heptin-2-ol, 5-heptin-3-ol, 5-hexyne-3-ol, and 4-pentyne-. At least one such as 2-ol is mentioned.
Among those specifically listed in the above formulas (IV) to (VI), 3-methyl-1-butyne-3- is preferable from the viewpoint of usability, cost, safety, and further exerting the effects of the present disclosure. It is desirable to use all, 3-methyl-1-pentyne-3-ol, 3,5-dimethyl-1-hexin-3-ol.
The synthetic methods of the compounds listed in the above formulas (IV) to (VI) are known and can be obtained by various production methods, or commercially available ones may be used. For example, as acetylene alcohols, commercially available Surfinol 61 (3,5-dimethyl-1-hexin-3-ol) and Orphine A (2,5-dimethylhexane-2,5) manufactured by Nissin Chemical Industry Co., Ltd. -Diol), Orphine B (3-methyl-1-butyne-3-ol), Orphine P (3-methyl-1-pentyne-3-ol), Orphine PD-002W, EXP. 4123, EXP. Examples include 4200, WE-003, SPC, and other Orphine systems.
　これらのアセチレン系界面活性剤の含有量（有効成分量）は、インク組成物全量に対して、０．１～３．０％とすることが好ましく、更に好ましくは、０．３～２．０％とすることが望ましい。このアセチレン系界面活性剤の含有量が０．１％未満であると、本開示の効果を十分に発揮することができない場合があり、一方、３．０％を越えると、紙面でのにじみや裏抜けが発生しやすくなり、好ましくない。 The content (active ingredient amount) of these acetylene-based surfactants is preferably 0.1 to 3.0%, more preferably 0.3 to 2.0%, based on the total amount of the ink composition. It is desirable to set it to%. If the content of this acetylene-based surfactant is less than 0.1%, the effects of the present disclosure may not be fully exerted, while if it exceeds 3.0%, bleeding or bleeding on the paper may occur. It is not preferable because strike-through is likely to occur.
〈水性ボールペン用インク組成物〉
　本開示の水性ボールペン用インク組成物には、上述の平均粒子径が０．５～６μｍのウレタン系着色樹脂粒子と、アセチレン系界面活性剤を含有することを特徴とするものであり、その他に、水溶性溶剤を含有することができ、また、上記ウレタン系着色樹脂粒子以外に汎用の着色剤を必要に応じて含有することができる。 <Ink composition for water-based ballpoint pens>
The ink composition for an aqueous ballpoint pen of the present disclosure is characterized by containing the above-mentioned urethane-based colored resin particles having an average particle diameter of 0.5 to 6 μm and an acetylene-based surfactant. , A water-soluble solvent can be contained, and a general-purpose colorant can be contained, if necessary, in addition to the urethane-based colored resin particles.
　用いることができる水溶性溶剤としては、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ポリエチレングリコール、３－ブチレングリコール、チオジエチレングリコール、グリセリン等のグリコール類や、エチレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテル、単独或いは混合して使用することができる。この水溶性溶剤の含有量は、インク組成物全量に対して、５～４０％とすることが望ましい。 Examples of the water-soluble solvent that can be used 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 ether. , Can be used alone or in combination. The content of this water-soluble solvent is preferably 5 to 40% with respect to the total amount of the ink composition.
　用いることができる着色剤としては、水溶性染料や、本開示の効果を損なわない範囲で顔料、例えば、無機顔料、有機顔料等も適宜量必要に応じて使用できる。
　水溶性染料としては、直接染料、酸性染料、食用染料、塩基性染料のいずれも本開示の効果を損なわない範囲で適宜量用いることができる。 As the colorant that can be used, water-soluble dyes and pigments such as inorganic pigments and organic pigments can be used in appropriate amounts as needed without impairing the effects of the present disclosure.
As the water-soluble dye, any of the direct dye, the acid dye, the edible dye, and the basic dye can be used in an appropriate amount as long as the effects of the present disclosure are not impaired.
　本開示の水性ボールペン用インク組成物には、少なくとも、上記平均粒子径が０．５～６μｍのウレタン系着色樹脂粒子と、アセチレン系界面活性剤を含有することを特徴とするものであり、上記着色樹脂粒子以外の着色剤、水溶性溶剤の他、残部として溶媒である水（水道水、精製水、蒸留水、イオン交換水、純水等）の他、本開示の効果を損なわない範囲で、分散剤、潤滑剤、増粘剤、ｐＨ調整剤、防錆剤、防腐剤もしくは防菌剤などを適宜含有することができる。 The water-based ink composition for a water-based ball pen of the present disclosure is characterized by containing at least urethane-based colored resin particles having an average particle diameter of 0.5 to 6 μm and an acetylene-based surfactant. In addition to colorants other than colored resin particles, water-soluble solvents, water as a solvent (tap water, purified water, distilled water, ion-exchanged water, pure water, etc.) as the balance, as long as the effects of the present disclosure are not impaired. , Dispersants, lubricants, thickeners, pH adjusters, rust preventives, preservatives, antibacterial agents and the like can be appropriately contained.
　用いることができる分散剤としては、ノニオン、アニオン界面活性剤や水溶性樹脂が用いられる。好ましくは水溶性高分子が用いられる。
　用いることができる潤滑剤としては、顔料の表面処理剤にも用いられる多価アルコールの脂肪酸エステル、糖の高級脂肪酸エステル、ポリオキシアルキレン高級脂肪酸エステル、アルキル燐酸エステルなどのノニオン系や、リン酸エステル、高級脂肪酸アミドのアルキルスルホン酸塩、アルキルアリルスルホン酸塩などのアニオン系、ポリアルキレングリコールの誘導体やポリエーテル変性シリコーンなどが挙げられる。
　用いることができる増粘剤としては、例えば、合成高分子、セルロースおよび多糖類からなる群から選ばれた少なくとも一種が望ましい。具体的には、アラビアガム、トラガカントガム、グアーガム、ローカストビーンガム、アルギン酸、カラギーナン、ゼラチン、キサンタンガム、ウェランガム、サクシノグリカン、ダイユータンガム、デキストラン、メチルセルロース、エチルセルロース、ヒドロキシエチルセルロース、カルボキシメチルセルロース、デンプングリコール酸及びその塩、ポリビニルピロリドン、ポリビニルメチルエーテル、ポリアクリル酸及びその塩、ポリエチレシオキサイド、酢酸ビニルとポリビニルピロリドンの共重合体、スチレン－アクリル酸共重合体及びその塩などが挙げられる。 As the dispersant that can be used, nonionic, anionic surfactant and water-soluble resin are used. A water-soluble polymer is preferably used.
Examples of the lubricant that can be used include nonionic compounds such as fatty acid esters of polyhydric alcohols, higher fatty acid esters of sugars, polyoxyalkylene higher fatty acid esters, and alkyl phosphate esters, which are also used as surface treatment agents for pigments, and phosphoric acid esters. , Alkyl sulfonate of higher fatty acid amide, anionic type such as alkyl allyl sulfonate, derivative of polyalkylene glycol, polyether-modified silicone and the like.
As the thickener that can be used, for example, at least one selected from the group consisting of synthetic polymers, cellulose and polysaccharides is desirable. Specifically, Arabic gum, tragacant gum, guar gum, locust bean gum, alginic acid, carrageenan, gelatin, xanthan gum, welan gum, succinoglycan, dieutan gum, dextran, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, starch glycolic acid and Examples thereof include the salt, polyvinylpyrrolidone, polyvinylmethyl ether, polyacrylic acid and a salt thereof, polyethyloxyxide, a copolymer of vinyl acetate and polyvinylpyrrolidone, a styrene-acrylic acid copolymer and a salt thereof.
　ｐＨ調整剤としては、アンモニア、尿素、モノエタノーアミン、ジエタノールアミン、トリエタノールアミンや、トリポリリン酸ナトリウム、炭酸ナトリウムなとの炭酸やリン酸のアルカリ金属塩、水酸化ナトリウムなどのアルカリ金属の水和物などが挙げられる。また、防錆剤としては、ベンゾトリアゾール、トリルトリアゾール、ジシクロへキシルアンモニウムナイトライト、サポニン類など、防腐剤もしくは防菌剤としては、フェノール、ナトリウムオマジン、安息香酸ナトリウム、チアゾリン系化合物、ベンズイミダゾール系化合物などが挙げられる。
　上記分散剤、潤滑剤、増粘剤、ｐＨ調整剤、防錆剤、防腐剤もしくは防菌剤などの各成分は、１種単独で使用してもよく、２種以上を併用してもよい。また、これらの市販品があればそれを使用することができる Acidity regulators include ammonia, urea, monoethanoamine, diethanolamine, triethanolamine, sodium tripolyphosphate, sodium carbonate and other carbonates, alkali metal salts of phosphoric acid, and alkali metal hydrates such as sodium hydroxide. And so on. In addition, rust preventives include benzotriazole, triltriazole, dicyclohexylammonium nitrate, saponins, etc., and preservatives or antibacterial agents include phenol, sodium omadin, sodium benzoate, thiazolin compounds, benzimidazole. Examples include system compounds.
Each component such as the dispersant, lubricant, thickener, pH adjuster, rust inhibitor, preservative or antibacterial agent may be used alone or in combination of two or more. .. Also, if you have these commercial products, you can use them.
　本開示の水性ボールペン用インク組成物は、少なくとも、上記平均粒子径が０．５～６μｍのウレタン系着色樹脂粒子と、アセチレン系界面活性剤と、水溶性溶剤、その他の各成分をボールペン用インクの用途に応じて適宜組み合わせて、ホモミキサー、ホモジナイザーもしくはディスパー等の攪拌機により撹拌混合することにより、更に必要に応じて、ろ過や遠心分離によってインク組成物中の粗大粒子を除去すること等によって水性ボールペン用インク組成物を調製することができる。 The water-based ballpoint pen ink composition of the present disclosure contains at least the urethane-based colored resin particles having an average particle diameter of 0.5 to 6 μm, an acetylene-based surfactant, a water-soluble solvent, and other components as the ballpoint pen ink. By appropriately combining the inks according to the intended use and stirring and mixing with a stirrer such as a homomixer, homogenizer or disper, and if necessary, removing coarse particles in the ink composition by filtration or centrifugation, etc. An ink composition for a ballpoint pen can be prepared.
　本開示の水性ボールペン用インク組成物は、他の水性インク組成物の製造方法と比べて特に変わるところはなく製造することができる。
　すなわち、本開示の水性ボールペン用インク組成物は、少なくとも、上記平均粒子径が０．５～６μｍのウレタン系着色樹脂粒子と、アセチレン系界面活性剤と、水溶性溶剤、その他の各成分をミキサー等、更に、例えば、強力な剪断を加えることができるビーズミル、ホモミキサー、ホモジナイザー等を用いて撹拌条件を好適な条件に設定等して混合撹拌することによって、水性ボールペン用インク組成物を製造することができる。
　また、本開示の水性ボールペン用インク組成物のｐＨ（２５℃）は、使用性、安全性、インク自身の安定性、インク収容体とのマッチング性の点からｐＨ調整剤などにより５～１０に調整されることが好ましく、更に好ましくは、６～９．５とすることが望ましい。 The ink composition for a water-based ballpoint pen of the present disclosure can be produced without any particular difference as compared with other methods for producing an water-based ink composition.
That is, in the ink composition for a water-based ballpoint pen of the present disclosure, at least the urethane-based colored resin particles having an average particle diameter of 0.5 to 6 μm, an acetylene-based surfactant, a water-soluble solvent, and other components are mixed. Further, for example, an ink composition for a water-based ballpoint pen is produced by mixing and stirring using a bead mill, a homomixer, a homogenizer, or the like capable of applying strong shearing, setting the stirring conditions to suitable conditions, and the like. be able to.
The pH (25 ° C.) of the ink composition for water-based ballpoint pens of the present disclosure is set to 5 to 10 depending on a pH adjuster or the like from the viewpoints of usability, safety, stability of the ink itself, and matching with the ink container. It is preferably adjusted, and more preferably 6 to 9.5.
　本開示の水性ボールペン用インク組成物は、ボールペンチップなどのペン先部を備えたボールペンに搭載される。
　本開示における水性ボールペンとしては、例えば、上記組成の水性ボールペン用インク組成物を直径が０．１８～２．０ｍｍのボールを備えたボールペン用インク収容体（リフィール）に収容すると共に、該インク収容体内に収容された水性インク組成物とは相溶性がなく、かつ、該水性インク組成物に対して比重が小さい物質、例えば、ポリブテン、シリコーンオイル、鉱油等がインク追従体として収容されるものが挙げられる。直径が上記範囲のボールを備えたものであれば、用いる水性ボールペンの構造などは、特に限定されず、特に、上記水性インク組成物をポリプロピレンチューブのインク収容管に充填し、先端のステンレスチップ（ボールは超鋼合金）を有するリフィールの水性ボールペンに仕上げたものが望ましい。
　更に、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。 The ink composition for a water-based ballpoint pen of the present disclosure is mounted on a ballpoint pen provided with a pen tip such as a ballpoint pen tip.
As the water-based ballpoint pen in the present disclosure, for example, the water-based ballpoint pen ink composition having the above composition is housed in a ballpoint pen ink container (refill) having a ball having a diameter of 0.18 to 2.0 mm, and the ink is stored. A substance that is incompatible with the water-based ink composition contained in the body and has a small specific gravity with respect to the water-based ink composition, for example, a substance containing polybutene, silicone oil, mineral oil, or the like as an ink follower. Can be mentioned. The structure of the water-based ballpoint pen to be used is not particularly limited as long as it includes balls having a diameter in the above range. In particular, the water-based ink composition is filled in an ink storage tube of a polypropylene tube, and a stainless steel tip at the tip ( It is desirable that the ball is finished in a refill water-based ballpoint pen having (super steel alloy).
Further, it may be a direct liquid type ballpoint pen provided with 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. ..
　好ましくは、水性ボールペンのボールの表面粗さＲａが１０ｎｍ未満であることが望ましく、特に好ましくは、該筆記ボールは、ボールの表面粗さＲａが４ｎｍ以下であることが望ましい。
　このとき、筆記ボールの表面粗さＲａが１０ｎｍ以上になると、書き味が段々低下することとなる。なお、本開示（後述する実施例を含む）における「表面粗さＲａ」は、非接触表面形状測定機（Ｚｙｇｏ社製ＮｅｗＶｉｅｗ７２００）により、レンズ倍率５０倍、評価長さ１００μｍ、ガウシアンフィルタ２５μｍの条件で設定し、それ以外はＪＩＳ　Ｂ０６０１（製品の幾何特性仕様－表面性状）に準拠するものとする。
　本開示の水性ボールペンでは、書き味を損なうことなく、本開示の効果を更に発揮できると共に、表面粗さが小さいボールを適用することが可能となる。 Preferably, the surface roughness Ra of the ball of the water-based ballpoint pen is less than 10 nm, and particularly preferably, the surface roughness Ra of the ball of the writing ball is 4 nm or less.
At this time, if the surface roughness Ra of the writing ball is 10 nm or more, the writing quality is gradually deteriorated. The "surface roughness Ra" in the present disclosure (including the examples described later) is defined by a non-contact surface shape measuring machine (NewView7200 manufactured by Zygo) under the conditions of a lens magnification of 50 times, an evaluation length of 100 μm, and a Gaussian filter of 25 μm. Other than that, it shall comply with JIS B0601 (Geometric characteristic specifications of the product-Surface texture).
The water-based ballpoint pen of the present disclosure can further exert the effects of the present disclosure without impairing the writing quality, and can apply a ball having a small surface roughness.
　また、本開示では、更なる本開示の効果を発揮する点等から、前記インク組成物は、ポリエチレンテレフタレートフィルム（ＰＥＴフィルム面、筆記面）とインクとの接触角が４０°以下であることが好ましい。筆記面とインクとの接触角が４０°以下とするためには、含有せしめる所定範囲の平均粒子径のアクリル系着色樹脂粒子種、アセチレン系界面活性剤種、並びに、これらの各含有量を好適に組み合わせることなどにより、調製することができる。本開示（後述する実施例を含む）において、接触角の測定には、自動接触角測定機（協和界面科学社製ＤＭ５００）を用いた。 Further, in the present disclosure, the contact angle between the polyethylene terephthalate film (PET film surface, writing surface) and the ink is 40 ° or less in the ink composition from the viewpoint of further exerting the effect of the present disclosure. preferable. In order to make the contact angle between the writing surface and the ink 40 ° or less, acrylic colored resin particle species, acetylene surfactant species, and their respective contents having an average particle diameter within a predetermined range to be contained are suitable. It can be prepared by combining with. In the present disclosure (including examples described later), an automatic contact angle measuring machine (DM500 manufactured by Kyowa Interface Science Co., Ltd.) was used for measuring the contact angle.
　このように構成される本開示の水性ボールペン用インク組成物にあっては、少なくとも、上記平均粒子径が０．５～６μｍのウレタン系着色樹脂粒子と、アセチレン系界面活性剤を含有することを特徴とするものであり、前記式（Ｉ）～（ＶＩ）などで示されるアセチレン系界面活性剤には、低い接触角を与え濡れ性を高める効果がある。これらのアセチレン系界面活性剤を使用することで、低温環境下で高粘度となりペン先から吐出しにくくなったインクでも高い濡れ性によりインクがボールに付着しやすくなり、筆記不良が発生しにくくなることが確認することができた。また、ボール表面粗さが大きいとインク濡れが良くなるが、その反面で書き味が低下する。本開示の水性ボールペン用インク組成物及び水性ボールペンでは、表面粗さが小さいボールを適用することが可能となり、良好な書き味と低温環境下での筆記性を更に高度に両立することができるものとなる。 The ink composition for an aqueous ballpoint pen of the present disclosure configured as described above contains at least the urethane-based colored resin particles having an average particle diameter of 0.5 to 6 μm and an acetylene-based surfactant. The acetylene-based surfactants represented by the formulas (I) to (VI) and the like are characterized by having a low contact angle and an effect of enhancing wettability. By using these acetylene-based surfactants, even if the ink has a high viscosity in a low temperature environment and is difficult to eject from the pen tip, the ink easily adheres to the ball due to its high wettability, and writing defects are less likely to occur. I was able to confirm that. Further, if the surface roughness of the ball is large, the ink wetness is improved, but on the other hand, the writing quality is deteriorated. In the ink composition for a water-based ballpoint pen and the water-based ballpoint pen of the present disclosure, it is possible to apply a ball having a small surface roughness, and it is possible to further achieve both good writing quality and writeability in a low temperature environment. It becomes.
　次に、用いる着色樹脂粒子の製造例１～２、水性ボールペン用インク組成物の実施例１～６及び比較例１～２により本開示を更に詳細に説明するが、本開示は下記実施例等に限定されるものではない。また、製造例１～２で得た着色樹脂粒子などの平均粒子径（Ｄ５０：μｍ）は、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。 Next, the present disclosure will be described in more detail with reference to Production Examples 1 and 2 of the colored resin particles to be used, Examples 1 to 6 of the ink composition for an aqueous ballpoint pen, and Comparative Examples 1 and 2. It is not limited to. The average particle size (D50: μm) of the colored resin particles obtained in Production Examples 1 and 2 was measured using a particle size distribution analyzer HRA9320-X100 manufactured by Nikkiso Co., Ltd.
〔製造例１：ウレタン系着色樹脂粒子１の製造〕
　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、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着色樹脂粒子（赤色粒子）を得た。
　この着色樹脂粒子の平均粒子径（Ｄ５０）は、３．２μｍであった。 [Production Example 1: Production of Urethane Colored Resin Particles 1]
While heating 11.5 parts by mass of ethylene glycol monobenzyl ether as an organic solvent to 60 ° C., 2.8 parts by mass of a water-insoluble dye (Valifast Red 1355, manufactured by Orient Chemical Industries Co., Ltd.) and diphenylmethane as a prepolymer were added. An oil phase solution was prepared by adding 7.2 parts by mass of a trimethylolpropane (1 mol) adduct (D-109, manufactured by Mitsui Chemical Industries, Ltd.) of diisocyanate (3 mol). On the other hand, while heating 200 parts by mass of distilled water to 60 ° C., 15 parts by mass of polyvinyl alcohol (PVA-205, manufactured by Kuraray Co., Ltd.) as a dispersant was dissolved therein to prepare an aqueous phase solution. 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 colored resin particles (red particles) were obtained by centrifuging the obtained dispersion.
The average particle size (D50) of the colored resin particles was 3.2 μm.
〔製造例２：ウレタン系着色樹脂粒子２の製造〕
　油相溶液として、エチレングリコールモノベンジルエーテル１１．６部と分散剤（ＤＩＳＰＥＲＢＹＫ－１１１、ビックケミー・ジャパン社製）１．８部とを６０℃に加温しながら、顔料（カーボンブラック、Ｃａｂｏｔ　Ｍｏｇｕｌ　Ｌ、キャボット社製）２．０部と、シナジスト（フタロシアニン顔料誘導体、ソルスパース５０００、ルーブリゾール社製）０．２部とを加えて十分分散させた。次いで、ここにプレポリマーとしてのキシリレンジイソシアネートのトリメチロールプロパン付加物（タケネート　Ｄ１１０Ｎ、三井化学社製）９．０質量部を加えて、油相溶液を作製した。水相溶液としては、蒸留水６００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着色樹脂粒子を得た。この着色樹脂粒子の平均粒子径（Ｄ５０）は、２．１μｍであった。 [Manufacturing Example 2: Production of Urethane-based Colored Resin Particles 2]
As an oil phase solution, 11.6 parts of ethylene glycol monobenzyl ether and 1.8 parts of a dispersant (DISPERBYK-111, manufactured by Big Chemie Japan Co., Ltd.) were heated to 60 ° C., and a pigment (carbon black, Cabot Mogul L) was used. , Cabot Corporation) 2.0 parts and Synagisto (phthalocyanine pigment derivative, Solsparse 5000, Lubrisol Co., Ltd.) 0.2 parts were added and sufficiently dispersed. Next, 9.0 parts by mass of a trimethylolpropane adduct of xylylene diisocyanate (Takenate D110N, manufactured by Mitsui Kagaku Co., Ltd.) as a prepolymer was added thereto to prepare an oil phase solution. As the aqueous phase solution, 600 parts by mass of distilled water is heated to 60 ° C., and 15 parts by mass of polyvinyl alcohol (PVA-205, manufactured by Kuraray Co., Ltd.) as a dispersant is dissolved therein to prepare an aqueous phase solution. did.
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. Colored resin particles were obtained by centrifuging the obtained dispersion. The average particle size (D50) of the colored resin particles was 2.1 μm.
〔実施例１～６及び比較例１～２〕
　上記製造例１、２のウレタン系着色性樹脂粒子を用いると共に、下記表１に示す配合組成などにより、常法により、各水性ボールペン用インク組成物を調整した。
　上記実施例１～６及び比較例１～２で得られた水性ボールペン用インク組成物について、上述の方法により、ＰＥＴフィルム面とインクとの接触角を測定すると共に、下記評価方法にて低温下（５℃下）での筆記性について評価を行った。
　これらの結果を下記表１に示す。 [Examples 1 to 6 and Comparative Examples 1 to 2]
The urethane-based colored resin particles of Production Examples 1 and 2 were used, and each water-based ballpoint pen ink composition was prepared by a conventional method according to the compounding composition shown in Table 1 below.
With respect to the ink compositions for water-based ballpoint pens obtained in Examples 1 to 6 and Comparative Examples 1 and 2, the contact angle between the PET film surface and the ink was measured by the above method, and at a low temperature by the following evaluation method. The writeability at (at 5 ° C.) was evaluated.
These results are shown in Table 1 below.
（低温下（５℃下）での筆記性の評価方法）
ＪＩＳ　Ｓ　６０６１：２０１０の７．３に示される試験用紙に、各インクを充填したボールペン（三菱鉛筆製　ＵＭ－１００、ボール径０．５ｍｍ、表面粗さ４ｎｍ）を用いて５℃環境下で直径４ｃｍの円を１０個連続で筆記し、下記評価基準で評価した。
＜評価基準＞
　　Ａ：すべて完全に筆記できた。
　　Ｂ：筆記できない部分が０ｍｍ超２０ｍｍ以下認められた。
　　Ｃ：筆記できない部分が２０ｍｍ超認められた。 (Evaluation method of writeability at low temperature (5 ° C))
Using a ballpoint pen (Mitsubishi Pencil UM-100, ball diameter 0.5 mm, surface roughness 4 nm) filled with each ink on the test paper shown in 7.3 of JIS S 6061: 2010, the diameter under a 5 ° C environment. Ten 4 cm circles were written in succession and evaluated according to the following evaluation criteria.
<Evaluation criteria>
A: I was able to write everything completely.
B: A part that could not be written was found to be more than 0 mm and 20 mm or less.
C: A part that could not be written was found to exceed 20 mm.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　上記表１の結果から明らかなように、本開示範囲となる実施例１～６の水性ボールペン用インク組成物は、本開示の範囲外となる比較例１～２に較べ、低温環境下であってもインク粘度の上昇が少なく、筆記不良が発生しにくい水性ボールペン用インク組成物及びそれを搭載した水性ボールペンとなることが確認された。 As is clear from the results in Table 1 above, the ink compositions for water-based ballpoint pens of Examples 1 to 6 which are within the scope of the present disclosure are in a low temperature environment as compared with Comparative Examples 1 and 2 which are outside the scope of the present disclosure. However, it was confirmed that the ink composition for a water-based ballpoint pen, which has a small increase in ink viscosity and is less likely to cause writing defects, and a water-based ballpoint pen equipped with the composition.
　水性ボールペンに好適なインク組成物が得られる。 An ink composition suitable for a water-based ballpoint pen can be obtained.

Claims (4)

  1. 　少なくとも、アセチレン系界面活性剤と、平均粒子径が０．５～６μｍのウレタン系着色樹脂粒子と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。 An ink composition for a water-based ballpoint pen, which comprises at least an acetylene-based surfactant and urethane-based colored resin particles having an average particle diameter of 0.5 to 6 μm.
  2. 　ポリエチレンテレフタレートフィルムとインクとの接触角が４０°以下であることを特徴とする請求項１記載の水性ボールペン用インク組成物。 The ink composition for a water-based ballpoint pen according to claim 1, wherein the contact angle between the polyethylene terephthalate film and the ink is 40 ° or less.
  3. 　請求項１又は２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。 A water-based ballpoint pen characterized in that the ink composition for a water-based ballpoint pen according to claim 1 or 2 is mounted.
  4. 　水性ボールペンのボールの表面粗さが１０ｎｍ未満であることを特徴とする請求項３記載の水性ボールペン。 The water-based ballpoint pen according to claim 3, wherein the surface roughness of the ball of the water-based ballpoint pen is less than 10 nm.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002226743A (en) * 2001-01-31 2002-08-14 Canon Inc Water-based ink, ink jet recording method using the same, recording unit, ink cartridge and ink jet recording apparatus
JP2005307106A (en) * 2004-04-26 2005-11-04 Pilot Corporation Ink for ball-point pen using oil-in-water type resin emulsion and ball-point pen using the ink
JP2006096015A (en) * 2004-09-30 2006-04-13 Pentel Corp Ball-point pen tip and ball-point pen using it
JP2010155347A (en) * 2008-12-26 2010-07-15 Pilot Corporation Ball-point pen
WO2011074634A1 (en) * 2009-12-17 2011-06-23 三菱鉛筆株式会社 Aqueous marking ink composition
WO2019082888A1 (en) * 2017-10-25 2019-05-02 株式会社パイロットコーポレーション Ink composition for water-based ballpoint pen, and water-based ballpoint pen including same
JP2020100731A (en) * 2018-12-21 2020-07-02 株式会社パイロットコーポレーション Aqueous ballpoint ink composition and aqueous ballpoint including the same

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002226743A (en) * 2001-01-31 2002-08-14 Canon Inc Water-based ink, ink jet recording method using the same, recording unit, ink cartridge and ink jet recording apparatus
JP2005307106A (en) * 2004-04-26 2005-11-04 Pilot Corporation Ink for ball-point pen using oil-in-water type resin emulsion and ball-point pen using the ink
JP2006096015A (en) * 2004-09-30 2006-04-13 Pentel Corp Ball-point pen tip and ball-point pen using it
JP2010155347A (en) * 2008-12-26 2010-07-15 Pilot Corporation Ball-point pen
WO2011074634A1 (en) * 2009-12-17 2011-06-23 三菱鉛筆株式会社 Aqueous marking ink composition
WO2019082888A1 (en) * 2017-10-25 2019-05-02 株式会社パイロットコーポレーション Ink composition for water-based ballpoint pen, and water-based ballpoint pen including same
JP2020100731A (en) * 2018-12-21 2020-07-02 株式会社パイロットコーポレーション Aqueous ballpoint ink composition and aqueous ballpoint including the same

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