WO2024005056A1 - Aqueous ink composition for writing utensil and writing utensil housing same - Google Patents

Aqueous ink composition for writing utensil and writing utensil housing same Download PDF

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Publication number
WO2024005056A1
WO2024005056A1 PCT/JP2023/023934 JP2023023934W WO2024005056A1 WO 2024005056 A1 WO2024005056 A1 WO 2024005056A1 JP 2023023934 W JP2023023934 W JP 2023023934W WO 2024005056 A1 WO2024005056 A1 WO 2024005056A1
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Prior art keywords
ink
pigment
ink composition
guanine
examples
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PCT/JP2023/023934
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French (fr)
Japanese (ja)
Inventor
遊之 尾関
Original Assignee
株式会社パイロットコーポレーション
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Publication of WO2024005056A1 publication Critical patent/WO2024005056A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
    • B43K—IMPLEMENTS FOR WRITING OR DRAWING
    • B43K7/00—Ball-point pens
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
    • B43K—IMPLEMENTS FOR WRITING OR DRAWING
    • B43K8/00—Pens with writing-points other than nibs or balls
    • B43K8/02—Pens with writing-points other than nibs or balls with writing-points comprising fibres, felt, or similar porous or capillary material
    • 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 disclosure relates to a water-based ink composition for writing instruments and a writing instrument containing the same. More specifically, the present invention relates to an aqueous ink composition for a writing instrument that has excellent pigment dispersion stability and is capable of forming clear handwriting with excellent concealment properties, and a writing instrument containing the same.
  • ink compositions for writing instruments using white pigments such as titanium oxide have been known in order to obtain handwriting with hiding properties.
  • ink compositions for writing instruments that can form pastel-like handwriting by blending colorants of other colors with such ink compositions with high hiding properties are also preferably used.
  • titanium oxide is a pigment with a high specific gravity
  • the pigment tends to settle over time, and when a hard cake is formed, it becomes difficult to redisperse the pigment.
  • writing instruments using ink compositions containing titanium oxide tend to lose handwriting density when stored with the writing tip facing upward, and the ink ejection properties tend to decrease when stored with the writing tip facing downward. It becomes easier to decrease. For this reason, studies are being conducted to increase the viscosity of the ink using thickeners and the like to suppress the precipitation of titanium oxide.
  • Patent Document 1 discloses an aqueous pigment composition comprising titanium oxide, an aluminum silicate pigment, and a specific resin.
  • Patent Document 2 discloses an aqueous ink composition comprising at least titanium oxide, succinoglycan, and water.
  • Patent Document 3 discloses a water-based ink for ballpoint pens consisting of titanium oxide and oleic acid.
  • Patent Document 4 describes an aqueous writing instrument comprising titanium oxide, a chromatic pigment, silica powder and/or aluminosilicate, a water-soluble resin, a specific dispersant, a surfactant, and water.
  • a pigmented ink is disclosed.
  • titanium oxide may settle over time and form a hard cake, or in the ink. It was difficult to stably disperse titanium oxide in an ink composition because color separation was likely to occur.
  • the present disclosure aims to provide a water-based ink composition for a writing instrument that has excellent pigment dispersion stability and can form clear handwriting with excellent concealment properties, and a writing instrument containing the same.
  • Aspect 1 of the present invention is The present invention is an aqueous ink composition for a writing instrument comprising at least a pigment containing a guanine pigment and water.
  • Aspect 2 of the present invention is The ink composition according to aspect 1, further comprising a dispersant.
  • Aspect 3 of the present invention is The ink composition according to aspect 2, wherein the dispersant has an acidic group and/or a salt of an acidic group.
  • Aspect 4 of the present invention is The ink composition according to any one of aspects 1 to 3, wherein the guanine pigment has an average particle diameter of 0.1 to 1 ⁇ m.
  • Aspect 5 of the present invention is The ink composition according to any one of aspects 1 to 4, wherein the content of the guanine pigment with respect to the total mass of the ink composition is 1 to 50% by mass.
  • Aspect 6 of the present invention is The ink composition according to any one of aspects 1 to 5, further comprising a colorant.
  • Aspect 7 of the present invention is A writing instrument containing the ink composition according to any one of aspects 1 to 6.
  • an aqueous ink composition for writing instruments using a pigment containing a guanine pigment in which the pigment is difficult to settle over time, has excellent pigment dispersion stability, and has a clear color with excellent hiding properties. It is possible to provide a water-based ink composition for a writing instrument that can form handwriting, and a writing instrument containing the same.
  • the aqueous ink composition for writing instruments (hereinafter sometimes referred to as "ink composition” or “ink”) according to the embodiment of the present invention contains at least a pigment containing a guanine pigment and water.
  • a pigment containing a guanine pigment contained in the aqueous ink composition according to the embodiment of the present invention.
  • the ink composition according to the embodiment of the present invention contains a guanine pigment.
  • a guanine pigment is a pigment made of guanine.
  • Guanine is one of the main bases constituting nucleic acids, and is an organic substance derived from living organisms. For example, it exists in a crystalline state on the body surface of fish such as hairtail, herring, and sardines. Crystalline guanine (guanine crystals) forms a layered structure on the body surface of these fish, reflecting or refracting light, so fish such as hairtail, herring, and sardines have a glossy (pearlescent) surface on their body surfaces. gender).
  • guanine is considered to be a highly safe compound, and is safe for the human body and the environment. It has little impact.
  • Guanine can be obtained from commercial products, but natural guanine crystals collected from fish such as hairtail, herring, and sardines may also be used. Furthermore, artificial guanine crystals obtained by dissolving commercially available or natural guanine crystals in a solvent and recrystallizing the crystals can also be used.
  • Titanium oxide which is conventionally used as a white pigment, has a high specific gravity and therefore tends to settle in the ink composition, and when it settles, it tends to form a hard cake, which may make redispersion difficult.
  • guanine pigment since guanine pigment has a lower specific gravity than titanium oxide, it is less likely to settle over time and has excellent dispersion stability, thereby suppressing the formation of a hard cake.
  • the ink composition according to the embodiment of the present invention uses a pigment containing a guanine pigment, so that the pigment is difficult to settle over time and has excellent dispersion stability. Therefore, the ink composition according to the embodiment of the present invention can form clear handwriting with excellent concealment properties at a uniform density. Further, even when the ink composition according to the embodiment of the present invention contains a colorant described below, separation of the guanine pigment and the colorant in the ink composition is suppressed. Therefore, the ink composition according to the embodiment of the present invention can form colored handwriting with concealing properties at a uniform density.
  • the average particle diameter of the guanine pigment is not particularly limited, but is preferably 0.1 to 1 ⁇ m, more preferably 0.2 to 0.95 ⁇ m, even more preferably 0.25 to 0.65 ⁇ m, and particularly preferably 0. It is in the range of .25 to 0.4 ⁇ m. When the average particle diameter is within the above range, the hiding properties of the ink composition and the dispersion stability of the guanine pigment are both highly compatible.
  • the average particle diameter was measured using a dynamic light scattering particle size distribution measuring device [manufactured by Microtrac Bell Co., Ltd., product name], which was calibrated based on values measured using standard samples or other measurement methods. : NANOTRAC FLEX] is the value of the average particle diameter (median diameter) on a volume basis. Note that even if the ink composition according to the embodiment of the present invention contains pigments other than guanine pigments, the above can be achieved by separating guanine and other pigments by density gradient centrifugation using the difference in specific gravity. Similarly, the average particle size of guanine alone can be measured.
  • the content of the guanine pigment with respect to the total mass of the ink composition is not particularly limited, but is preferably in the range of 1 to 50% by mass, more preferably 5 to 30% by mass.
  • the content of the guanine pigment exceeds 50% by mass, the ink ejection stability of a writing instrument containing the ink composition tends to decrease, and writing defects such as blurring and line skipping tend to occur.
  • the content is less than 1% by mass, it will be difficult to obtain a suitable handwriting density for a writing instrument, and the concealability of handwriting will be likely to be impaired.
  • the guanine pigment is not particularly limited as long as it can be dispersed in the ink composition.
  • the guanine pigment can be produced, for example, by mechanically pulverizing commercially available products or natural or artificial guanine crystals into particles using various dispersing machines such as jet mills, attritors, and bead mills. Alternatively, it can also be produced by dissolving commercially available or natural guanine crystals in a solvent and recrystallizing them into particles.
  • a colored guanine pigment itself can also be used.
  • the ink composition according to the embodiment of the present invention can further contain a dispersant.
  • the dispersant adsorbs to the surface of the guanine pigment and separates the guanine pigments from each other while keeping the distance between the guanine pigments above a certain level and preventing agglomeration, improving the dispersibility of the guanine pigment in the ink. be able to. Further, even when guanine pigments aggregate with each other to form aggregates, since aggregates with low density are formed, hard cake formation after the guanine pigments are precipitated can be easily suppressed.
  • dispersant examples include surfactants, polymer dispersants, inorganic compounds, and the like.
  • surfactant used as a dispersant examples include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and the like.
  • polymer dispersants used as dispersants include polyvinyl butyral; polyvinyl ether; ketone resin; carboxylic acid such as styrene-maleic acid copolymer, styrene-acrylic acid copolymer, acrylic acid-sulfonic acid copolymer
  • examples include resins containing groups; hydroxyethyl cellulose and derivatives thereof; acrylic polymers; PO/EO adducts; amine oligomers of polyesters.
  • Examples of the inorganic compound used as a dispersant include pyrophosphate, hexametaphosphate, and the like.
  • the dispersant preferably has acidic groups and/or salts of acidic groups.
  • An acidic group and/or a salt of an acidic group easily binds to guanine (for example, -NH 2 group in guanine, etc.), and the dispersant tends to gather around the guanine, so it is excellent as a dispersant.
  • the acidic group include a phosphoric acid group, a carboxy group, a sulfonic acid group, a phosphoric acid ester group, a sulfuric acid ester group, a nitric acid ester group, a phosphorous acid group, a phosphonic acid group, and a sulfinic acid group.
  • salts of acidic groups include metal salts such as potassium salts and sodium salts of the above-mentioned acidic groups, and 2-amino-2-methyl-1-propanol salts. These may be contained in one molecule or in combination of two or more.
  • Commercially available dispersants having acidic groups and/or salts of acidic groups include, for example, DISPER BYK series from BYK Chemie Japan Co., Ltd., Florene series from Kyoeisha Kagaku Co., Ltd., Aron series from Toagosei Co., Ltd., and BASF Japan Co., Ltd.
  • a dispersant having an acidic group and/or a salt of an acidic group can also function as a surfactant and/or a lubricant, such as a phosphate ester surfactant, but the embodiment of the present invention It is treated as a dispersant.
  • the molecular weight (mass average molecular weight) may be 300 or more and 200,000 or less, or 300 or more and 50,000 or less.
  • the dispersant preferably has an acid value. This makes it easier for the dispersant to bind to guanine.
  • the dispersant it is preferable that at least one of the following groups (a) to (e) is satisfied.
  • the acid value of the dispersant is 100 mgKOH/g or more
  • the acid value is 5 to 15 mgKOH/g, and the comb-shaped structure (i.e., a structure in which branch polymer parts are grafted to the main polymer part)
  • Both acid value and amine value are 15 or more and less than 30.
  • Examples of commercially available dispersants that have an acidic group and/or a salt of an acidic group and satisfy the above (a) include DISPER BYK-102 [manufactured by BYK Chemie Japan Co., Ltd.] and Joncryl 57J [manufactured by BASF Japan Co., Ltd.]. (manufactured by BASF Japan Ltd.), Jonkryl 63J (manufactured by BASF Japan Ltd.), Jonkryl 70J (manufactured by BASF Japan Ltd.), and the like.
  • Examples of commercially available dispersants having an acidic group and/or a salt of an acidic group and satisfying the above (b) include Solsperse 46000 (manufactured by Nippon Lubrizol Co., Ltd.) and Solsperse 47000 (manufactured by Nippon Lubrizol Co., Ltd.). [manufactured]] etc.
  • Examples of commercially available dispersants having an acidic group and/or a salt of an acidic group and satisfying the above (c) include Joncryl 57J [manufactured by BASF Japan Ltd.] and Joncryl 63J [manufactured by BASF Japan Ltd.]. [manufactured by BASF Japan Co., Ltd.], and Jonkryl 70J [manufactured by BASF Japan Co., Ltd.].
  • the acrylic-sulfonic acid copolymer may be in the form of a metal salt (preferably a sodium salt) or an unneutralized type, and is preferably an unneutralized type.
  • Examples of commercially available dispersants that have an acidic group and/or a salt of an acidic group and satisfy the above (e) include DISPER BYK-2010 [manufactured by BYK-Chemie Japan Co., Ltd.], Florene G-700AMP [Kyoeisha Chemical Co., Ltd.] Co., Ltd.].
  • the content of the dispersant relative to the guanine pigment is not particularly limited, but is preferably 0.1 to 100% by mass, more preferably 1 to 100% by mass.
  • the amount is 50% by weight, more preferably 5 to 30% by weight.
  • the content of the dispersant is within the above range, the dispersibility of the guanine pigment in the ink composition can be maintained more stably.
  • An ink composition according to an embodiment of the present invention comprises water.
  • Water is used as a dispersion medium to disperse the guanine. It is also possible to use an organic solvent or the like as a dispersion medium.
  • guanine is sparingly soluble in organic solvents (that is, slightly soluble), it is insoluble in water. It is important to use water in order to make more effective use of water.
  • many organic solvents have a small specific gravity (for example, ethanol has a specific gravity of 0.789), and when an organic solvent is used as a dispersion medium, the difference in specific gravity between the organic solvent and guanine becomes large, causing water to evaporate.
  • Water is not particularly limited, and examples include tap water, ion-exchanged water, ultrafiltrated water, and distilled water.
  • the content of water relative to the total mass of the ink composition is not particularly limited, but is preferably in the range of 10 to 90% by mass, more preferably 30 to 80% by mass.
  • the ink composition according to the embodiment of the present invention may further contain a colorant.
  • a colorant By using a guanine pigment and a coloring agent in combination, an ink composition exhibiting a colored (pastel-like color) having concealing properties can be obtained.
  • the colorant is not particularly limited as long as it is a dye or pigment that can be dissolved or dispersed in a solvent.
  • dyes examples include acid dyes, basic dyes, direct dyes, oil-soluble dyes, and disperse dyes.
  • acidic dyes examples include New Coccin (C.I. 16255), Tartrazine (C.I. 19140), Acid Blue Black 10B (C.I. 20470), Guinea Green (C.I. 42085), and Brilliant. Blue FCF (C.I.42090), Acid Violet 6B (C.I.42640), Soluble Blue (C.I.42755), Naphthalene Green (C.I.44025), Eosin (C.I.45380) , phloxine (C.I. 45410), erythrosin (C.I. 45430), nigrosine (C.I. 50420), acidflavin (C.I. 56205), and the like.
  • Examples of basic dyes include chrysoidine (C.I.11270), methyl violet FN (C.I.42535), crystal violet (C.I.42555), malachite green (C.I.42000), and Victoria blue.
  • Examples include FB (C.I.44045), Rhodamine B (C.I.45170), Acridine Orange NS (C.I.46005), and Methylene Blue B (C.I.52015).
  • direct dyes examples include Congo Red (C.I.22120), Direct Sky Blue 5B (C.I.24400), Violet BB (C.I.27905), and Direct Deep Black EX (C.I.30235). , Kayaras Black G Conch (C.I. 35225), Direct Fast Black G (C.I. 35255), and Phthalocyanine Blue (C.I. 74180).
  • oil-soluble dyes examples include C.I. I. Solvent Black 7, C. I. Solvent Black 123, C. I. Solvent Blue 2, C. I. Solvent Blue 25, C. I. Solvent Blue 55, C. I. Solvent Blue 70, C. I. Solvent Red 8, C. I. Solvent Red 49, C. I. Solvent Red 100, C. I. Solvent Violet 8, C. I. Solvent Violet 21, C. I. Solvent Green 3, C. I. Solvent Yellow 21, C. I. Solvent Yellow 44, C. I. Solvent Yellow 61, C. I. An example is Solvent Orange 37.
  • disperse dyes examples include C.I. I. Disperse Yellow 82, C. I. Disperse Yellow 3, C. I. Disperse Yellow 54, C. I. Disperse Red 191, C. I. Disperse Red 60, C. I. An example is Disperse Violet 57.
  • pigments examples include inorganic pigments, organic pigments, glitter pigments, fluorescent pigments, and luminescent pigments.
  • inorganic pigments examples include carbon black, iron black, yellow iron oxide, Bengara, and ultramarine blue.
  • organic pigments examples include azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, thioindigo pigments, anthraquinone pigments, Examples include quinophthalone pigments, diketopyrrolopyrrole pigments, threne pigments, indigo pigments, phthalone pigments, methine/azomethine pigments, and metal complex pigments.
  • the pigment it is also possible to use a water-dispersed pigment, etc., in which the pigment is finely and stably dispersed in an aqueous medium using a surfactant and/or resin in advance.
  • resins for dispersing pigments include polyamide, urethane resin, polyester, epoxy resin, melamine resin, phenol resin, silicone resin, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, polystyrene, and acrylic.
  • acrylic resins include acid resins, maleic acid resins, gum arabic, cellulose, dextran, casein, derivatives thereof, and copolymers of the above resins.
  • Glittering pigments include metallic luster pigments in which the surface of a core material such as glass pieces is coated with gold, silver, etc., natural mica, synthetic mica, flaky aluminum oxide, etc., and metal oxides such as titanium oxide on the surface of a core material such as flaky aluminum oxide.
  • fluorescent pigments examples include fluorescent pigments in the form of synthetic resin fine particles in which various fluorescent dyes are made into a solid solution in a resin matrix.
  • Luminescent pigments are general-purpose pigments that have the property of absorbing and accumulating light from the sun and/or electric lamps, and gradually emitting light in a dark place (this is called afterglow). Examples include phosphorescent pigments such as CaS/Bi type, CaSrS/Bi type, ZnS/Cu type, ZnCdS/Cu type, and SrAl2O4/rare earth metal type.
  • One type of colorant or a combination of two or more types can be used.
  • a pigment dispersant can be used as necessary.
  • the pigment dispersant include anionic and nonionic surfactants; anionic polymers such as polyacrylic acid and styrene-acrylic acid; nonionic polymers such as PVP and PVA.
  • dyes or pigments are effective when used as they are, but microcapsule pigments in which dyes or pigments are encapsulated in microcapsules, and/or resin particles containing dyes or pigments may also be used as colorants. Can be done. In particular, dyes or pigments can be isolated and protected from the external environment by being encapsulated in microcapsules, and the water resistance and light resistance of the encapsulated material can be improved.
  • a microcapsule pigment can be formed by encapsulating a colored body in which the above dye or pigment is dissolved or dispersed in an oily medium in microcapsules.
  • oil-based media examples include monobasic acid esters, dibasic acid monoesters, dibasic acid diesters, esters such as partial or complete esters of polyhydric alcohols, aromatic hydrocarbons such as alkylbenzenes and alkylnaphthalenes, and higher-grade esters.
  • esters such as partial or complete esters of polyhydric alcohols, aromatic hydrocarbons such as alkylbenzenes and alkylnaphthalenes, and higher-grade esters.
  • examples include alcohols, ketones, and ethers.
  • the oil-based medium can be used alone or in combination of two or more.
  • Microcapsule pigments can be microencapsulated using conventionally known isocyanate-based interfacial polymerization methods, melamine-formalin-based in-situ polymerization methods, in-liquid curing coating methods, phase separation methods from aqueous solutions, and phase separation methods from organic solvents. , melting and dispersion cooling method, air suspension coating method, spray drying method, etc., which are appropriately selected depending on the application.
  • the material for the capsule include epoxy resin, urea resin, urethane resin, and isocyanate resin.
  • a secondary resin film can be further provided on the surface of the microcapsules to impart durability or to modify the surface characteristics for practical use.
  • resin particles containing a dye examples include resin particles in which the above-described dye is homogeneously dissolved or dispersed, and resin particles in which a dye is dyed onto the resin particles.
  • the resin constituting the resin particles is not particularly limited, but thermosetting resins are preferred.
  • Thermosetting resins are preferable because they have better solvent resistance and heat resistance than thermoplastic resins, and they also have better migration resistance for the dyes they contain, which prevents dyes from eluting from the resin. be.
  • thermosetting resins guanamine resin or melamine resin is preferable because they can further suppress dye elution.
  • Examples of the resin particles containing a pigment include resin particles in which the above pigment is homogeneously dispersed in the resin particles, and resin particles in which the surface of the resin particles is coated with a pigment.
  • the resin constituting the resin particles is not particularly limited, and general-purpose resins can be used.
  • the resin particles can be produced by a pulverization method, a spray drying method, or a polymerization method in which polymerization is performed in the presence of a dye or pigment in an aqueous or oily medium.
  • polymerization methods include suspension polymerization, suspension polycondensation, dispersion polymerization, and emulsion polymerization.
  • the shape of the resin particles is not particularly limited, and spherical, polygonal, flat, and other resin particles can be used. Among these, it is preferable to use spherical resin particles.
  • the content of the colorant with respect to the total mass of the ink composition is not particularly limited, but is preferably from 0.01 to The amount is 50% by weight, more preferably 0.1 to 30% by weight.
  • the content of the colorant exceeds 50% by mass, the ink ejection properties of the writing instrument containing the ink composition tend to decrease, and writing defects such as blurring and line skipping tend to occur.
  • the content is less than 0.01% by mass, it becomes difficult to obtain a suitable handwriting density as a writing instrument.
  • thermochromic materials that change color due to temperature changes and/or photochromic materials that change color due to light irradiation. These color changes may be reversible or irreversible. Reversible thermochromic materials and/or reversible photochromic materials are suitable because they can repeatedly exhibit color changes due to temperature changes or light irradiation.
  • the reversible thermochromic material includes (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reaction that determines the temperature at which the color reaction of the components (a) and (b) above occurs.
  • Examples include reversible thermochromic compositions comprising a medium.
  • the heat-decolorizing type means that the color is decolored by heating and the color is developed by cooling.
  • This reversible thermochromic composition changes color before and after a predetermined temperature (color change point), becomes decolored at a temperature above the high temperature side discoloration point, and changes color at a temperature below the low temperature side discoloration point.
  • the heat-decolorizing type means that the color is decolored by heating and the color develops by cooling.
  • the shape of the curve plotting the change in color density due to temperature change is such that the shape of the curve is such that the temperature increases from a lower side than the discoloration temperature range, and vice versa.
  • the reversible thermochromic composition has a complete color development temperature t 1 in a freezing room or in a cold room. Specify the temperature that can only be obtained from the ground, etc., and the complete discoloration temperature t4 to be within the range of frictional heat from a friction body and the temperature that can be obtained from a familiar heating body such as a hair dryer, and specify the ⁇ H value between 40 and 100 degrees Celsius. By doing so, it is possible to effectively maintain the color exhibited under normal conditions (in the everyday living temperature range).
  • the temperature that can only be obtained in a freezing room, a cold region, etc. is in the range of -50 to 0°C, preferably in the range of -40 to -5°C, and more preferably in the range of -30 to -10°C.
  • the temperature obtained from a familiar heating element such as a hair dryer is in the range of 50 to 95°C, preferably 50 to 90°C, more preferably 60 to 80°C.
  • thermochromic compositions using gallic acid ester, which are described in Japanese Patent Publication No. 51-44706, Japanese Patent Application Laid-Open No. 2003-253149, etc., can also be used.
  • the heat coloring type means that the color develops when heated and the color disappears when cooled.
  • the reversible thermochromic composition is a compatible solution containing the above components (a), (b), and (c) as essential components, and the proportion of each component depends on the concentration, color change temperature, color change form, and each component. Depends on the type.
  • the component ratio at which desired characteristics can be obtained is (a) component 1 to (b) component 0.1 to 100, preferably 0.1 to 50, more preferably 0.5 to 20, ( c) Component ranges from 1 to 800, preferably from 5 to 200, more preferably from 10 to 100 (all the above ratios are parts by mass).
  • Examples of reversible photochromic materials include spirooxazine derivatives and spiropyran, which develop color when irradiated with sunlight, ultraviolet light, or blue light with a peak emission wavelength in the range of 400 to 495 nm, and disappear when irradiation is stopped.
  • Examples include photochromic compounds such as derivatives and naphthopyran derivatives.
  • spirooxazine derivatives include conventionally known indolinospirobenzoxazine compounds, indolinospironaphthoxazine compounds, indolinospirophenanthrooxazine compounds, and indolinospiroquinolinooxazine compounds.
  • photochromic compounds having photomemory properties include conventionally known fulgide derivatives, diarylethene derivatives, and the like.
  • a reversible photochromic composition in which the above photochromic compound is dissolved in various oligomers can also be used.
  • oligomers include styrene oligomers, acrylic oligomers, terpene oligomers, and terpene phenol oligomers.
  • styrenic oligomer examples include low molecular weight polystyrene, styrene/ ⁇ -methylstyrene copolymer, ⁇ -methylstyrene polymer, ⁇ -methylstyrene/vinyltoluene copolymer, and the like.
  • acrylic oligomer examples include acrylic ester copolymers.
  • terpene oligomer examples include ⁇ -pinene polymer, ⁇ -pinene polymer, and d-limonene polymer.
  • terpene phenol oligomer examples include ⁇ -pinene/phenol copolymer.
  • One type of oligomer or a combination of two or more types can be used.
  • thermochromic composition or reversible photochromic composition is effective when used as is, but it may be encapsulated in microcapsules to form a reversible thermochromic microcapsule pigment or a reversible photochromic microcapsule pigment. Alternatively, it can be dispersed in a thermoplastic resin or thermosetting resin to form reversible thermochromic resin particles or reversible photochromic resin particles, and used as a coloring agent applied to the embodiments of the present invention. can.
  • thermochromic microcapsule pigments and reversible photochromic microcapsule pigments may be referred to as "microcapsule pigments”
  • reversible thermochromic resin particles and reversible photochromic resin particles may be referred to as "resin particles”.
  • the reversible thermochromic composition or reversible photochromic composition is preferably encapsulated in microcapsules to form a reversible thermochromic microcapsule pigment or a reversible photochromic microcapsule pigment.
  • encapsulating it in microcapsules it is possible to construct chemically and physically stable microcapsule pigments, and furthermore, under various usage conditions, reversible thermochromic compositions or reversible photochromic compositions This is because the same composition can be maintained and the same effects can be achieved.
  • Microencapsulation can be achieved using conventionally known isocyanate-based interfacial polymerization methods, melamine-formalin-based in-situ polymerization methods, in-liquid curing coating methods, phase separation methods from aqueous solutions, phase separation methods from organic solvents, and melting and dispersion cooling. method, air suspension coating method, spray drying method, etc., which are appropriately selected depending on the purpose.
  • the material for the capsule include epoxy resin, urea resin, urethane resin, and isocyanate resin.
  • a secondary resin film can be further provided on the surface of the microcapsules to impart durability or to modify the surface characteristics for practical use.
  • the above microcapsule pigment preferably has a mass ratio of inclusions to wall film of 7:1 to 1:1, and when the mass ratio of inclusions to wall film is within the above range, Decrease in color density and sharpness can be prevented. More preferably, the mass ratio of inclusions to wall membrane is 6:1 to 1:1.
  • a microcapsule pigment that exhibits color change behavior from colored (1) to colored (2) can also be obtained.
  • the content of the colorant relative to the total weight of the ink composition is not particularly limited, but is preferably 5 to 40% by weight, more preferably 10 to 40% by weight. %, more preferably in the range of 15 to 35% by weight. If the content of the colorant exceeds 40% by mass, the ink ejection properties of the writing instrument containing the ink composition will be reduced, and writing defects such as blurring and line skipping will likely occur. On the other hand, if the content is less than 5% by mass, it is difficult to obtain suitable discoloration properties and handwriting density as a writing instrument, and it becomes difficult to fully satisfy the discoloration function.
  • the average particle diameter of the reversible thermochromic microcapsule pigment or resin particles or the reversible photochromic microcapsule pigment or resin particles is preferably 0.01 to 5 ⁇ m, more preferably 0.1 to 3 ⁇ m, and even more preferably 0. It is in the range of .5 to 3 ⁇ m.
  • the average particle diameter of the above-mentioned microcapsule pigment or resin particles exceeds 5 ⁇ m, it becomes difficult to obtain good ink ejectability when used in a writing instrument.
  • the average particle diameter is less than 0.01 ⁇ m, it becomes difficult to exhibit high-density color development.
  • the average particle diameter determines the particle area using image analysis particle size distribution measurement software [manufactured by Mountech Co., Ltd., product name: Macview], and calculate the projected area circle equivalent diameter from the area of the particle area. (Heywood diameter) is calculated, and the value is measured as the average particle diameter of particles equivalent to an equal-volume sphere based on the calculated value.
  • the particle diameter of all or most of the particles exceeds 0.2 ⁇ m, use a particle size distribution analyzer [manufactured by Beckman Coulter Co., Ltd., product name: Multisizer 4e] to divide the particles into equal volumes by the Coulter method. It is also possible to measure as the average particle diameter of particles equivalent to spheres.
  • a laser diffraction/scattering particle size distribution measuring device manufactured by Horiba, Ltd., product name: LA- 300] to measure the volume-based particle diameter and average particle diameter.
  • the ink composition according to the embodiment of the present invention can contain optional components within a range that does not impair the effects of the embodiment of the present invention.
  • the ink composition according to the embodiment of the present invention can be blended with a thickener to suppress aggregation and sedimentation of the pigment, thereby making it possible to obtain an ink composition having good stability over time.
  • a thickener conventionally known substances can be used, but it is preferable to use a substance that can impart shear thinning properties to the ink composition (shear thinning properties imparting agent).
  • An ink composition using a shear thinning agent has a high viscosity and is difficult to flow when it is left standing or under low stress, and easily lowers its viscosity when external stress is applied. Therefore, when not writing, ink leakage, ink separation and backflow can be prevented, and when writing, it is easy to improve the stability of ink discharge from the pen tip.
  • the ink composition when such an ink composition is used in a writing instrument (ballpoint pen) equipped with a ballpoint tip as a pen nib, the ink composition is high in viscosity when left standing without shearing stress, so the ink composition may not be present inside the ballpoint pen. is stably maintained. Therefore, during writing, strong shear stress is applied to the ink composition due to the rotation of the ball, and the ink composition near the ball is more likely to have a lower viscosity, so that the ink discharge stability can be improved.
  • the content of the thickener with respect to the total mass of the ink composition is not particularly limited, but is preferably 0.1 to 20% by mass. is within the range of
  • shear thinning agents include water-soluble polysaccharides, polymers with a molecular weight of 100,000 to 150,000 whose main component is an alkyl ester of methacrylic acid, crosslinked poly-N-vinylcarboxylic acid amide, benzylidene sorbitol, and its like.
  • examples include derivatives, benzylidene xylitol and its derivatives, alkali-thickened acrylic resins, cross-linked acrylic acid polymers, inorganic fine particles, nonionic surfactants with an HLB value of 8 to 12, metal salts or amine salts of dialkyl sulfosuccinic acid, etc. can.
  • shear thinning agent One type of shear thinning agent or a combination of two or more types can be used.
  • water-soluble polysaccharides examples include xanthan gum, welan gum, zetasea gum, diutan gum, macrohomopsis gum, and succinoglycan, which is an organic acid-modified heteropolysaccharide whose constituent monosaccharides are glucose and galactose (with an average molecular weight of about 1 million to 8,000,000), guar gum, locust bean gum and its derivatives, hydroxyethyl cellulose, alginate alkyl esters, glucomannan, agar, carrageenan, and other carbohydrates with gelling ability extracted from seaweed.
  • the ink composition according to the embodiment of the present invention may contain a polymer flocculant.
  • Polymer flocculants create a loose cross-linking effect between pigments, allowing the pigments to form loose aggregates via the polymer flocculant, suppressing direct aggregation of pigments and dispersing pigments. Stability can be improved.
  • the polymer flocculant has the effect of suppressing sedimentation of the pigment in the ink composition in the capillary gaps of the ink storage body provided in the marking pen described below. Therefore, it is suitable that an ink composition containing a polymer flocculant is applied to a marking pen equipped with an ink storage body.
  • the polymer flocculant can also be used in combination with the above-mentioned dispersant.
  • the dispersibility of loose aggregates formed via the polymer flocculant can be improved.
  • the content of the polymer flocculant with respect to the total mass of the ink composition is not particularly limited, but is preferably 0.05 to 1. It is in the range of % by mass.
  • polymer flocculants examples include polyvinylpyrrolidone, polyethylene oxide, water-soluble polysaccharides, and the like.
  • water-soluble polysaccharides examples include gum tragacanth, guar gum, pullulan, cyclodextrin, and water-soluble cellulose derivatives.
  • water-soluble cellulose derivatives include carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxyethylmethylcellulose, and hydroxypropylmethylcellulose.
  • the ink composition according to the embodiment of the present invention can contain a surfactant, and the surface tension of the ink composition can be adjusted to an appropriate range.
  • Surfactants used to adjust the surface tension include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and any of them can be suitably used.
  • the content of the surfactant used for adjusting surface tension with respect to the total mass of the ink composition is not particularly limited. However, it is preferably in the range of 0.01 to 2% by weight, more preferably 0.05 to 1% by weight.
  • a pH adjuster can be added to the ink composition according to the embodiment of the present invention, and the pH of the ink composition can be adjusted to an appropriate range.
  • Various acidic or basic substances can be used as the pH adjuster.
  • acidic substances include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid, boric acid, lactic acid, citric acid, tartaric acid, and malic acid.
  • Examples of basic substances include ammonia, sodium carbonate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium hydroxide, potassium hydroxide, sodium acetate, and alkanols such as monoethanolamine, diethanolamine, and triethanolamine. Amines can also be applied.
  • the content of the pH adjuster based on the total mass of the ink composition is not particularly limited, but is preferably 0.1 to 5% by mass. , more preferably in the range of 0.5 to 2% by mass.
  • the ink composition according to the embodiment of the present invention can contain a water-soluble organic solvent that is compatible with water, and can suppress water evaporation from the nib of a writing instrument.
  • water-soluble organic solvents examples include ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thioethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, and ethylene glycol monomethyl.
  • Ether ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone etc. can be exemplified.
  • the water-soluble organic solvents can be used alone or in combination of two or more.
  • the content of the water-soluble organic solvent with respect to the total mass of the ink composition is not particularly limited, but is preferably 1 to 40% by mass. , more preferably 5 to 30% by weight, and still more preferably 10 to 25% by weight. If the content of the water-soluble organic solvent exceeds 40% by mass, the ink viscosity tends to increase, the ink ejection performance of the writing instrument containing the ink composition decreases, and writing defects such as blurring and line skipping are likely to occur. On the other hand, if the content is less than 1% by mass, the effect of suppressing moisture evaporation will be poor.
  • the ink composition according to the embodiment of the present invention may contain a water-soluble resin such as an alkyd resin, an acrylic resin, a styrene-maleic acid copolymer, a cellulose derivative, a polyvinylpyrrolidone, a polyvinyl alcohol, or a dextrin. It can provide adhesion and viscosity to paper surfaces.
  • a water-soluble resin such as an alkyd resin, an acrylic resin, a styrene-maleic acid copolymer, a cellulose derivative, a polyvinylpyrrolidone, a polyvinyl alcohol, or a dextrin. It can provide adhesion and viscosity to paper surfaces.
  • One type of water-soluble resin or a combination of two or more types can be used.
  • the content of the water-soluble resin with respect to the total mass of the ink composition is not particularly limited, but is preferably 1 to 30% by mass, or more. It is preferably in the range of 1 to 10% by mass.
  • the ink composition according to the embodiment of the present invention may also contain various other additives as necessary.
  • additives examples include rust preventives, antiseptics, antifungal agents, bubble absorbers, wetting agents, antifoaming agents, specific gravity adjusters, and the like.
  • rust preventive agent examples include dicyclohexylammonium nitrite, diisopropylammonium nitrite, and saponin.
  • Preservatives or antifungal agents include carbolic acid, sodium salt of 1,2-benzothiazolin 3-one, sodium benzoate, sodium dehydroacetate, potassium sorbate, propyl paraoxybenzoate, 2,3,5,6-tetra Examples include chloro-4-(methylsulfonyl)pyridine.
  • Foam absorbers include ascorbic acids, erythorbic acids, ⁇ -tocopherol, catechins, synthetic polyphenols, kojic acid, alkylhydroxylamines, oxime derivatives, ⁇ -glucosylrutin, ⁇ -lipoic acid, phosphonates, phosphinates, Examples include sulfites, sulfoxylates, dithionites, thiosulfates, and thiourea dioxide.
  • wetting agents include reduced or non-reduced starch hydrolysates, disaccharides such as trehalose, oligosaccharides, sucrose, cyclodextrin, glucose, dextrin, sorbitol, mannitol, sodium pyrophosphate, and the like.
  • a lubricant can also be blended into the ink composition.
  • the lubricant improves the lubricity between the ball receiving seat provided inside the tip body and the ball provided at the front end of the tip body, making it easier to prevent wear on the ball receiving seat and improving the writing feel. It is something that can be done.
  • lubricant examples include higher fatty acids such as oleic acid, nonionic surfactants having long-chain alkyl groups, and polyether-modified silicone oil.
  • the method for producing the ink composition according to the embodiment of the present invention is not particularly limited, and any conventionally known method can be used.
  • the ink composition is prepared by stirring a mixture of the above-mentioned components with various stirrers such as propeller stirring, homodisper, or homomixer, or by dispersing it with various dispersion machines such as bead mills. can manufacture things.
  • the viscosity characteristics are not particularly limited.
  • ink compositions with viscosity characteristics such as high shear thinning ink compositions (gel inks), low viscosity and low shear thinning ink compositions, and low viscosity non-shear thinning ink compositions (Newtonian inks). objects can be used.
  • the guanine pigment applied to the embodiment of the present invention has excellent dispersion stability, and the pigment does not easily settle even if the ink composition has a low viscosity.
  • the following ink compositions are suitable.
  • the ink composition according to the embodiment of the present invention is used for a ballpoint pen, its viscosity is determined by the dispersion stability of the pigment when measured at a rotation speed of 1 rpm (shear rate 3.84 sec -1 ) in an environment of 20°C.
  • the following ranges are preferable because the properties can be more stabilized.
  • the viscosity of the ink composition in this case is preferably in the range of 1 to 2000 mPa ⁇ s, more preferably 10 to 1500 mPa ⁇ s, and still more preferably 100 to 1000 mPa ⁇ s.
  • the viscosity when measured at a rotational speed of 100 rpm (shear rate 384 sec -1 ) in an environment of 20°C, the viscosity is within the following range because the ink ejection performance from the tip of a ballpoint pen can be made good. is preferred.
  • the viscosity of the ink composition in this case is preferably in the range of 1 to 200 mPa ⁇ s, more preferably 10 to 100 mPa ⁇ s, and even more preferably 20 to 50 mPa ⁇ s.
  • the viscosity of the ink composition is within the above range, the dispersion stability of the pigment and the free flowability of the ink within the mechanism of the ballpoint pen can be maintained at a high level.
  • the viscosity of the ink composition was measured using a rheometer [manufactured by TA Instruments, product name: Discovery HR-2, cone plate (diameter 40 mm, angle 1°)] by placing the ink in an environment of 20°C. , a rotation speed of 1 rpm (shear rate 3.84 sec ⁇ 1 ), or a rotation speed of 100 rpm (shear rate 384 sec ⁇ 1 ).
  • the viscosity of the ink composition is determined to have a high fluidity of the ink and a high dispersion stability of the pigment when measured at a rotation speed of 50 rpm in an environment of 20°C.
  • the following ranges are preferable because they can be maintained at the same level.
  • the viscosity of the ink composition in this case is preferably in the range of 1 to 30 mPa ⁇ s, more preferably 1 to 20 mPa ⁇ s, even more preferably 1 to 10 mPa ⁇ s.
  • the viscosity of the ink composition was measured using an E-type rotational viscometer [manufactured by Toki Sangyo Co., Ltd., product name: RE-85L, cone rotor: standard type (1°34' x R24)]. This is a value measured with the composition placed in an environment at 20°C.
  • the ink composition according to the embodiment of the present invention is used for a ballpoint pen or a marking pen, its pH is preferably in the range of 6 to 10, more preferably 7 to 9.
  • the pH is within the above range, excessive increase in viscosity and deterioration of the ink composition can be suppressed.
  • the pH of the ink composition is a value measured using a pH meter [manufactured by DKK Toa Co., Ltd., product name: IM-40S] with the ink placed in an environment of 20°C.
  • the structure and shape of the ballpoint pen itself are not particularly limited. It is used as
  • a ballpoint pen tip consists of a tip body and a ball provided at the front end of the tip body.
  • a ballpoint pen tip is a tip in which a ball is held in a ball holding part where the tip of the tip body made of a metal pipe is deformed by pressing inward from the outer surface, or a tip made of a metal pipe with a ball held in the tip body.
  • An example is one in which a spring body urges forward.
  • the material of the chip body and the ball is not particularly limited, and examples thereof include cemented carbide (carbide), stainless steel, ruby, ceramic, resin, and rubber. Furthermore, the ball can also be subjected to surface treatment such as DLC coating.
  • the diameter of the ball is generally 0.2 to 3 mm, preferably 0.2 to 2 mm, more preferably 0.2 to 1.5 mm, and still more preferably 0.2 to 1 mm.
  • An example of the ink filling mechanism is an ink container that can be directly filled with ink.
  • the ink container for example, a molded body made of a thermoplastic resin such as polyethylene, polypropylene, polyethylene terephthalate, or nylon, or a metal tubular body is used.
  • a thermoplastic resin such as polyethylene, polypropylene, polyethylene terephthalate, or nylon
  • a ballpoint pen refill (hereinafter sometimes referred to as "refill") can be formed by connecting a ballpoint pen tip to the ink container directly or via a connecting member and directly filling the ink container with ink. can.
  • a ballpoint pen can be formed by housing this refill in the barrel.
  • An ink backflow prevention body is filled at the rear end of the ink filled in the ink container.
  • the ink backflow preventer include a liquid stopper or a solid stopper.
  • the liquid stopper consists of a non-volatile liquid and/or a slightly volatile liquid, such as vaseline, spindle oil, castor oil, olive oil, refined mineral oil, liquid paraffin, polybutene, ⁇ -olefin, oligomer or cooligomer of ⁇ -olefin, dimethyl
  • a slightly volatile liquid such as vaseline, spindle oil, castor oil, olive oil, refined mineral oil, liquid paraffin, polybutene, ⁇ -olefin, oligomer or cooligomer of ⁇ -olefin, dimethyl
  • silicone oil methylphenyl silicone oil, amino-modified silicone oil, polyether-modified silicone oil, and fatty acid-modified silicone oil.
  • the non-volatile liquid and/or the hardly volatile liquid can be used alone or in combination of two or more.
  • a thickener to the non-volatile liquid and/or the slightly volatile liquid to thicken it to a suitable viscosity.
  • Thickeners include, for example, silica with a hydrophobically treated surface, fine particle silica with a methylated surface, aluminum silicate, swelling mica, clay-based thickeners such as hydrophobically treated bentonite and montmorillonite; magnesium stearate. , fatty acid metal soaps such as calcium stearate, aluminum stearate, and zinc stearate; dextrin-based compounds such as tribenzylidene sorbitol, fatty acid amide, amide-modified polyethylene wax, hydrogenated castor oil, and fatty acid dextrin; and cellulose-based compounds.
  • solid plugs examples include solid plugs made of polyethylene, polypropylene, polymethylpentene, and the like.
  • the above-mentioned liquid plug and solid plug can also be used in combination.
  • a ballpoint pen equipped with a ballpoint pen tip and an ink filling mechanism further includes an ink supply mechanism for supplying the ink filled in the ink filling mechanism to the pen tip. may be provided.
  • the ink supply mechanism is not particularly limited, and includes, for example, (1) a mechanism that includes an ink guide core made of a fiber bundle or the like as an ink flow rate regulator and supplies ink to the pen tip through this intervening mechanism; ) A mechanism that includes a comb groove-shaped ink flow rate regulator and supplies ink to the pen tip through this intervening mechanism; (3) A large number of disc bodies are arranged in parallel with comb groove-shaped intervals, and the disc bodies are arranged in parallel in the axial direction. A slit-shaped ink guide groove running vertically through the pen core and a ventilation groove wider than the groove are provided, and an ink guide core for guiding ink from the ink filling mechanism to the pen tip is arranged at the axis of the pen core. Examples include a mechanism that supplies ink to the pen tip.
  • the material of the pen core is not particularly limited as long as it is a synthetic resin that can be injection molded into a comb-like structure with a large number of discs.
  • the synthetic resin include general-purpose polycarbonate, polypropylene, polyethylene, acrylonitrile-butadiene-styrene copolymer (ABS resin), and the like.
  • ABS resin acrylonitrile-butadiene-styrene copolymer
  • ABS resin acrylonitrile-butadiene-styrene copolymer
  • an ink storage body that can be filled with ink can be used as the ink filling mechanism.
  • the ink storage body is a fiber bundle in which crimped fibers are bundled in the longitudinal direction.
  • the ink storage body is a fiber bundle in which crimped fibers are bundled in the longitudinal direction, and is built into a plastic cylinder or a covering such as a film so that the porosity is in the range of approximately 40 to 90%. It is configured by adjusting.
  • an ink storage body impregnated with ink is housed in the ink storage body, and an ink supply mechanism is provided at the front end of the ink storage body so as to be connected to the ink storage body.
  • a ballpoint pen refill including a ballpoint pen tip, an ink filling mechanism, and an ink supply mechanism can also be formed by connecting the tip to the ink supply mechanism directly or via a connecting member.
  • the ink storage body houses an ink storage body impregnated with ink, and an ink supply mechanism is provided inside the ink storage body so as to be connected to the ink storage body, and a ballpoint pen is connected to the ink supply mechanism.
  • a ballpoint pen refill can also be formed by connecting the tip to the ink container directly or via a connecting member.
  • the structure of the ballpoint pen that accommodates the ink composition according to the embodiment of the present invention is as follows: (1) It has an ink container filled with ink in the barrel, and the ink container is provided with a direct or connecting member. (2) A ballpoint pen whose end face is filled with an ink backflow preventer; (2) A ballpoint pen whose barrel is directly filled with ink and a comb-shaped ink flow regulator, or a fiber bundle, etc.
  • a ballpoint pen that is equipped with a mechanism for supplying ink to the nib by interposing an ink guiding core as an ink flow rate regulator;
  • An example is a ballpoint pen, etc., which is equipped with a mechanism for supplying ink to the pen tip.
  • the structure and shape of the marking pen itself are not particularly limited.
  • a marking pen refill including a marking pen tip and an ink filling mechanism is used. Or it can be filled into a marking pen.
  • a porous material with continuous pores selected from a conventional general-purpose material with a porosity in the range of 30 to 70%, such as a resin-processed fiber, a fusion-processed heat-fusible fiber, a felt material, etc.
  • a resin-processed fiber such as a resin-processed fiber, a fusion-processed heat-fusible fiber, a felt material, etc.
  • An example is a member or a synthetic resin extrusion molded body having a plurality of ink outlet holes extending in the axial direction, and one end can be processed into a shape according to the purpose such as a bullet shape, a rectangular shape, a chisel shape, etc. and used for practical use. be done.
  • the ink filling mechanism is an ink storage body that can be filled with ink.
  • the ink occlusion body is a fiber bundle in which crimped fibers are bundled in the longitudinal direction.
  • the ink storage body is a fiber bundle in which crimped fibers are bundled in the longitudinal direction, and the porosity is adjusted to a range of approximately 40 to 90% by incorporating it into a plastic cylinder or a covering such as a film. configured.
  • a marking pen is formed by accommodating an ink absorbing body impregnated with ink in the barrel, and connecting the marking pen tip to the barrel directly or through a connecting member so as to be connected to the ink absorbing body. be able to.
  • the marking pen refill can be made by accommodating an ink storage body impregnated with ink in the ink storage body, and connecting the marking pen tip to the ink storage body directly or through a connecting member. (hereinafter sometimes referred to as a "refill") can be formed.
  • a marking pen can be formed by housing this refill in a barrel.
  • the ink container for example, a molded body made of a thermoplastic resin such as polyethylene, polypropylene, polyethylene terephthalate, or nylon, or a metal tubular body is used.
  • a thermoplastic resin such as polyethylene, polypropylene, polyethylene terephthalate, or nylon
  • the marking pen equipped with a marking pen tip and an ink filling mechanism may further include an ink supply mechanism for supplying the ink composition to be filled in the ink filling mechanism to the pen tip.
  • the ink supply mechanism is not particularly limited, and for example, in addition to the ink supply mechanism included in the ballpoint pen described above, it may include (4) an ink flow rate regulator using a valve mechanism, and ink is supplied to the pen tip by opening the valve. Examples include mechanisms for
  • the valve mechanism can be a conventionally general-purpose pumping type that opens by pressing the tip, and preferably has a spring pressure that allows the valve to be opened by pressure from a pen.
  • an ink storage body that can be directly filled with ink can be used as the ink filling mechanism.
  • the barrel itself may be used as an ink filling mechanism to directly fill ink.
  • the ink storage body houses an ink storage body impregnated with ink, and an ink supply mechanism is provided at the front end of the ink storage body so as to be connected to the ink storage body, and markings are provided so as to connect to the ink supply mechanism.
  • a marking pen refill including a marking pen tip, an ink filling mechanism, and an ink supply mechanism can also be formed by connecting the pen tip to the ink supply mechanism directly or via a connecting member.
  • an ink storage body impregnated with ink is housed in the ink storage body, and an ink supply mechanism is provided inside the ink storage body so as to be connected to the ink storage body, and markings are provided so as to be connected to the ink supply mechanism.
  • a marking pen refill can also be formed by connecting the pen tip to the ink reservoir directly or via a connecting member.
  • the configuration of the marking pen that accommodates the ink composition according to the embodiment of the present invention is as follows: (1) An ink storage body made of a fiber bundle impregnated with ink is housed in the barrel, and capillary gaps are formed. (2) A marking pen in which a marking pen tip made of a fiber processed body or a resin molded body is connected to a barrel directly or through a connecting member so that the ink storage body and the tip are connected to the barrel; (2) a barrel; A marking pen, which is directly filled with ink and is equipped with a mechanism for supplying ink to the pen tip by interposing an ink guide core made of a comb-shaped ink flow rate regulator or a fiber bundle as an ink flow rate regulator, (3 ) A marking pen with a mechanism in which the barrel is directly filled with ink and a mechanism for supplying ink to the nib via the above-mentioned pen core; (4) A marking pen that is equipped with a mechanism that supplies ink to the nib via the above-mentioned pen core
  • stirring is performed to stir the ink in the ink container or barrel filled with the ink in order to facilitate redispersion of the pigment.
  • a stirring body such as a ball.
  • the shape of the stirring body include a spherical body and a rod-shaped body.
  • the material of the stirring body is not particularly limited, and examples include metal, ceramic, resin, and glass.
  • a writing instrument such as a ballpoint pen or a marking pen according to an embodiment of the present invention can also be in the form of an ink cartridge as a removable structure. In this case, after the ink stored in the ink cartridge of the writing instrument is used up, the writing instrument can be used again by replacing it with a new ink cartridge.
  • the ink cartridge used is one that doubles as a barrel that constitutes the writing instrument by being connected to the writing instrument body, or one that covers and protects the barrel (rear barrel) after being connected to the writing instrument body.
  • the ink cartridge can also be used with writing instruments in which the writing instrument body and ink cartridge are connected before use, and with the user of the writing instrument connecting the ink cartridge inside the barrel during use. It may be any of those that are housed in the shaft cylinder in an unconnected state so as to start.
  • a writing instrument such as a ballpoint pen or a marking pen according to an embodiment of the present invention is provided with a cap that is attached to cover the pen tip (writing tip) to make it a cap-type writing instrument, so that the pen tip dries and prevents writing. It is possible to prevent the writing tip from being lost and the writing tip from being contaminated or damaged.
  • a writing instrument such as a ballpoint pen or a marking pen in which a refill is stored in the barrel can be made into a retractable writing instrument by providing a retractable mechanism in the barrel that allows the writing tip to retract from the barrel. , it is possible to prevent the writing tip from being contaminated or damaged.
  • Any retractable writing instrument can be used as long as the writing tip is housed in the barrel with the writing tip exposed to the outside air, and the writing tip protrudes from the barrel opening by the operation of the retractable mechanism.
  • an operating section (clip) that can be moved in the front-rear direction from the rear side wall of the barrel is protruded radially outward, and by sliding the operating section forward, the front end of the barrel can be moved.
  • a rear end knock that makes the writing tip come out and go out from the opening at the front end of the barrel by pushing forward the operating section provided at the rear end of the barrel.
  • a side-knock-type ejection mechanism that causes the writing tip to protrude and retract from the front end opening of the barrel by pressing an operating part protruding from the outer surface of the side wall of the barrel in the radial direction; (4) a shaft;
  • An example is a rotary ejection mechanism that causes the writing tip to protrude and retract from the front end opening of the barrel by rotating an operating section at the rear of the barrel.
  • Ballpoint pens and marking pens are not limited to the configurations described above; they may be equipped with tips of different shapes, tips that produce ink of different tones or hues, or tips of different shapes. Additionally, it may be a composite writing instrument (double-ended type, pen-tip type, etc.) in which the tone or hue of the ink derived from each tip is different.
  • thermochromic composition a reversible thermochromic microcapsule pigment, a reversible thermochromic resin particle, or the like
  • a writing instrument containing an ink composition is used to coat the writing surface.
  • the handwriting formed can be discolored by rubbing with a finger or by using a heating or cooling tool.
  • heating tools include electrical heating discoloration tools equipped with a resistance heating element such as a PTC element, heat discoloration tools filled with a medium such as hot water, heat discoloration tools using steam or laser light, hair dryers, etc.
  • a resistance heating element such as a PTC element
  • heat discoloration tools filled with a medium such as hot water
  • heat discoloration tools using steam or laser light etc.
  • friction members and friction bodies are preferable because they can be changed in color by a simple method.
  • cooling device examples include an energized cold/heat discoloration device using a Peltier element, a cold/heat discoloration device filled with a refrigerant such as cold water and/or ice chips, a cold storage agent, and applications for refrigerators and freezers.
  • an elastic body such as an elastomer or plastic foam, which has a rich elastic feel and can generate appropriate friction and generate frictional heat during rubbing, but plastic molded bodies, stone, wood, etc. Metal, cloth, etc. can also be used.
  • the handwriting may be rubbed using a general eraser used for erasing pencil handwriting, but since eraser scum is generated during rubbing, the above-mentioned friction member that hardly generates eraser scum and A friction body is preferably used.
  • Examples of the material for the friction member and the friction body include silicone resin, styrene-ethylene-butadiene-styrene block copolymer (SEBS resin), and the like.
  • SEBS resin is more preferably used because silicone resin tends to adhere to areas erased by rubbing and handwriting tends to be repelled when written repeatedly.
  • the above-mentioned friction member or friction body may be a member of any shape separate from the writing instrument, but by providing it on the writing instrument, it can be made highly portable. Further, a writing instrument set can also be obtained by combining a writing instrument and a friction member or friction body of an arbitrary shape that is separate from the writing instrument.
  • the friction member or the location where the friction body is provided is not particularly limited.
  • the cap itself may be formed from a friction member
  • the barrel itself may be formed from a friction member
  • a clip may be provided.
  • the clip itself may be formed of a friction member, or a friction member or a friction body may be provided at the tip (top) of the cap, the rear end of the barrel (the portion where the writing tip is not provided), or the like.
  • the friction member or the location where the friction body is provided is not particularly limited.
  • the barrel itself is formed of a friction member, or if a clip is further provided, the clip itself is A friction member or a friction body may be provided in the vicinity of the opening of the barrel, at the rear end of the barrel (the part where the writing tip is not provided), or in the knock portion.
  • the ink composition according to the embodiment of the present invention can be used for purposes other than writing instruments.
  • printing ink used for screen printing, offset printing, process printing, gravure printing, coater, tampo printing, etc. for brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, dip coating, etc. It can be used as a paint; an inkjet ink; an ultraviolet curable ink; an ink for applicators; an ink for stamps; a paint; a cosmetic; and a coloring liquid for textiles.
  • Example 1 Preparation of pigment dispersion 10 parts of guanine [manufactured by Tokyo Chemical Industry Co., Ltd.], 2.5 parts of a dispersant [manufactured by Toagosei Co., Ltd., product name: Aron A-12SL (solid content: 40%)], 87.5 parts of water were mixed. Then, 200 parts of zirconia beads with a diameter of 1.4 to 1.6 mm were added as a media, and pulverization and dispersion treatment was performed using a bead mill for 6 hours to prepare a pigment dispersion (guanine pigment dispersion).
  • the content of the dispersant with respect to the total mass of the pigment dispersion was 1%, and the content of the dispersant with respect to the guanine pigment was 10%. Furthermore, the average particle diameter of the guanine pigment dispersed in the pigment dispersion was measured by the above method and was found to be 0.35 ⁇ m.
  • Examples 2-4 Preparation of Pigment Dispersion
  • Each of the pigment dispersions of Examples 2 to 4 was prepared in the same manner as in Example 1, except that the types and amounts of the materials to be blended were changed to those listed in Table 1 below.
  • the content ratio of the dispersant to the total mass of the pigment dispersion, the content ratio of the dispersant to the guanine pigment, and the average particle diameter of the guanine pigment dispersed in the pigment dispersion are shown in Table 1 below.
  • Comparative example 1 Preparation of pigment dispersion 10 parts of titanium oxide [manufactured by Teika Co., Ltd., product name: JR-707] and a dispersant [manufactured by BYK Chemie Japan Co., Ltd., product name: DISPER BYK-190 (solid content: 40%) ] and 87.5 parts of water were mixed. Then, 100 parts of glass beads with a diameter of 2.0 mm were added as a media, and pulverization and dispersion treatment was performed using a bead mill for 1 hour to prepare a pigment dispersion (titanium oxide dispersion).
  • the content of the dispersant with respect to the total mass of the pigment dispersion was 1%, and the content of the dispersant with respect to titanium oxide was 10%.
  • the average particle diameter of titanium oxide dispersed in the pigment dispersion was 0.3 ⁇ m.
  • Example 5 Preparation of water-based ink composition for writing instruments 20 parts of guanine [manufactured by Tokyo Chemical Industry Co., Ltd.] and a dispersant [manufactured by Toagosei Co., Ltd., product name: Aron A-12SL (solid content: 40%)] 7.5 1 part and 72.5 parts of water were mixed. Then, 200 parts of zirconia beads with a diameter of 1.4 to 1.6 mm were added as a media, and pulverization and dispersion treatment was performed using a bead mill for 5 hours to prepare a water-based ink composition for writing instruments. Note that the content of the dispersant with respect to the total mass of the ink composition was 3%, and the content of the dispersant with respect to the guanine pigment was 15%.
  • the ink storage body made of polyester sliver covered with a synthetic resin film is impregnated with the above water-based ink composition for writing instruments, and the result is housed in a barrel made of polypropylene resin, and a resin-treated pen made of polyester fiber is attached to the tip of the barrel.
  • the body (shell-shaped) was assembled in a connected state via a resin holder, and a cap was attached to produce a filling-type writing instrument (marking pen).
  • Comparative example 2 Preparation of water-based ink composition for writing instruments 20 parts of titanium oxide [manufactured by Teika Co., Ltd., product name: JR-707] and a dispersant [manufactured by BYK Chemie Japan Co., Ltd., product name: DISPER BYK-190 (solid content: 40%)] and 72.5 parts of water were mixed. Then, 100 parts of glass beads with a diameter of 2.0 mm were added as a media, and pulverization and dispersion treatment was performed using a bead mill for 1 hour to prepare a water-based ink composition for writing instruments. Note that the content of the dispersant with respect to the total mass of the ink composition was 3%, and the content of the dispersant with respect to titanium oxide was 15%.
  • B The white color of the handwriting was slightly lighter than the initial handwriting, but it had a level of concealment that was not a problem in practical use.
  • C The color of the handwriting was lighter than the initial handwriting, and the concealability was low. It was insufficient. Or it was impossible to write.
  • Example 6 Preparation of water-based ink composition for writing instruments 20 parts of guanine [manufactured by Tokyo Kasei Kogyo Co., Ltd.] and a dispersant [manufactured by BYK Chemie Japan Co., Ltd., product name: DISPER BYK-2010 (solid content: 40%)]7. 5 parts and 72.5 parts of water were mixed. Then, 200 parts of zirconia beads with a diameter of 1.4 to 1.6 mm were added as a media, and pulverization and dispersion treatment was performed using a bead mill for 5 hours to prepare a pigment dispersion (guanine pigment dispersion).
  • the content of the dispersant i.e., the total of "DISPER BYK-2010” and “Plysurf AL" with respect to the total mass of the ink composition is 3.6%, and the content of the dispersant for the guanine pigment (i.e., "DISPER BYK-2010") is 3.6%. 2010" and "Plysurf AL) is 21%.
  • the tip provided in the ballpoint pen refill is stored in the barrel while being exposed to the outside air, and the front end of the barrel is pushed forward by the operating section provided at the rear end of the barrel.
  • a rear end knock-type retractable structure is provided in which the tip protrudes from the opening.
  • Example 6 When the ballpoint pen of Example 6 was used to write by hand on black high-quality paper (medium thickness, manufactured by Katsueisha Co., Ltd.) at room temperature (20°C), there were no writing defects such as blurring or line skipping. , a clear white handwriting was formed. In addition, this handwriting concealed the writing surface and was a good handwriting with excellent concealment properties.
  • black high-quality paper medium thickness, manufactured by Katsueisha Co., Ltd.
  • Example 7 Preparation of pigment dispersion 10 parts of guanine [manufactured by Tokyo Chemical Industry Co., Ltd.], 2.5 parts of a dispersant [manufactured by Toagosei Co., Ltd., product name: Aron A-12SL (solid content: 40%)], 87.5 parts of water were mixed. Then, 200 parts of zirconia beads with a diameter of 1.4 to 1.6 mm were added as a media, and pulverization and dispersion treatment was performed using a bead mill for 6 hours to prepare a pigment dispersion (guanine pigment dispersion).
  • the content of the dispersant with respect to the total mass of the pigment dispersion was 1%, and the content of the dispersant with respect to the guanine pigment was 10%. Furthermore, the average particle diameter of the guanine pigment dispersed in the pigment dispersion was measured by the above method and was found to be 0.35 ⁇ m.
  • Examples 8-13 Preparation of Pigment Dispersion
  • Each of the pigment dispersions of Examples 8 to 13 was prepared in the same manner as Example 7, except that the types and amounts of the materials to be blended were changed to those listed in Table 5 below.
  • the content ratio of the dispersant to the total mass of the pigment dispersion, the content ratio of the dispersant to the guanine pigment, and the average particle diameter of the guanine pigment dispersed in the pigment dispersion are shown in Table 5 below.
  • the colored layer was clearly white and had good hiding properties, and the black color of the underlying paper was not visible through the colored layer. Furthermore, since the guanine pigment had excellent dispersibility in the liquid composition, the colored layer had a uniform concentration and a good appearance.

Abstract

This ink composition for a writing utensil contains at least water and pigments including a guanine pigment.

Description

筆記具用水性インキ組成物およびそれを収容してなる筆記具Water-based ink composition for writing instruments and writing instruments containing the same
　本開示は筆記具用水性インキ組成物およびそれを収容してなる筆記具に関する。さらに詳細には、顔料の分散安定性に優れ、隠蔽性に富む明瞭な筆跡を形成できる筆記具用水性インキ組成物およびそれを収容してなる筆記具に関する。 The present disclosure relates to a water-based ink composition for writing instruments and a writing instrument containing the same. More specifically, the present invention relates to an aqueous ink composition for a writing instrument that has excellent pigment dispersion stability and is capable of forming clear handwriting with excellent concealment properties, and a writing instrument containing the same.
　従来、隠蔽性を有する筆跡を得るために、酸化チタンなどの白色顔料を用いた筆記具用インキ組成物が知られている。さらに、このような隠蔽性の高いインキ組成物に、その他の色の着色剤を配合することによりパステル調の筆跡が形成できる筆記具用インキ組成物も好ましく用いられる。 Conventionally, ink compositions for writing instruments using white pigments such as titanium oxide have been known in order to obtain handwriting with hiding properties. Furthermore, ink compositions for writing instruments that can form pastel-like handwriting by blending colorants of other colors with such ink compositions with high hiding properties are also preferably used.
　しかしながら、酸化チタンは比重の大きい顔料であるため、時間の経過に伴って顔料が沈降し易く、ハードケーキが形成されると顔料の再分散が困難となるという問題があった。また、酸化チタンを含有するインキ組成物を用いた筆記具は、筆記先端部を上向きにして保管した場合に筆跡濃度が低下し易くなり、筆記先端部を下向きにして保管した場合にインキ吐出性が低下し易くなる。このため、増粘剤などを用いてインキを高粘度として酸化チタンの沈降を抑制する検討が行われている。しかしながら、このような高粘度のインキ組成物を適用できる筆記具には制限があった。また、酸化チタンとその他の色の着色剤を併用したインキ組成物においては、酸化チタンと着色剤間の比重差により、インキに色別れが生じることがあった。そこで、酸化チタンの沈降を抑制したり、ハードケーキの形成を抑制したりする検討が行われている（例えば、特許文献１～４参照）。 However, since titanium oxide is a pigment with a high specific gravity, the pigment tends to settle over time, and when a hard cake is formed, it becomes difficult to redisperse the pigment. In addition, writing instruments using ink compositions containing titanium oxide tend to lose handwriting density when stored with the writing tip facing upward, and the ink ejection properties tend to decrease when stored with the writing tip facing downward. It becomes easier to decrease. For this reason, studies are being conducted to increase the viscosity of the ink using thickeners and the like to suppress the precipitation of titanium oxide. However, there are limitations to the writing instruments to which such high viscosity ink compositions can be applied. Furthermore, in ink compositions that use titanium oxide and colorants of other colors in combination, color separation may occur in the ink due to the difference in specific gravity between titanium oxide and the colorant. Therefore, studies are being conducted to suppress the precipitation of titanium oxide and the formation of hard cakes (see, for example, Patent Documents 1 to 4).
　特許文献１には、酸化チタンと、ケイ酸アルミニウム系顔料と、特定の樹脂とからなる水性顔料組成物が開示されている。 Patent Document 1 discloses an aqueous pigment composition comprising titanium oxide, an aluminum silicate pigment, and a specific resin.
　また、特許文献２には、酸化チタンと、サクシノグリカンと、水とから少なくともなる水性インキ組成物が開示されている。 Further, Patent Document 2 discloses an aqueous ink composition comprising at least titanium oxide, succinoglycan, and water.
　また、特許文献３には、酸化チタンと、オレイン酸とからなるボールペン用水性インキが開示されている。 Further, Patent Document 3 discloses a water-based ink for ballpoint pens consisting of titanium oxide and oleic acid.
　また、特許文献４には、酸化チタンと、有彩色顔料と、シリカ粉末および／またはアルミノケイ酸塩と、水溶性樹脂と、特定の分散剤と、界面活性剤と、水とからなる筆記具用水性顔料インキが開示されている。 Furthermore, Patent Document 4 describes an aqueous writing instrument comprising titanium oxide, a chromatic pigment, silica powder and/or aluminosilicate, a water-soluble resin, a specific dispersant, a surfactant, and water. A pigmented ink is disclosed.
　上記の組成物（インキ組成物）は、特定の化合物を用いることにより酸化チタンの沈降速度を遅くすることはできるものの、経時的に酸化チタンが沈降してハードケーキを形成したり、インキ中で色別れを生じたりし易く、インキ組成物中で酸化チタンを安定的に分散させることは困難であった。 Although it is possible to slow down the settling rate of titanium oxide by using a specific compound in the above composition (ink composition), titanium oxide may settle over time and form a hard cake, or in the ink. It was difficult to stably disperse titanium oxide in an ink composition because color separation was likely to occur.
特開昭５９－２１７７７６号公報Japanese Unexamined Patent Publication No. 59-217776 特開平８－１１３７５２号公報Japanese Unexamined Patent Publication No. 8-113752 特開平１０－２５１５８８号公報Japanese Patent Application Publication No. 10-251588 特開平１１－２１７５３２号公報Japanese Patent Application Publication No. 11-217532
　本開示は、顔料の分散安定性に優れると共に、隠蔽性に富む明瞭な筆跡を形成できる筆記具用水性インキ組成物およびそれを収容してなる筆記具を提供しようとするものである。 The present disclosure aims to provide a water-based ink composition for a writing instrument that has excellent pigment dispersion stability and can form clear handwriting with excellent concealment properties, and a writing instrument containing the same.
　本発明の態様１は、
　少なくとも、グアニン顔料を含む顔料と、水とを含んでなる筆記具用水性インキ組成物である。 Aspect 1 of the present invention is
The present invention is an aqueous ink composition for a writing instrument comprising at least a pigment containing a guanine pigment and water.
　本発明の態様２は、
　分散剤をさらに含んでなる、態様１に記載のインキ組成物である。 Aspect 2 of the present invention is
The ink composition according to aspect 1, further comprising a dispersant.
　本発明の態様３は、
　前記分散剤は、酸性基及び／又は酸性基の塩を有する、態様２に記載のインキ組成物である。 Aspect 3 of the present invention is
The ink composition according to aspect 2, wherein the dispersant has an acidic group and/or a salt of an acidic group.
　本発明の態様４は、
　前記グアニン顔料の平均粒子径が０．１～１μｍである、態様１乃至３のいずれか１つに記載のインキ組成物である。 Aspect 4 of the present invention is
The ink composition according to any one of aspects 1 to 3, wherein the guanine pigment has an average particle diameter of 0.1 to 1 μm.
　本発明の態様５は、
　前記インキ組成物の総質量に対する前記グアニン顔料の含有率が、１～５０質量％である、態様１乃至４のいずれか１つに記載のインキ組成物である。 Aspect 5 of the present invention is
The ink composition according to any one of aspects 1 to 4, wherein the content of the guanine pigment with respect to the total mass of the ink composition is 1 to 50% by mass.
　本発明の態様６は、
　着色剤をさらに含んでなる、態様１乃至５のいずれか１つに記載のインキ組成物である。 Aspect 6 of the present invention is
The ink composition according to any one of aspects 1 to 5, further comprising a colorant.
　本発明の態様７は、
　態様１乃至６のいずれか１つに記載のインキ組成物を収容してなる、筆記具である。 Aspect 7 of the present invention is
A writing instrument containing the ink composition according to any one of aspects 1 to 6.
　本発明の実施形態によれば、グアニン顔料を含む顔料を用いる筆記具用水性インキ組成物であって、顔料が経時的に沈降し難く、顔料の分散安定性に優れ、さらに隠蔽性に富む明瞭な筆跡を形成できる筆記具用水性インキ組成物およびそれを収容してなる筆記具を提供できる。 According to an embodiment of the present invention, there is provided an aqueous ink composition for writing instruments using a pigment containing a guanine pigment, in which the pigment is difficult to settle over time, has excellent pigment dispersion stability, and has a clear color with excellent hiding properties. It is possible to provide a water-based ink composition for a writing instrument that can form handwriting, and a writing instrument containing the same.
　本発明の実施形態による筆記具用水性インキ組成物（以下、「インキ組成物」、または「インキ」と表すことがある）は、少なくとも、グアニン顔料を含む顔料と、水とを含んでなる。以下に、本発明の実施形態によるインキ組成物を構成する各成分について説明する。 The aqueous ink composition for writing instruments (hereinafter sometimes referred to as "ink composition" or "ink") according to the embodiment of the present invention contains at least a pigment containing a guanine pigment and water. Each component constituting the ink composition according to the embodiment of the present invention will be explained below.
　本発明の実施形態によるインキ組成物は、グアニン顔料を含有する。グアニン顔料とは、グアニンからなる顔料である。 The ink composition according to the embodiment of the present invention contains a guanine pigment. A guanine pigment is a pigment made of guanine.
　グアニンは、核酸を構成する主な塩基のうちの一つで、生物由来の有機物であり、例えば、タチウオ、ニシン、およびイワシ等の魚類の体表面において結晶状態で存在する。結晶状態のグアニン（グアニン結晶）は、これらの魚類の体表面において積層構造を形成して、光を反射あるいは屈折させるため、タチウオ、ニシン、およびイワシ等の魚類は体表面に光沢性（真珠光沢性）を有する。 Guanine is one of the main bases constituting nucleic acids, and is an organic substance derived from living organisms. For example, it exists in a crystalline state on the body surface of fish such as hairtail, herring, and sardines. Crystalline guanine (guanine crystals) forms a layered structure on the body surface of these fish, reflecting or refracting light, so fish such as hairtail, herring, and sardines have a glossy (pearlescent) surface on their body surfaces. gender).
　また、グアニン結晶を原料として得られる魚鱗箔は、真珠光沢性を示す顔料として化粧品および食品添加物に利用されていることから、グアニンは化合物自体の安全性が高いと考えられ、人体および環境に対する影響が少ないものである。 In addition, fish scale foil obtained using guanine crystals as a raw material is used as a pearlescent pigment in cosmetics and food additives, so guanine is considered to be a highly safe compound, and is safe for the human body and the environment. It has little impact.
　グアニンは市販品から入手することができるが、タチウオ、ニシン、およびイワシ等の魚類から採取した天然グアニン結晶であってもよい。また、市販品あるいは天然のグアニン結晶を溶媒に溶解し、再結晶させることにより得られる人工グアニン結晶を用いることもできる。 Guanine can be obtained from commercial products, but natural guanine crystals collected from fish such as hairtail, herring, and sardines may also be used. Furthermore, artificial guanine crystals obtained by dissolving commercially available or natural guanine crystals in a solvent and recrystallizing the crystals can also be used.
　本発明の実施形態に適用されるグアニン顔料は、高い屈折率（ｎ＝１．８～２．０）を有するため白色を呈し、筆跡に隠蔽性を付与する効果を奏する。白色を呈する顔料として従来用いられる酸化チタンは、比重が大きいためインキ組成物中で沈降し易く、沈降した場合にハードケーキを形成し易いため、再分散が困難となる場合がある。これに対してグアニン顔料は、酸化チタンに比べて比重が小さいため経時的に沈降し難く、分散安定性に優れるものであり、ハードケーキの形成が抑制される。 The guanine pigment applied to the embodiment of the present invention has a high refractive index (n=1.8 to 2.0), so it exhibits white color and has the effect of providing concealment to handwriting. Titanium oxide, which is conventionally used as a white pigment, has a high specific gravity and therefore tends to settle in the ink composition, and when it settles, it tends to form a hard cake, which may make redispersion difficult. On the other hand, since guanine pigment has a lower specific gravity than titanium oxide, it is less likely to settle over time and has excellent dispersion stability, thereby suppressing the formation of a hard cake.
　本発明の実施形態によるインキ組成物は、グアニン顔料を含む顔料を用いることにより、顔料が経時的に沈降し難く、分散安定性に優れるものである。このため、本発明の実施形態によるインキ組成物は、隠蔽性に富む明瞭な筆跡を均一な濃度で形成することができる。また、本発明の実施形態によるインキ組成物は、後述する着色剤を含有する場合であっても、インキ組成物中におけるグアニン顔料および着色剤の分離が抑制される。このため、本発明の実施形態によるインキ組成物は、隠蔽性を有する有色を呈する筆跡を均一な濃度で形成することができる。 The ink composition according to the embodiment of the present invention uses a pigment containing a guanine pigment, so that the pigment is difficult to settle over time and has excellent dispersion stability. Therefore, the ink composition according to the embodiment of the present invention can form clear handwriting with excellent concealment properties at a uniform density. Further, even when the ink composition according to the embodiment of the present invention contains a colorant described below, separation of the guanine pigment and the colorant in the ink composition is suppressed. Therefore, the ink composition according to the embodiment of the present invention can form colored handwriting with concealing properties at a uniform density.
　グアニン顔料の平均粒子径は特に限定されるものではないが、好ましくは０．１～１μｍ、より好ましくは０．２～０．９５μｍ、さらに好ましくは０．２５～０．６５μｍ、特に好ましくは０．２５～０．４μｍの範囲である。平均粒子径が上記の範囲内にあることにより、インキ組成物の隠蔽性とグアニン顔料の分散安定性とが、高度に両立される。 The average particle diameter of the guanine pigment is not particularly limited, but is preferably 0.1 to 1 μm, more preferably 0.2 to 0.95 μm, even more preferably 0.25 to 0.65 μm, and particularly preferably 0. It is in the range of .25 to 0.4 μm. When the average particle diameter is within the above range, the hiding properties of the ink composition and the dispersion stability of the guanine pigment are both highly compatible.
　平均粒子径は、標準試料または他の測定方法を用いて計測した数値を基にしてキャリブレーションを行った、動的光散乱式粒子径分布測定装置〔マイクロトラック・ベル（株）製，製品名：ＮＡＮＯＴＲＡＣ　ＦＬＥＸ〕を用いて測定した、体積基準による平均粒子径（メジアン径）の値である。
　なお、本発明の実施形態によるインキ組成物がグアニン顔料以外の顔料等を含む場合においても、比重差を利用した密度勾配遠心法により、グアニンと他の顔料等とを分離することで、上記と同様にグアニン単独の平均粒子径を測定することができる。 The average particle diameter was measured using a dynamic light scattering particle size distribution measuring device [manufactured by Microtrac Bell Co., Ltd., product name], which was calibrated based on values measured using standard samples or other measurement methods. : NANOTRAC FLEX] is the value of the average particle diameter (median diameter) on a volume basis.
Note that even if the ink composition according to the embodiment of the present invention contains pigments other than guanine pigments, the above can be achieved by separating guanine and other pigments by density gradient centrifugation using the difference in specific gravity. Similarly, the average particle size of guanine alone can be measured.
　インキ組成物の総質量に対するグアニン顔料の含有率は、特に限定されるものではないが、好ましくは１～５０質量％、より好ましくは５～３０質量％の範囲である。グアニン顔料の含有率が５０質量％を超えると、インキ組成物を収容した筆記具のインキ吐出安定性が低下し易く、カスレおよび線飛び等の筆記不良が発生し易くなる。一方、含有率が１質量％未満では、筆記具としての好適な筆跡濃度が得られ難くなると共に、筆跡の隠蔽性を損ない易くなる。 The content of the guanine pigment with respect to the total mass of the ink composition is not particularly limited, but is preferably in the range of 1 to 50% by mass, more preferably 5 to 30% by mass. When the content of the guanine pigment exceeds 50% by mass, the ink ejection stability of a writing instrument containing the ink composition tends to decrease, and writing defects such as blurring and line skipping tend to occur. On the other hand, if the content is less than 1% by mass, it will be difficult to obtain a suitable handwriting density for a writing instrument, and the concealability of handwriting will be likely to be impaired.
　グアニン顔料としては、インキ組成物中で分散可能なものであれば特に限定されるものではない。グアニン顔料は、例えば、市販品、あるいは、天然または人工グアニン結晶を、ジェットミル、アトライター、ビーズミル等の各種分散機を用いて機械的に粉砕して粒状とすることにより製造することができる。または、市販品あるいは天然グアニン結晶を溶媒に溶解し、粒状に再結晶化させることにより製造することもできる。グアニン顔料として、グアニン顔料自体が着色されたものを用いることもできる。 The guanine pigment is not particularly limited as long as it can be dispersed in the ink composition. The guanine pigment can be produced, for example, by mechanically pulverizing commercially available products or natural or artificial guanine crystals into particles using various dispersing machines such as jet mills, attritors, and bead mills. Alternatively, it can also be produced by dissolving commercially available or natural guanine crystals in a solvent and recrystallizing them into particles. As the guanine pigment, a colored guanine pigment itself can also be used.
　本発明の実施形態によるインキ組成物には、さらに分散剤を配合させることができる。分散剤はグアニン顔料の表面に吸着して、グアニン顔料を相互に離間させながら、グアニン顔料同士の距離を一定以上に保ち凝集を防ぐことができるため、インキ中におけるグアニン顔料の分散性を向上させることができる。また、グアニン顔料同士が凝集して凝集体が形成される場合であっても、密度の低い凝集体が形成されるため、グアニン顔料が沈降した後のハードケーキ化を抑制し易くなる。 The ink composition according to the embodiment of the present invention can further contain a dispersant. The dispersant adsorbs to the surface of the guanine pigment and separates the guanine pigments from each other while keeping the distance between the guanine pigments above a certain level and preventing agglomeration, improving the dispersibility of the guanine pigment in the ink. be able to. Further, even when guanine pigments aggregate with each other to form aggregates, since aggregates with low density are formed, hard cake formation after the guanine pigments are precipitated can be easily suppressed.
　分散剤としては、界面活性剤、高分子分散剤、無機化合物等が挙げられる。 Examples of the dispersant include surfactants, polymer dispersants, inorganic compounds, and the like.
　分散剤として用いられる界面活性剤としては、ノニオン系界面活性剤、アニオン系界面活性剤、カチオン系界面活性剤、両性界面活性剤等が挙げられる。 Examples of the surfactant used as a dispersant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and the like.
　分散剤として用いられる高分子分散剤としては、例えば、ポリビニルブチラール；ポリビニルエーテル；ケトン樹脂；スチレン－マレイン酸共重合体、スチレン－アクリル酸共重合体、アクリル酸－スルホン酸共重合体等のカルボキシ基を含有する樹脂；ヒドロキシエチルセルロースおよびその誘導体；アクリル系高分子；ＰＯ・ＥＯ付加物；ポリエステルのアミン系オリゴマー等を例示できる。 Examples of polymer dispersants used as dispersants include polyvinyl butyral; polyvinyl ether; ketone resin; carboxylic acid such as styrene-maleic acid copolymer, styrene-acrylic acid copolymer, acrylic acid-sulfonic acid copolymer Examples include resins containing groups; hydroxyethyl cellulose and derivatives thereof; acrylic polymers; PO/EO adducts; amine oligomers of polyesters.
　分散剤として用いられる無機化合物としては、例えば、ピロリン酸塩、ヘキサメタリン酸塩等が挙げられる。 Examples of the inorganic compound used as a dispersant include pyrophosphate, hexametaphosphate, and the like.
　本発明の一実施形態によれば、分散剤は、酸性基及び／又は酸性基の塩を有することが好ましい。酸性基及び／又は酸性基の塩は、グアニン（例えばグアニン中の－ＮＨ２基等）と結合しやすく、グアニン周辺に分散剤が集まり易いため、分散剤としての効果に優れる。酸性基としては、リン酸基、カルボキシ基、スルホン酸基、リン酸エステル基、硫酸エステル基、硝酸エステル基、亜リン酸基、ホスホン酸基、スルフィン酸基等を挙げることができる。酸性基の塩としては、上記の酸性基のカリウム塩、ナトリウム塩等の金属塩、または２－アミノ－２－メチル－１－プロパノール塩等を挙げることができる。これらは、１分子中に１種、または２種以上組み合わせて含まれてもよい。
　酸性基及び／又は酸性基の塩を有する市販の分散剤としては、例えばビックケミー・ジャパン（株）のＤＩＳＰＥＲ　ＢＹＫシリーズ、共栄社化学（株）のフローレンシリーズ、東亞合成（株）のアロンシリーズ、ＢＡＳＦジャパン（株）のジョンクリルシリーズ、日本ルーブリゾール（株）のソルスパースシリーズなどから入手することが可能である。なお、酸性基及び／又は酸性基の塩を有する分散剤は、リン酸エステル系界面活性剤などのように、界面活性剤及び／又は潤滑剤等としても機能し得るが、本発明の実施形態においては分散剤として取り扱う。 According to one embodiment of the invention, the dispersant preferably has acidic groups and/or salts of acidic groups. An acidic group and/or a salt of an acidic group easily binds to guanine (for example, -NH 2 group in guanine, etc.), and the dispersant tends to gather around the guanine, so it is excellent as a dispersant. Examples of the acidic group include a phosphoric acid group, a carboxy group, a sulfonic acid group, a phosphoric acid ester group, a sulfuric acid ester group, a nitric acid ester group, a phosphorous acid group, a phosphonic acid group, and a sulfinic acid group. Examples of the salts of acidic groups include metal salts such as potassium salts and sodium salts of the above-mentioned acidic groups, and 2-amino-2-methyl-1-propanol salts. These may be contained in one molecule or in combination of two or more.
Commercially available dispersants having acidic groups and/or salts of acidic groups include, for example, DISPER BYK series from BYK Chemie Japan Co., Ltd., Florene series from Kyoeisha Kagaku Co., Ltd., Aron series from Toagosei Co., Ltd., and BASF Japan Co., Ltd. It can be obtained from the Jonkryl series by Nippon Lubrizol Co., Ltd., the Solsperse series by Nippon Lubrizol Co., Ltd., etc. Note that a dispersant having an acidic group and/or a salt of an acidic group can also function as a surfactant and/or a lubricant, such as a phosphate ester surfactant, but the embodiment of the present invention It is treated as a dispersant.
　本発明の一実施形態によれば、分子量（質量平均分子量）が３００以上２０００００以下であってもよく、３００以上５００００以下であってもよい。 According to one embodiment of the present invention, the molecular weight (mass average molecular weight) may be 300 or more and 200,000 or less, or 300 or more and 50,000 or less.
　本発明の一実施形態によれば、分散剤は酸価を有することが好ましい。これにより、分散剤がグアニンとより結合しやすくなる。 According to one embodiment of the present invention, the dispersant preferably has an acid value. This makes it easier for the dispersant to bind to guanine.
　本発明の一実施形態によれば、以下の（ａ）～（ｅ）からなる群のうちいずれか１つ以上を満たすことが好ましい。これにより、分散剤がグアニンとさらに結合しやすくなる。
（ａ）：分散剤の酸価が１００ｍｇＫＯＨ／ｇ以上
（ｂ）：酸価が５～１５ｍｇＫＯＨ／ｇであり、かつ櫛型構造（すなわち、幹ポリマー部に枝ポリマー部がグラフト結合した構造）を有する
（ｃ）：カルボキシ基含有スチレン－アクリル共重合体を含む
（ｄ）：アクリル－スルホン酸系共重合体を含む
（ｅ）：酸価およびアミン価が共に１５以上３０未満である According to one embodiment of the present invention, it is preferable that at least one of the following groups (a) to (e) is satisfied. This makes it easier for the dispersant to further bind to guanine.
(a): The acid value of the dispersant is 100 mgKOH/g or more (b): The acid value is 5 to 15 mgKOH/g, and the comb-shaped structure (i.e., a structure in which branch polymer parts are grafted to the main polymer part) (c): Contains a carboxyl group-containing styrene-acrylic copolymer (d): Contains an acrylic-sulfonic acid copolymer (e): Both acid value and amine value are 15 or more and less than 30.
　酸性基及び／又は酸性基の塩を有し、かつ上記（ａ）を満たす市販の分散剤としては、例えば、ＤＩＳＰＥＲ　ＢＹＫ－１０２〔ビックケミー・ジャパン（株）製〕、ジョンクリル５７Ｊ〔ＢＡＳＦジャパン（株）製〕、ジョンクリル６３Ｊ〔ＢＡＳＦジャパン（株）製〕、ジョンクリル７０J〔ＢＡＳＦジャパン（株）製〕などが挙げられる。 Examples of commercially available dispersants that have an acidic group and/or a salt of an acidic group and satisfy the above (a) include DISPER BYK-102 [manufactured by BYK Chemie Japan Co., Ltd.] and Joncryl 57J [manufactured by BASF Japan Co., Ltd.]. (manufactured by BASF Japan Ltd.), Jonkryl 63J (manufactured by BASF Japan Ltd.), Jonkryl 70J (manufactured by BASF Japan Ltd.), and the like.
　酸性基及び／又は酸性基の塩を有し、かつ上記（ｂ）を満たす市販の分散剤としては、例えば、ソルスパース４６０００〔日本ルーブリゾール（株）製〕、ソルスパース４７０００〔日本ルーブリゾール（株）製〕などが挙げられる。 Examples of commercially available dispersants having an acidic group and/or a salt of an acidic group and satisfying the above (b) include Solsperse 46000 (manufactured by Nippon Lubrizol Co., Ltd.) and Solsperse 47000 (manufactured by Nippon Lubrizol Co., Ltd.). [manufactured]] etc.
　酸性基及び／又は酸性基の塩を有し、かつ上記（ｃ）を満たす市販の分散剤としては、例えば、ジョンクリル５７Ｊ〔ＢＡＳＦジャパン（株）製〕、ジョンクリル６３Ｊ〔ＢＡＳＦジャパン（株）製〕、ジョンクリル７０J〔ＢＡＳＦジャパン（株）製〕などが挙げられる。 Examples of commercially available dispersants having an acidic group and/or a salt of an acidic group and satisfying the above (c) include Joncryl 57J [manufactured by BASF Japan Ltd.] and Joncryl 63J [manufactured by BASF Japan Ltd.]. [manufactured by BASF Japan Co., Ltd.], and Jonkryl 70J [manufactured by BASF Japan Co., Ltd.].
　酸性基及び／又は酸性基の塩を有し、かつ上記（ｄ）を満たす市販の分散剤としては、例えば、アロンＡ－１２ＳＬ〔東亞合成（株）製〕、アロンＡ－６０１６Ａ〔東亞合成（株）製〕、アロンＡ－６０１７〔東亞合成（株）製〕、アロンＡ－６０２０〔東亞合成（株）製〕、アロンＡ－６０３１〔東亞合成（株）製〕などが挙げられる。アクリル－スルホン酸系共重合体は、金属塩（好ましくはナトリウム塩）または未中和型であってもよく、好ましくは未中和型である。 Commercially available dispersants that have an acidic group and/or a salt of an acidic group and satisfy the above (d) include, for example, Aron A-12SL [manufactured by Toagosei Co., Ltd.], Aron A-6016A [manufactured by Toagosei Co., Ltd.] Aron A-6017 [manufactured by Toagosei Co., Ltd.], Aron A-6020 [manufactured by Toagosei Co., Ltd.], Aron A-6031 [manufactured by Toagosei Co., Ltd.], and the like. The acrylic-sulfonic acid copolymer may be in the form of a metal salt (preferably a sodium salt) or an unneutralized type, and is preferably an unneutralized type.
　酸性基及び／又は酸性基の塩を有し、かつ上記（ｅ）を満たす市販の分散剤としては、例えば、ＤＩＳＰＥＲ　ＢＹＫ－２０１０〔ビックケミー・ジャパン（株）製〕、フローレンＧ－７００ＡＭＰ〔共栄社化学（株）製〕などが挙げられる。 Examples of commercially available dispersants that have an acidic group and/or a salt of an acidic group and satisfy the above (e) include DISPER BYK-2010 [manufactured by BYK-Chemie Japan Co., Ltd.], Florene G-700AMP [Kyoeisha Chemical Co., Ltd.] Co., Ltd.].
　本発明の実施形態によるインキ組成物が分散剤を含む場合、グアニン顔料に対する分散剤の含有率は、特に限定されるものではないが、好ましくは０．１～１００質量％、より好ましくは１～５０質量％、さらに好ましくは５～３０質量％の範囲である。分散剤の含有率が上記の範囲内にあることにより、インキ組成物中におけるグアニン顔料の分散性をより安定的に維持させることができる。 When the ink composition according to the embodiment of the present invention contains a dispersant, the content of the dispersant relative to the guanine pigment is not particularly limited, but is preferably 0.1 to 100% by mass, more preferably 1 to 100% by mass. The amount is 50% by weight, more preferably 5 to 30% by weight. When the content of the dispersant is within the above range, the dispersibility of the guanine pigment in the ink composition can be maintained more stably.
　本発明の実施形態によるインキ組成物は、水を含んでなる。水は、グアニンを分散させる分散媒として使用される。分散媒として、有機溶媒等を使用することも考えられる。しかし、グアニンは、有機溶媒には難溶である（すなわち若干溶解する）のに対し、水には不溶であることから、グアニンの効果（すなわち白色を呈し、筆跡に隠蔽性を付与する効果）をより有効に発揮させる上で、水を用いることが重要である。また、有機溶媒には、比重が小さいものが多く（例えば、エタノールであれば比重０．７８９）、有機溶媒を分散媒として用いた場合、有機溶媒とグアニンとの比重差が大きくなり、水を用いる場合と比べてグアニンが沈降しやすくなる。そのため、グアニンの分散性の観点でも水を用いることが重要である。
　水としては特に制限されるものではなく、例えば、水道水、イオン交換水、限外ろ過水、蒸留水等を例示できる。 An ink composition according to an embodiment of the present invention comprises water. Water is used as a dispersion medium to disperse the guanine. It is also possible to use an organic solvent or the like as a dispersion medium. However, while guanine is sparingly soluble in organic solvents (that is, slightly soluble), it is insoluble in water. It is important to use water in order to make more effective use of water. In addition, many organic solvents have a small specific gravity (for example, ethanol has a specific gravity of 0.789), and when an organic solvent is used as a dispersion medium, the difference in specific gravity between the organic solvent and guanine becomes large, causing water to evaporate. Compared to the case where guanine is used, it becomes easier to precipitate guanine. Therefore, it is important to use water also from the viewpoint of dispersibility of guanine.
Water is not particularly limited, and examples include tap water, ion-exchanged water, ultrafiltrated water, and distilled water.
　インキ組成物の総質量に対する水の含有率は、特に限定されるものではないが、好ましくは１０～９０質量％、より好ましくは３０～８０質量％の範囲である。 The content of water relative to the total mass of the ink composition is not particularly limited, but is preferably in the range of 10 to 90% by mass, more preferably 30 to 80% by mass.
　本発明の実施形態によるインキ組成物には、さらに着色剤を配合させることができる。
　グアニン顔料と着色剤を併用させることにより、隠蔽性を有する有色（パステル調の色）を呈するインキ組成物とすることができる。 The ink composition according to the embodiment of the present invention may further contain a colorant.
By using a guanine pigment and a coloring agent in combination, an ink composition exhibiting a colored (pastel-like color) having concealing properties can be obtained.
　着色剤としては、溶媒に溶解または分散可能な、染料または顔料であれば特に限定されるものではない。 The colorant is not particularly limited as long as it is a dye or pigment that can be dissolved or dispersed in a solvent.
　染料としては、酸性染料、塩基性染料、直接染料、油溶性染料、分散染料等が挙げられる。 Examples of dyes include acid dyes, basic dyes, direct dyes, oil-soluble dyes, and disperse dyes.
　酸性染料としては、例えば、ニューコクシン（Ｃ．Ｉ．１６２５５）、タートラジン（Ｃ．Ｉ．１９１４０）、アシッドブルーブラック１０Ｂ（Ｃ．Ｉ．２０４７０）、ギニアグリーン（Ｃ．Ｉ．４２０８５）、ブリリアントブルーＦＣＦ（Ｃ．Ｉ．４２０９０）、アシッドバイオレット６Ｂ（Ｃ．Ｉ．４２６４０）、ソルブルブルー（Ｃ．Ｉ．４２７５５）、ナフタレングリーン（Ｃ．Ｉ．４４０２５）、エオシン（Ｃ．Ｉ．４５３８０）、フロキシン（Ｃ．Ｉ．４５４１０）、エリスロシン（Ｃ．Ｉ．４５４３０）、ニグロシン（Ｃ．Ｉ．５０４２０）、アシッドフラビン（Ｃ．Ｉ．５６２０５）等を例示できる。 Examples of acidic dyes include New Coccin (C.I. 16255), Tartrazine (C.I. 19140), Acid Blue Black 10B (C.I. 20470), Guinea Green (C.I. 42085), and Brilliant. Blue FCF (C.I.42090), Acid Violet 6B (C.I.42640), Soluble Blue (C.I.42755), Naphthalene Green (C.I.44025), Eosin (C.I.45380) , phloxine (C.I. 45410), erythrosin (C.I. 45430), nigrosine (C.I. 50420), acidflavin (C.I. 56205), and the like.
　塩基性染料としては、例えば、クリソイジン（Ｃ．Ｉ．１１２７０）、メチルバイオレットＦＮ（Ｃ．Ｉ．４２５３５）、クリスタルバイオレット（Ｃ．Ｉ．４２５５５）、マラカイトグリーン（Ｃ．Ｉ．４２０００）、ビクトリアブルーＦＢ（Ｃ．Ｉ．４４０４５）、ローダミンＢ（Ｃ．Ｉ．４５１７０）、アクリジンオレンジＮＳ（Ｃ．Ｉ．４６００５）、メチレンブルーＢ（Ｃ．Ｉ．５２０１５）等を例示できる。 Examples of basic dyes include chrysoidine (C.I.11270), methyl violet FN (C.I.42535), crystal violet (C.I.42555), malachite green (C.I.42000), and Victoria blue. Examples include FB (C.I.44045), Rhodamine B (C.I.45170), Acridine Orange NS (C.I.46005), and Methylene Blue B (C.I.52015).
　直接染料としては、例えば、コンゴーレッド（Ｃ．Ｉ．２２１２０）、ダイレクトスカイブルー５Ｂ（Ｃ．Ｉ．２４４００）、バイオレットＢＢ（Ｃ．Ｉ．２７９０５）、ダイレクトディープブラックＥＸ（Ｃ．Ｉ．３０２３５）、カヤラスブラックＧコンク（Ｃ．Ｉ．３５２２５）、ダイレクトファーストブラックＧ（Ｃ．Ｉ．３５２５５）、フタロシアニンブルー（Ｃ．Ｉ．７４１８０）等を例示できる。 Examples of direct dyes include Congo Red (C.I.22120), Direct Sky Blue 5B (C.I.24400), Violet BB (C.I.27905), and Direct Deep Black EX (C.I.30235). , Kayaras Black G Conch (C.I. 35225), Direct Fast Black G (C.I. 35255), and Phthalocyanine Blue (C.I. 74180).
　油溶性染料としては、例えば、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ　Ｂｌａｃｋ　７、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ　Ｂｌａｃｋ　１２３、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ　Ｂｌｕｅ　２、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ　Ｂｌｕｅ　２５、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ　Ｂｌｕｅ　５５、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ　Ｂｌｕｅ　７０、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ　Ｒｅｄ　８、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ　Ｒｅｄ　４９、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ　Ｒｅｄ　１００、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ　Ｖｉｏｌｅｔ　８、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ　Ｖｉｏｌｅｔ　２１、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ　Ｇｒｅｅｎ　３、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ　Ｙｅｌｌｏｗ　２１、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ　Ｙｅｌｌｏｗ　４４、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ　Ｙｅｌｌｏｗ　６１、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ　Ｏｒａｎｇｅ　３７等を例示できる。 Examples of oil-soluble dyes include C.I. I. Solvent Black 7, C. I. Solvent Black 123, C. I. Solvent Blue 2, C. I. Solvent Blue 25, C. I. Solvent Blue 55, C. I. Solvent Blue 70, C. I. Solvent Red 8, C. I. Solvent Red 49, C. I. Solvent Red 100, C. I. Solvent Violet 8, C. I. Solvent Violet 21, C. I. Solvent Green 3, C. I. Solvent Yellow 21, C. I. Solvent Yellow 44, C. I. Solvent Yellow 61, C. I. An example is Solvent Orange 37.
　分散染料としては、例えば、Ｃ．Ｉ．Ｄｉｓｐｅｒｓｅ　Ｙｅｌｌｏｗ　８２、Ｃ．Ｉ．Ｄｉｓｐｅｒｓｅ　Ｙｅｌｌｏｗ　３、Ｃ．Ｉ．Ｄｉｓｐｅｒｓｅ　Ｙｅｌｌｏｗ　５４、Ｃ．Ｉ．Ｄｉｓｐｅｒｓｅ　Ｒｅｄ　１９１、Ｃ．Ｉ．Ｄｉｓｐｅｒｓｅ　Ｒｅｄ　６０、Ｃ．Ｉ．Ｄｉｓｐｅｒｓｅ　Ｖｉｏｌｅｔ　５７等を例示できる。 Examples of disperse dyes include C.I. I. Disperse Yellow 82, C. I. Disperse Yellow 3, C. I. Disperse Yellow 54, C. I. Disperse Red 191, C. I. Disperse Red 60, C. I. An example is Disperse Violet 57.
　顔料としては、無機顔料、有機顔料、光輝性顔料、蛍光顔料、蓄光顔料等が挙げられる。 Examples of pigments include inorganic pigments, organic pigments, glitter pigments, fluorescent pigments, and luminescent pigments.
　無機顔料としては、例えば、カーボンブラック、鉄黒、黄色酸化鉄、弁柄、群青等を例示できる。 Examples of inorganic pigments include carbon black, iron black, yellow iron oxide, Bengara, and ultramarine blue.
　有機顔料としては、例えば、アゾ系顔料、フタロシアニン系顔料、キナクリドン系顔料、ペリレン系顔料、ペリノン系顔料、イソインドリノン系顔料、イソインドリン系顔料、ジオキサジン系顔料、チオインジゴ系顔料、アントラキノン系顔料、キノフタロン系顔料、ジケトピロロピロール系顔料、スレン系顔料、インジゴ系顔料、フタロン系顔料、メチン・アゾメチン系顔料、金属錯体系顔料等を例示できる。 Examples of organic pigments include azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, thioindigo pigments, anthraquinone pigments, Examples include quinophthalone pigments, diketopyrrolopyrrole pigments, threne pigments, indigo pigments, phthalone pigments, methine/azomethine pigments, and metal complex pigments.
　顔料としては、予め界面活性剤及び／又は樹脂を用いて顔料を微細に安定的に水性媒体中に分散させた、水分散顔料等を用いることもできる。 As the pigment, it is also possible to use a water-dispersed pigment, etc., in which the pigment is finely and stably dispersed in an aqueous medium using a surfactant and/or resin in advance.
　顔料を分散する樹脂としては、例えば、ポリアミド、ウレタン樹脂、ポリエステル、エポキシ樹脂、メラミン樹脂、フェノール樹脂、シリコーン樹脂、ポリビニルアルコール、ポリビニルピロリドン、ポリ酢酸ビニル、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリスチレン、アクリル酸樹脂、マレイン酸樹脂、アラビアゴム、セルロース、デキストラン、カゼイン、およびそれらの誘導体、上記の樹脂の共重合体等を例示できる。 Examples of resins for dispersing pigments include polyamide, urethane resin, polyester, epoxy resin, melamine resin, phenol resin, silicone resin, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, polystyrene, and acrylic. Examples include acid resins, maleic acid resins, gum arabic, cellulose, dextran, casein, derivatives thereof, and copolymers of the above resins.
　光輝性顔料としては、ガラス片等の芯物質の表面を金、銀等で被覆した金属光沢顔料、天然雲母、合成雲母、薄片状酸化アルミニウム等の芯物質の表面を酸化チタン等の金属酸化物で被覆したパール顔料、コレステリック液晶型顔料、金属粉顔料、フィルム等の基材に形成したアルミニウム等の金属蒸着膜を剥離して得られる金属顔料、無色透明または着色透明フィルムにアルミニウム等の金属蒸着膜を形成し粉末処理した金属顔料等が挙げられる。 Glittering pigments include metallic luster pigments in which the surface of a core material such as glass pieces is coated with gold, silver, etc., natural mica, synthetic mica, flaky aluminum oxide, etc., and metal oxides such as titanium oxide on the surface of a core material such as flaky aluminum oxide. pearl pigments, cholesteric liquid crystal pigments, metal powder pigments, metal pigments obtained by peeling off metal vapor-deposited films such as aluminum formed on base materials such as films, and metal vapor-deposited films such as aluminum on colorless transparent or colored transparent films. Examples include metal pigments that have been formed into a film and processed into powder.
　蛍光顔料としては、各種蛍光性染料を樹脂マトリックス中に固溶体化した合成樹脂微細粒子状の蛍光顔料が挙げられる。 Examples of the fluorescent pigment include fluorescent pigments in the form of synthetic resin fine particles in which various fluorescent dyes are made into a solid solution in a resin matrix.
　蓄光顔料としては、太陽及び／又は電灯等の光線を吸収、蓄積し、暗所において光を徐々に放出して発光する（これを残光とよんでいる）特性を有するものであれば汎用のものが用いられ、ＣａＳ／Ｂｉ系、ＣａＳｒＳ／Ｂｉ系、ＺｎＳ／Ｃｕ系、ＺｎＣｄＳ／Ｃｕ系、ＳｒＡｌ２Ｏ４／稀土類金属系等の蓄光顔料が挙げられる。 Luminescent pigments are general-purpose pigments that have the property of absorbing and accumulating light from the sun and/or electric lamps, and gradually emitting light in a dark place (this is called afterglow). Examples include phosphorescent pigments such as CaS/Bi type, CaSrS/Bi type, ZnS/Cu type, ZnCdS/Cu type, and SrAl2O4/rare earth metal type.
　着色剤は一種、または二種以上を併用して用いることができる。 One type of colorant or a combination of two or more types can be used.
　着色剤として上記の顔料を用いる場合、必要に応じて顔料分散剤を用いることができる。顔料分散剤としては、アニオン系、ノニオン系等の界面活性剤；ポリアクリル酸、スチレン－アクリル酸等のアニオン性高分子；ＰＶＰ、ＰＶＡ等の非イオン性高分子等が挙げられる。 When using the above pigments as colorants, a pigment dispersant can be used as necessary. Examples of the pigment dispersant include anionic and nonionic surfactants; anionic polymers such as polyacrylic acid and styrene-acrylic acid; nonionic polymers such as PVP and PVA.
　上記した染料または顔料は、そのまま用いても有効であるが、染料または顔料をマイクロカプセルに内包させたマイクロカプセル顔料、及び／又は、染料または顔料を含有させた樹脂粒子も、着色剤として用いることができる。特に、染料または顔料は、マイクロカプセルに内包させることにより外部環境から隔離、保護され、内包物の耐水性および耐光性を向上させることができる。 The above-mentioned dyes or pigments are effective when used as they are, but microcapsule pigments in which dyes or pigments are encapsulated in microcapsules, and/or resin particles containing dyes or pigments may also be used as colorants. Can be done. In particular, dyes or pigments can be isolated and protected from the external environment by being encapsulated in microcapsules, and the water resistance and light resistance of the encapsulated material can be improved.
　マイクロカプセル顔料は、上記した染料または顔料を油性媒体中に溶解または分散させた着色体を、マイクロカプセルに内包させることによって形成することができる。 A microcapsule pigment can be formed by encapsulating a colored body in which the above dye or pigment is dissolved or dispersed in an oily medium in microcapsules.
　油性媒体としては、例えば、一塩基酸エステル、二塩基酸モノエステル、二塩基酸ジエステル、多価アルコールの部分エステルないし完全エステル等のエステル類、アルキルベンゼン、アルキルナフタレン等の芳香族炭化水素類、高級アルコール類、ケトン類、エーテル類等を例示できる。 Examples of oil-based media include monobasic acid esters, dibasic acid monoesters, dibasic acid diesters, esters such as partial or complete esters of polyhydric alcohols, aromatic hydrocarbons such as alkylbenzenes and alkylnaphthalenes, and higher-grade esters. Examples include alcohols, ketones, and ethers.
　油性媒体は一種、または二種以上を併用して用いることができる。 The oil-based medium can be used alone or in combination of two or more.
　マイクロカプセル顔料のマイクロカプセル化は、従来公知のイソシアネート系の界面重合法、メラミン－ホルマリン系等のｉｎ　Ｓｉｔｕ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、スプレードライング法等があり、用途に応じて適宜選択される。カプセルの材質としては、例えば、エポキシ樹脂、尿素樹脂、ウレタン樹脂、イソシアネート樹脂等を例示できる。 Microcapsule pigments can be microencapsulated using conventionally known isocyanate-based interfacial polymerization methods, melamine-formalin-based in-situ polymerization methods, in-liquid curing coating methods, phase separation methods from aqueous solutions, and phase separation methods from organic solvents. , melting and dispersion cooling method, air suspension coating method, spray drying method, etc., which are appropriately selected depending on the application. Examples of the material for the capsule include epoxy resin, urea resin, urethane resin, and isocyanate resin.
　マイクロカプセルの表面には、目的に応じてさらに二次的な樹脂皮膜を設けて耐久性を付与させたり、表面特性を改質させて実用に供することもできる。 Depending on the purpose, a secondary resin film can be further provided on the surface of the microcapsules to impart durability or to modify the surface characteristics for practical use.
　染料を含有させた樹脂粒子としては、樹脂粒子中に上記した染料が均質に溶解または分散された樹脂粒子、および樹脂粒子に染料が染着された樹脂粒子等が挙げられる。 Examples of resin particles containing a dye include resin particles in which the above-described dye is homogeneously dissolved or dispersed, and resin particles in which a dye is dyed onto the resin particles.
　樹脂粒子を構成する樹脂としては特に限定されるものではないが、熱硬化性樹脂が好ましい。
　熱硬化性樹脂は、熱可塑性樹脂と比較して耐溶剤性および耐熱性に優れると共に、含有される染料の耐移行性にも優れており、樹脂から染料が溶出することを抑制できるため好適である。
　熱硬化性樹脂の中でも、染料の溶出をいっそう抑制できることから、グアナミン樹脂またはメラミン樹脂が好ましい。 The resin constituting the resin particles is not particularly limited, but thermosetting resins are preferred.
Thermosetting resins are preferable because they have better solvent resistance and heat resistance than thermoplastic resins, and they also have better migration resistance for the dyes they contain, which prevents dyes from eluting from the resin. be.
Among thermosetting resins, guanamine resin or melamine resin is preferable because they can further suppress dye elution.
　顔料を含有させた樹脂粒子としては、樹脂粒子中に上記した顔料が均質に分散された樹脂粒子、および樹脂粒子の表面が顔料で被覆された樹脂粒子等が挙げられる。 Examples of the resin particles containing a pigment include resin particles in which the above pigment is homogeneously dispersed in the resin particles, and resin particles in which the surface of the resin particles is coated with a pigment.
　樹脂粒子を構成する樹脂としては特に限定されるものではなく、汎用の樹脂を用いることができる。 The resin constituting the resin particles is not particularly limited, and general-purpose resins can be used.
　樹脂粒子は、粉砕法、スプレードライング法、あるいは、水性または油性媒体中において、染料または顔料の存在下で重合する重合法により製造することができる。重合法としては、懸濁重合法、懸濁重縮合法、分散重合法、乳化重合法等が挙げられる。 The resin particles can be produced by a pulverization method, a spray drying method, or a polymerization method in which polymerization is performed in the presence of a dye or pigment in an aqueous or oily medium. Examples of polymerization methods include suspension polymerization, suspension polycondensation, dispersion polymerization, and emulsion polymerization.
　樹脂粒子の形状としては特に限定されるものではなく、真球状、楕円球状、略球状等の球状、多角形状、扁平状等の樹脂粒子を用いることができる。これらの中でも、球状の樹脂粒子を用いることが好ましい。 The shape of the resin particles is not particularly limited, and spherical, polygonal, flat, and other resin particles can be used. Among these, it is preferable to use spherical resin particles.
　着色剤が染料もしくは顔料、または、上記したマイクロカプセル顔料もしくは樹脂粒子である場合、インキ組成物の総質量に対する着色剤の含有率は、特に限定されるものではないが、好ましくは０．０１～５０質量％、より好ましくは０．１～３０質量％の範囲である。着色剤の含有率が５０質量％を超えると、インキ組成物を収容した筆記具のインキ吐出性が低下し易く、カスレおよび線飛び等の筆記不良が発生し易くなる。一方、含有率が０．０１質量％未満では、筆記具としての好適な筆跡濃度が得られ難くなる。 When the colorant is a dye or pigment, or the above-mentioned microcapsule pigment or resin particles, the content of the colorant with respect to the total mass of the ink composition is not particularly limited, but is preferably from 0.01 to The amount is 50% by weight, more preferably 0.1 to 30% by weight. When the content of the colorant exceeds 50% by mass, the ink ejection properties of the writing instrument containing the ink composition tend to decrease, and writing defects such as blurring and line skipping tend to occur. On the other hand, if the content is less than 0.01% by mass, it becomes difficult to obtain a suitable handwriting density as a writing instrument.
　着色剤として、温度変化により色変化する熱変色性材料、及び／又は光の照射により色変化する光変色性材料等の変色性材料を用いることもできる。これらの色変化は可逆的であっても、不可逆的であってもよい。温度変化あるいは光の照射により繰り返し色変化を発現できることから、可逆熱変色性材料及び／又は可逆光変色性材料が好適である。 As the colorant, it is also possible to use color-changing materials such as thermochromic materials that change color due to temperature changes and/or photochromic materials that change color due to light irradiation. These color changes may be reversible or irreversible. Reversible thermochromic materials and/or reversible photochromic materials are suitable because they can repeatedly exhibit color changes due to temperature changes or light irradiation.
　可逆熱変色性材料としては、（イ）電子供与性呈色性有機化合物、（ロ）電子受容性化合物、（ハ）上記（イ）、（ロ）成分の呈色反応の生起温度を決める反応媒体からなる可逆熱変色性組成物が挙げられる。 The reversible thermochromic material includes (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reaction that determines the temperature at which the color reaction of the components (a) and (b) above occurs. Examples include reversible thermochromic compositions comprising a medium.
　可逆熱変色性組成物としては、特公昭５１－４４７０６号公報、特公昭５１－４４７０７号公報、特公平１－２９３９８号公報等に記載された、ヒステリシス幅（ΔＨ）が比較的小さい特性（ΔＨ＝１～７℃）を有する加熱消色型の可逆熱変色性組成物を用いることができる。加熱消色型とは、加熱により消色し、冷却により発色することを意味する。この可逆熱変色性組成物は、所定の温度（変色点）を境としてその前後で変色し、高温側変色点以上の温度域で消色状態、低温側変色点以下の温度域で発色状態を呈し、両状態のうち常温域では特定の一方の状態しか存在せず、もう一方の状態は、その状態が発現するのに要した熱または冷熱が適用されている間は維持されるが、熱または冷熱の適用がなくなれば常温域で呈する状態に戻る。 The reversible thermochromic composition has the characteristic (ΔH) of relatively small hysteresis width (ΔH) described in Japanese Patent Publication No. 51-44706, Japanese Patent Publication No. 51-44707, Japanese Patent Publication No. 1-29398, etc. = 1 to 7° C.) can be used. The heat-decolorizing type means that the color is decolored by heating and the color is developed by cooling. This reversible thermochromic composition changes color before and after a predetermined temperature (color change point), becomes decolored at a temperature above the high temperature side discoloration point, and changes color at a temperature below the low temperature side discoloration point. Out of the two states, only one specific state exists in the normal temperature range, and the other state is maintained as long as the heat or cold necessary for that state to occur is applied, but Or, if the application of cold or heat is removed, it returns to the state it exhibits at room temperature.
　可逆熱変色性組成物としては、特公平４－１７１５４号公報、特開平７－１７９７７７号公報、特開平７－３３９９７号公報、特開平８－３９９３６号公報、特開２００５－１３６９号公報等に記載されているヒステリシス幅が大きい特性（ΔＨ＝８～８０℃）を有する加熱消色型の可逆熱変色性組成物を用いることもできる。加熱消色型とは、加熱により消色し、冷却により発色することを意味する。この可逆熱変色性組成物は、温度変化による発色濃度の変化をプロットした曲線の形状が、温度を変色温度域より低温側から上昇させていく場合と、逆に変色温度域より高温側から下降させていく場合とで大きく異なる経路を辿って変色し、完全発色温度ｔ１以下の温度域での発色状態、または完全消色温度ｔ４以上の高温域での消色状態が、特定温度域〔発色開始温度ｔ２～消色開始温度ｔ３の間の温度域（実質二相保持温度域）〕で色彩記憶性を有する。 Reversible thermochromic compositions are described in JP-A-4-17154, JP-A-7-179777, JP-A-7-33997, JP-A-8-39936, JP-A-2005-1369, etc. It is also possible to use a heat-erasable reversible thermochromic composition having the described characteristic of having a large hysteresis width (ΔH=8 to 80° C.). The heat-decolorizing type means that the color is decolored by heating and the color develops by cooling. In this reversible thermochromic composition, the shape of the curve plotting the change in color density due to temperature change is such that the shape of the curve is such that the temperature increases from a lower side than the discoloration temperature range, and vice versa. The color changes following a very different path depending on the case, and the color development state in the temperature range below the complete color development temperature t 1 , or the color discoloration state in the high temperature range above the complete color development temperature t 4 , is the specific temperature range. It has color memory in the [temperature range between the coloring start temperature t 2 and the discoloration start temperature t 3 (substantially two-phase retention temperature range)].
　なお、本発明の実施形態に上記の色彩記憶性を有する可逆熱変色性組成物を適用する場合、可逆熱変色性組成物としては、具体的には、完全発色温度ｔ１を冷凍室、寒冷地等でしか得られない温度、かつ、完全消色温度ｔ４を摩擦体による摩擦熱、ヘアドライヤー等身近な加熱体から得られる温度の範囲に特定し、ΔＨ値を４０～１００℃に特定することにより、常態（日常の生活温度域）で呈する色彩の保持に有効に機能させることができる。 In addition, when applying the above-mentioned reversible thermochromic composition having color memory to the embodiment of the present invention, specifically, the reversible thermochromic composition has a complete color development temperature t 1 in a freezing room or in a cold room. Specify the temperature that can only be obtained from the ground, etc., and the complete discoloration temperature t4 to be within the range of frictional heat from a friction body and the temperature that can be obtained from a familiar heating body such as a hair dryer, and specify the ΔH value between 40 and 100 degrees Celsius. By doing so, it is possible to effectively maintain the color exhibited under normal conditions (in the everyday living temperature range).
　冷凍室、寒冷地等でしか得られない温度は、－５０～０℃であり、好ましくは－４０～－５℃、より好ましくは－３０～－１０℃の範囲である。
　ヘアドライヤー等身近な加熱体から得られる温度は、５０～９５℃であり、好ましくは５０～９０℃、より好ましくは６０～８０℃の範囲である。 The temperature that can only be obtained in a freezing room, a cold region, etc. is in the range of -50 to 0°C, preferably in the range of -40 to -5°C, and more preferably in the range of -30 to -10°C.
The temperature obtained from a familiar heating element such as a hair dryer is in the range of 50 to 95°C, preferably 50 to 90°C, more preferably 60 to 80°C.
　可逆熱変色性組成物として、特公昭５１－４４７０６号公報、特開２００３－２５３１４９号公報等に記載された、没食子酸エステルを用いた加熱発色型の可逆熱変色性組成物を用いることもできる。加熱発色型とは、加熱により発色し、冷却により消色することを意味する。 As the reversible thermochromic composition, heat coloring type reversible thermochromic compositions using gallic acid ester, which are described in Japanese Patent Publication No. 51-44706, Japanese Patent Application Laid-Open No. 2003-253149, etc., can also be used. . The heat coloring type means that the color develops when heated and the color disappears when cooled.
　可逆熱変色性組成物は、上記の（イ）、（ロ）、（ハ）成分を必須成分とする相溶体であり、各成分の割合は、濃度、変色温度、変色形態、および各成分の種類に左右される。一般的に所望の特性が得られる成分比は、（イ）成分１に対して、（ロ）成分０．１～１００、好ましくは０．１～５０、より好ましくは０．５～２０、（ハ）成分１～８００、好ましくは５～２００、より好ましくは１０～１００の範囲である（上記した割合はいずれも質量部である）。 The reversible thermochromic composition is a compatible solution containing the above components (a), (b), and (c) as essential components, and the proportion of each component depends on the concentration, color change temperature, color change form, and each component. Depends on the type. In general, the component ratio at which desired characteristics can be obtained is (a) component 1 to (b) component 0.1 to 100, preferably 0.1 to 50, more preferably 0.5 to 20, ( c) Component ranges from 1 to 800, preferably from 5 to 200, more preferably from 10 to 100 (all the above ratios are parts by mass).
　可逆光変色性材料としては、太陽光、紫外光、または、ピーク発光波長が４００～４９５ｎｍの範囲にある青色光を照射すると発色し、照射を止めると消色する従来公知のスピロオキサジン誘導体、スピロピラン誘導体、ナフトピラン誘導体等のフォトクロミック化合物が挙げられる。 Examples of reversible photochromic materials include spirooxazine derivatives and spiropyran, which develop color when irradiated with sunlight, ultraviolet light, or blue light with a peak emission wavelength in the range of 400 to 495 nm, and disappear when irradiation is stopped. Examples include photochromic compounds such as derivatives and naphthopyran derivatives.
　スピロオキサジン誘導体としては、例えば、従来公知のインドリノスピロベンゾオキサジン系化合物、インドリノスピロナフトオキサジン系化合物、インドリノスピロフェナントロオキサジン系化合物、インドリノスピロキノリノオキサジン系化合物等を例示できる。 Examples of spirooxazine derivatives include conventionally known indolinospirobenzoxazine compounds, indolinospironaphthoxazine compounds, indolinospirophenanthrooxazine compounds, and indolinospiroquinolinooxazine compounds.
　さらに、光メモリー性（色彩記憶性光変色性）を有するフォトクロミック化合物として、例えば、従来公知のフルギド誘導体、ジアリールエテン誘導体等を例示できる。 Furthermore, examples of photochromic compounds having photomemory properties (color memory and photochromic properties) include conventionally known fulgide derivatives, diarylethene derivatives, and the like.
　また、可逆光変色性材料として、上記のフォトクロミック化合物を各種オリゴマーに溶解した可逆光変色性組成物を用いることもできる。
　オリゴマーとしては、スチレン系オリゴマー、アクリル系オリゴマー、テルペン系オリゴマー、テルペンフェノール系オリゴマーが挙げられる。 Further, as the reversible photochromic material, a reversible photochromic composition in which the above photochromic compound is dissolved in various oligomers can also be used.
Examples of oligomers include styrene oligomers, acrylic oligomers, terpene oligomers, and terpene phenol oligomers.
　スチレン系オリゴマーとしては、例えば、低分子量ポリスチレン、スチレン・α－メチルスチレン共重合体、α－メチルスチレン重合体、α－メチルスチレン・ビニルトルエン共重合体等を例示できる。 Examples of the styrenic oligomer include low molecular weight polystyrene, styrene/α-methylstyrene copolymer, α-methylstyrene polymer, α-methylstyrene/vinyltoluene copolymer, and the like.
　アクリル系オリゴマーとしては、例えば、アクリル酸エステル共重合体等を例示できる。 Examples of the acrylic oligomer include acrylic ester copolymers.
　テルペン系オリゴマーとしては、例えば、α－ピネン重合体、β－ピネン重合体、ｄ－リモネン重合体等を例示できる。 Examples of the terpene oligomer include α-pinene polymer, β-pinene polymer, and d-limonene polymer.
　テルペンフェノール系オリゴマーとしては、例えば、α－ピネン・フェノール共重合体等を例示できる。 Examples of the terpene phenol oligomer include α-pinene/phenol copolymer.
　フォトクロミック化合物を各種オリゴマーに溶解することにより、フォトクロミック化合物の耐光性を向上させると共に、発色濃度の向上、さらには変色感度を調整することができる。 By dissolving the photochromic compound in various oligomers, it is possible to improve the light resistance of the photochromic compound, improve the color density, and further adjust the discoloration sensitivity.
　オリゴマーは一種、または二種以上を併用して用いることができる。 One type of oligomer or a combination of two or more types can be used.
　上記した可逆熱変色性組成物または可逆光変色性組成物は、そのまま用いても有効であるが、マイクロカプセルに内包して可逆熱変色性マイクロカプセル顔料または可逆光変色性マイクロカプセル顔料を形成したり、熱可塑性樹脂または熱硬化性樹脂中に分散させて可逆熱変色性樹脂粒子または可逆光変色性樹脂粒子を形成したりして、本発明の実施形態に適用される着色剤として用いることもできる。
　なお、以下において、可逆熱変色性マイクロカプセル顔料および可逆光変色性マイクロカプセル顔料を「マイクロカプセル顔料」と、可逆熱変色性樹脂粒子および可逆光変色性樹脂粒子を「樹脂粒子」と表すことがある。 The above-mentioned reversible thermochromic composition or reversible photochromic composition is effective when used as is, but it may be encapsulated in microcapsules to form a reversible thermochromic microcapsule pigment or a reversible photochromic microcapsule pigment. Alternatively, it can be dispersed in a thermoplastic resin or thermosetting resin to form reversible thermochromic resin particles or reversible photochromic resin particles, and used as a coloring agent applied to the embodiments of the present invention. can.
In addition, in the following, reversible thermochromic microcapsule pigments and reversible photochromic microcapsule pigments may be referred to as "microcapsule pigments", and reversible thermochromic resin particles and reversible photochromic resin particles may be referred to as "resin particles". be.
　可逆熱変色性組成物または可逆光変色性組成物は、マイクロカプセルに内包して可逆熱変色性マイクロカプセル顔料または可逆光変色性マイクロカプセル顔料とすることが好ましい。これは、マイクロカプセルに内包させることにより、化学的、物理的に安定なマイクロカプセル顔料を構成することができ、さらに、種々の使用条件において可逆熱変色性組成物または可逆光変色性組成物は同一の組成に保たれ、同一の作用効果を奏することができるからである。 The reversible thermochromic composition or reversible photochromic composition is preferably encapsulated in microcapsules to form a reversible thermochromic microcapsule pigment or a reversible photochromic microcapsule pigment. By encapsulating it in microcapsules, it is possible to construct chemically and physically stable microcapsule pigments, and furthermore, under various usage conditions, reversible thermochromic compositions or reversible photochromic compositions This is because the same composition can be maintained and the same effects can be achieved.
　マイクロカプセル化は、従来公知のイソシアネート系の界面重合法、メラミン－ホルマリン系等のｉｎ　Ｓｉｔｕ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、スプレードライング法等があり、用途に応じて適宜選択される。カプセルの材質としては、例えば、エポキシ樹脂、尿素樹脂、ウレタン樹脂、イソシアネート樹脂等を例示できる。 Microencapsulation can be achieved using conventionally known isocyanate-based interfacial polymerization methods, melamine-formalin-based in-situ polymerization methods, in-liquid curing coating methods, phase separation methods from aqueous solutions, phase separation methods from organic solvents, and melting and dispersion cooling. method, air suspension coating method, spray drying method, etc., which are appropriately selected depending on the purpose. Examples of the material for the capsule include epoxy resin, urea resin, urethane resin, and isocyanate resin.
　マイクロカプセルの表面には、目的に応じてさらに二次的な樹脂皮膜を設けて耐久性を付与させたり、表面特性を改質させて実用に供することもできる。 Depending on the purpose, a secondary resin film can be further provided on the surface of the microcapsules to impart durability or to modify the surface characteristics for practical use.
　上記のマイクロカプセル顔料は、内包物：壁膜の質量比が７：１～１：１であることが好ましく、内包物と壁膜の質量比が上記の範囲内にあることにより、発色時の色濃度および鮮明性の低下を防止することができる。より好ましくは、内包物：壁膜の質量比が６：１～１：１である。 The above microcapsule pigment preferably has a mass ratio of inclusions to wall film of 7:1 to 1:1, and when the mass ratio of inclusions to wall film is within the above range, Decrease in color density and sharpness can be prevented. More preferably, the mass ratio of inclusions to wall membrane is 6:1 to 1:1.
　マイクロカプセル顔料中に一般の染料または顔料等の非変色性着色剤を配合させることにより、有色（１）から有色（２）への変色挙動を呈するマイクロカプセル顔料とすることもできる。 By blending a non-color-changing coloring agent such as a general dye or pigment into a microcapsule pigment, a microcapsule pigment that exhibits color change behavior from colored (1) to colored (2) can also be obtained.
　着色剤が上記した変色性材料である場合、インキ組成物の総質量に対する着色剤の含有率は、特に限定されるものではないが、好ましくは５～４０質量％、より好ましくは１０～４０質量％、さらに好ましくは１５～３５質量％の範囲である。着色剤の含有率が４０質量％を超えると、インキ組成物を収容した筆記具のインキ吐出性が低下し、カスレおよび線飛び等の筆記不良が発生し易くなる。一方、含有率が５質量％未満では、筆記具としての好適な変色性および筆跡濃度が得られ難く、変色機能を十分に満たすことができ難くなる。 When the colorant is the color-changing material described above, the content of the colorant relative to the total weight of the ink composition is not particularly limited, but is preferably 5 to 40% by weight, more preferably 10 to 40% by weight. %, more preferably in the range of 15 to 35% by weight. If the content of the colorant exceeds 40% by mass, the ink ejection properties of the writing instrument containing the ink composition will be reduced, and writing defects such as blurring and line skipping will likely occur. On the other hand, if the content is less than 5% by mass, it is difficult to obtain suitable discoloration properties and handwriting density as a writing instrument, and it becomes difficult to fully satisfy the discoloration function.
　可逆熱変色性マイクロカプセル顔料もしくは樹脂粒子、または、可逆光変色性マイクロカプセル顔料もしくは樹脂粒子の平均粒子径は、好ましくは０．０１～５μｍ、より好ましくは０．１～３μｍ、さらに好ましくは０．５～３μｍの範囲である。上記のマイクロカプセル顔料または樹脂粒子の平均粒子径が５μｍを超えると、筆記具に用いた場合に良好なインキ吐出性が得られ難くなる。一方、平均粒子径が０．０１μｍ未満では、高濃度の発色性を示し難くなる。 The average particle diameter of the reversible thermochromic microcapsule pigment or resin particles or the reversible photochromic microcapsule pigment or resin particles is preferably 0.01 to 5 μm, more preferably 0.1 to 3 μm, and even more preferably 0. It is in the range of .5 to 3 μm. When the average particle diameter of the above-mentioned microcapsule pigment or resin particles exceeds 5 μm, it becomes difficult to obtain good ink ejectability when used in a writing instrument. On the other hand, if the average particle diameter is less than 0.01 μm, it becomes difficult to exhibit high-density color development.
　なお、平均粒子径の測定は、画像解析式粒度分布測定ソフトウェア〔マウンテック（株）製、製品名：マックビュー〕を用いて粒子の領域を判定し、粒子の領域の面積から投影面積円相当径（Ｈｅｙｗｏｏｄ径）を算出し、その値による等体積球相当の粒子の平均粒子径として測定した値である。 To measure the average particle diameter, determine the particle area using image analysis particle size distribution measurement software [manufactured by Mountech Co., Ltd., product name: Macview], and calculate the projected area circle equivalent diameter from the area of the particle area. (Heywood diameter) is calculated, and the value is measured as the average particle diameter of particles equivalent to an equal-volume sphere based on the calculated value.
　また、全ての粒子或いは大部分の粒子の粒子径が０．２μｍを超える場合は、粒度分布測定装置〔ベックマン・コールター（株）製、製品名：Ｍｕｌｔｉｓｉｚｅｒ　４ｅ〕を用いて、コールター法により等体積球相当の粒子の平均粒子径として測定することも可能である。 In addition, if the particle diameter of all or most of the particles exceeds 0.2 μm, use a particle size distribution analyzer [manufactured by Beckman Coulter Co., Ltd., product name: Multisizer 4e] to divide the particles into equal volumes by the Coulter method. It is also possible to measure as the average particle diameter of particles equivalent to spheres.
　さらに、上記したソフトウェアまたはコールター法による測定装置を用いて計測した数値を基にして、キャリブレーションを行ったレーザー回折／散乱式粒子径分布測定装置〔（株）堀場製作所製、製品名：ＬＡ－３００〕を用いて、体積基準の粒子径および平均粒子径を測定しても良い。 Furthermore, a laser diffraction/scattering particle size distribution measuring device (manufactured by Horiba, Ltd., product name: LA- 300] to measure the volume-based particle diameter and average particle diameter.
　本発明の実施形態によるインキ組成物には、上記した必須成分のほかに、本発明の実施形態の効果を損なわない範囲で任意成分を配合させることができる。 In addition to the above-mentioned essential components, the ink composition according to the embodiment of the present invention can contain optional components within a range that does not impair the effects of the embodiment of the present invention.
　本発明の実施形態によるインキ組成物には、増粘剤を配合させることができ、顔料の凝集および沈降を抑制して、良好な経時安定性を有するインキ組成物とすることができる。
　増粘剤としては、従来公知の物質を用いることが可能であるが、インキ組成物に剪断減粘性を付与できる物質（剪断減粘性付与剤）を用いることが好ましい。 The ink composition according to the embodiment of the present invention can be blended with a thickener to suppress aggregation and sedimentation of the pigment, thereby making it possible to obtain an ink composition having good stability over time.
As the thickener, conventionally known substances can be used, but it is preferable to use a substance that can impart shear thinning properties to the ink composition (shear thinning properties imparting agent).
　剪断減粘性付与剤を用いたインキ組成物は、静置状態、あるいは応力の低いときには高粘度で流動し難く、外部から応力が加わった際に容易に低粘度化する。このため、非筆記時には、インキの漏出を防止したり、インキの分離および逆流を防止したりすることができ、筆記時には、ペン先からのインキ吐出安定性を良好とすることが容易となる。 An ink composition using a shear thinning agent has a high viscosity and is difficult to flow when it is left standing or under low stress, and easily lowers its viscosity when external stress is applied. Therefore, when not writing, ink leakage, ink separation and backflow can be prevented, and when writing, it is easy to improve the stability of ink discharge from the pen tip.
　とりわけ、ペン先としてボールペンチップを備えた形態の筆記具（ボールペン）にこのようなインキ組成物を用いた際には、剪断応力が加わらない静置時には高粘度であるため、ボールペン内にインキ組成物が安定的に保持される。このため、筆記時にはボールの回転によりインキ組成物に強い剪断応力が加わり、ボール近傍のインキ組成物がより低粘度化し易くなることから、インキ吐出安定性を良好とすることができる。 In particular, when such an ink composition is used in a writing instrument (ballpoint pen) equipped with a ballpoint tip as a pen nib, the ink composition is high in viscosity when left standing without shearing stress, so the ink composition may not be present inside the ballpoint pen. is stably maintained. Therefore, during writing, strong shear stress is applied to the ink composition due to the rotation of the ball, and the ink composition near the ball is more likely to have a lower viscosity, so that the ink discharge stability can be improved.
　本発明の実施形態によるインキ組成物が増粘剤を含む場合、インキ組成物の総質量に対する増粘剤の含有率は、特に限定されるものではないが、好ましくは０．１～２０質量％の範囲である。 When the ink composition according to the embodiment of the present invention contains a thickener, the content of the thickener with respect to the total mass of the ink composition is not particularly limited, but is preferably 0.1 to 20% by mass. is within the range of
　剪断減粘性付与剤としては、例えば、水溶性多糖類、メタクリル酸のアルキルエステルを主成分とする分子量１０万～１５万の重合体、ポリ－Ｎ－ビニルカルボン酸アミド架橋物、ベンジリデンソルビトールおよびその誘導体、ベンジリデンキシリトールおよびその誘導体、アルカリ増粘型アクリル樹脂、架橋性アクリル酸重合体、無機質微粒子、ＨＬＢ値が８～１２のノニオン系界面活性剤、ジアルキルスルホコハク酸の金属塩またはアミン塩等を例示できる。 Examples of shear thinning agents include water-soluble polysaccharides, polymers with a molecular weight of 100,000 to 150,000 whose main component is an alkyl ester of methacrylic acid, crosslinked poly-N-vinylcarboxylic acid amide, benzylidene sorbitol, and its like. Examples include derivatives, benzylidene xylitol and its derivatives, alkali-thickened acrylic resins, cross-linked acrylic acid polymers, inorganic fine particles, nonionic surfactants with an HLB value of 8 to 12, metal salts or amine salts of dialkyl sulfosuccinic acid, etc. can.
　剪断減粘性付与剤は一種、または二種以上を併用して用いることができる。 One type of shear thinning agent or a combination of two or more types can be used.
　水溶性多糖類としては、例えば、キサンタンガム、ウェランガム、ゼータシーガム、ダイユータンガム、マクロホモプシスガム、構成単糖がグルコースとガラクトースの有機酸修飾ヘテロ多糖体であるサクシノグリカン（平均分子量が約１００万～８００万）、グアーガム、ローカストビーンガムおよびその誘導体、ヒドロキシエチルセルロース、アルギン酸アルキルエステル類、グルコマンナン、寒天およびカラゲニン等の海藻より抽出されるゲル化能を有する炭水化物等を例示できる。 Examples of water-soluble polysaccharides include xanthan gum, welan gum, zetasea gum, diutan gum, macrohomopsis gum, and succinoglycan, which is an organic acid-modified heteropolysaccharide whose constituent monosaccharides are glucose and galactose (with an average molecular weight of about 1 million to 8,000,000), guar gum, locust bean gum and its derivatives, hydroxyethyl cellulose, alginate alkyl esters, glucomannan, agar, carrageenan, and other carbohydrates with gelling ability extracted from seaweed.
　本発明の実施形態によるインキ組成物には、高分子凝集剤を配合させることができる。高分子凝集剤は、顔料間に緩い橋かけ作用を生じさせ、顔料が高分子凝集剤を介して緩やかな凝集体を形成するため、顔料同士が直接凝集することを抑制して、顔料の分散安定性を向上させることができる。
　高分子凝集剤は、後述するマーキングペンに備えられるインキ吸蔵体の毛細間隙において、インキ組成物中の顔料の沈降を抑制する効果を奏する。よって、高分子凝集剤を配合するインキ組成物は、インキ吸蔵体を備えるマーキングペンに適用されることが好適である。 The ink composition according to the embodiment of the present invention may contain a polymer flocculant. Polymer flocculants create a loose cross-linking effect between pigments, allowing the pigments to form loose aggregates via the polymer flocculant, suppressing direct aggregation of pigments and dispersing pigments. Stability can be improved.
The polymer flocculant has the effect of suppressing sedimentation of the pigment in the ink composition in the capillary gaps of the ink storage body provided in the marking pen described below. Therefore, it is suitable that an ink composition containing a polymer flocculant is applied to a marking pen equipped with an ink storage body.
　高分子凝集剤は、上記した分散剤と併用させることもできる。高分子凝集剤と分散剤の両者を併用する場合、高分子凝集剤を介して形成される緩やかな凝集体の分散性を向上させることができる。 The polymer flocculant can also be used in combination with the above-mentioned dispersant. When both a polymer flocculant and a dispersant are used together, the dispersibility of loose aggregates formed via the polymer flocculant can be improved.
　本発明の実施形態によるインキ組成物が高分子凝集剤を含む場合、インキ組成物の総質量に対する高分子凝集剤の含有率は、特に限定されるものではないが、好ましくは０．０５～１質量％の範囲である。 When the ink composition according to the embodiment of the present invention contains a polymer flocculant, the content of the polymer flocculant with respect to the total mass of the ink composition is not particularly limited, but is preferably 0.05 to 1. It is in the range of % by mass.
　高分子凝集剤としては、ポリビニルピロリドン、ポリエチレンオキサイド、水溶性多糖類等が挙げられる。 Examples of polymer flocculants include polyvinylpyrrolidone, polyethylene oxide, water-soluble polysaccharides, and the like.
　水溶性多糖類としては、例えば、トラガントガム、グアーガム、プルラン、サイクロデキストリン、水溶性セルロース誘導体等を例示できる。 Examples of water-soluble polysaccharides include gum tragacanth, guar gum, pullulan, cyclodextrin, and water-soluble cellulose derivatives.
　水溶性セルロース誘導体としては、例えば、カルボキシメチルセルロース、メチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシエチルメチルセルロース、ヒドロキシプロピルメチルセルロース等を例示できる。 Examples of water-soluble cellulose derivatives include carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxyethylmethylcellulose, and hydroxypropylmethylcellulose.
　本発明の実施形態によるインキ組成物には、界面活性剤を配合させることができ、インキ組成物の表面張力を適切な範囲に調整することができる。
　表面張力の調整に用いる界面活性剤には、ノニオン系界面活性剤、アニオン系界面活性剤、カチオン系界面活性剤、両性界面活性剤等があるが、何れも好適に用いることができる。 The ink composition according to the embodiment of the present invention can contain a surfactant, and the surface tension of the ink composition can be adjusted to an appropriate range.
Surfactants used to adjust the surface tension include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and any of them can be suitably used.
　本発明の実施形態によるインキ組成物が表面張力の調整に用いる界面活性剤を含む場合、インキ組成物の総質量に対する表面張力の調整に用いる界面活性剤の含有率は、特に限定されるものではないが、好ましくは０．０１～２質量％、より好ましくは０．０５～１質量％の範囲である。 When the ink composition according to the embodiment of the present invention contains a surfactant used for adjusting surface tension, the content of the surfactant used for adjusting surface tension with respect to the total mass of the ink composition is not particularly limited. However, it is preferably in the range of 0.01 to 2% by weight, more preferably 0.05 to 1% by weight.
　本発明の実施形態によるインキ組成物には、ｐＨ調整剤を配合させることができ、インキ組成物のｐＨを適切な範囲に調整することができる。ｐＨ調整剤としては、各種の酸性物質または塩基性物質を用いることができる。 A pH adjuster can be added to the ink composition according to the embodiment of the present invention, and the pH of the ink composition can be adjusted to an appropriate range. Various acidic or basic substances can be used as the pH adjuster.
　酸性物質としては、例えば、塩酸、硫酸、硝酸、リン酸、炭酸、ホウ酸、乳酸、クエン酸、酒石酸、リンゴ酸等を例示できる。 Examples of acidic substances include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid, boric acid, lactic acid, citric acid, tartaric acid, and malic acid.
　塩基性物質としては、アンモニア、炭酸ナトリウム、リン酸水素ナトリウム、リン酸水素カリウム、水酸化ナトリウム、水酸化カリウム、酢酸ナトリウム等を例示でき、また、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等のアルカノールアミン類を適用することもできる。 Examples of basic substances include ammonia, sodium carbonate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium hydroxide, potassium hydroxide, sodium acetate, and alkanols such as monoethanolamine, diethanolamine, and triethanolamine. Amines can also be applied.
　本発明の実施形態によるインキ組成物がｐＨ調整剤を含む場合、インキ組成物の総質量に対するｐＨ調整剤の含有率は、特に限定されるものではないが、好ましくは０．１～５質量％、より好ましくは０．５～２質量％の範囲である。 When the ink composition according to the embodiment of the present invention contains a pH adjuster, the content of the pH adjuster based on the total mass of the ink composition is not particularly limited, but is preferably 0.1 to 5% by mass. , more preferably in the range of 0.5 to 2% by mass.
　本発明の実施形態によるインキ組成物には、水と相溶性のある水溶性有機溶剤を配合させることができ、筆記具のペン先からの水分蒸発を抑制することができる。 The ink composition according to the embodiment of the present invention can contain a water-soluble organic solvent that is compatible with water, and can suppress water evaporation from the nib of a writing instrument.
　水溶性有機溶剤としては、例えば、エタノール、プロパノール、ブタノール、グリセリン、ソルビトール、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、エチレングリコール、ジエチレングリコール、チオエチレングリコール、ポリエチレングリコール、プロピレングリコール、ブチレングリコール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノブチルエーテル、エチレングリコールモノメチルエーテルアセテート、スルフォラン、２－ピロリドン、Ｎ－メチル－２－ピロリドン等を例示できる。 Examples of water-soluble organic solvents include ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thioethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, and ethylene glycol monomethyl. Ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone etc. can be exemplified.
　水溶性有機溶剤は一種、または二種以上を併用して用いることができる。 The water-soluble organic solvents can be used alone or in combination of two or more.
　本発明の実施形態によるインキ組成物が水溶性有機溶剤を含む場合、インキ組成物の総質量に対する水溶性有機溶剤の含有率は、特に限定されるものではないが、好ましくは１～４０質量％、より好ましくは５～３０質量％、さらに好ましくは１０～２５質量％の範囲である。水溶性有機溶剤の含有率が４０質量％を超えるとインキ粘度が高くなり易く、インキ組成物を収容した筆記具のインキ吐出性が低下し、カスレおよび線飛び等の筆記不良を生じ易くなる。一方、含有率が１質量％未満では水分蒸発を抑制する効果に乏しくなる。 When the ink composition according to the embodiment of the present invention contains a water-soluble organic solvent, the content of the water-soluble organic solvent with respect to the total mass of the ink composition is not particularly limited, but is preferably 1 to 40% by mass. , more preferably 5 to 30% by weight, and still more preferably 10 to 25% by weight. If the content of the water-soluble organic solvent exceeds 40% by mass, the ink viscosity tends to increase, the ink ejection performance of the writing instrument containing the ink composition decreases, and writing defects such as blurring and line skipping are likely to occur. On the other hand, if the content is less than 1% by mass, the effect of suppressing moisture evaporation will be poor.
　本発明の実施形態によるインキ組成物には、例えば、アルキッド樹脂、アクリル樹脂、スチレン－マレイン酸共重合体、セルロース誘導体、ポリビニルピロリドン、ポリビニルアルコール、デキストリン等の水溶性樹脂を配合させることができ、紙面への固着性および粘性を付与することができる。 The ink composition according to the embodiment of the present invention may contain a water-soluble resin such as an alkyd resin, an acrylic resin, a styrene-maleic acid copolymer, a cellulose derivative, a polyvinylpyrrolidone, a polyvinyl alcohol, or a dextrin. It can provide adhesion and viscosity to paper surfaces.
　水溶性樹脂は一種、または二種以上を併用して用いることができる。 One type of water-soluble resin or a combination of two or more types can be used.
　本発明の実施形態によるインキ組成物が水溶性樹脂を含む場合、インキ組成物の総質量に対する水溶性樹脂の含有率は、特に限定されるものではないが、好ましくは１～３０質量％、より好ましくは１～１０質量％の範囲である。 When the ink composition according to the embodiment of the present invention contains a water-soluble resin, the content of the water-soluble resin with respect to the total mass of the ink composition is not particularly limited, but is preferably 1 to 30% by mass, or more. It is preferably in the range of 1 to 10% by mass.
　本発明の実施形態によるインキ組成物には、その他必要に応じて、各種添加剤を配合させることもできる。 The ink composition according to the embodiment of the present invention may also contain various other additives as necessary.
　添加剤としては、例えば、防錆剤、防腐剤あるいは防黴剤、気泡吸収剤、湿潤剤、消泡剤、比重調整剤等を例示できる。 Examples of additives include rust preventives, antiseptics, antifungal agents, bubble absorbers, wetting agents, antifoaming agents, specific gravity adjusters, and the like.
　防錆剤としては、例えば、ジシクロヘキシルアンモニウムナイトライト、ジイソプロピルアンモニウムナイトライト、サポニン等が例示できる。 Examples of the rust preventive agent include dicyclohexylammonium nitrite, diisopropylammonium nitrite, and saponin.
　防腐剤あるいは防黴剤としては、石炭酸、１，２－ベンゾチアゾリン３－オンのナトリウム塩、安息香酸ナトリウム、デヒドロ酢酸ナトリウム、ソルビン酸カリウム、パラオキシ安息香酸プロピル、２，３，５，６－テトラクロロ－４－（メチルスルフォニル）ピリジン等が例示できる。 Preservatives or antifungal agents include carbolic acid, sodium salt of 1,2-benzothiazolin 3-one, sodium benzoate, sodium dehydroacetate, potassium sorbate, propyl paraoxybenzoate, 2,3,5,6-tetra Examples include chloro-4-(methylsulfonyl)pyridine.
　気泡吸収剤としては、アスコルビン酸類、エリソルビン酸類、α－トコフェロール、カテキン類、合成ポリフェノール、コウジ酸、アルキルヒドロキシルアミン、オキシム誘導体、α－グルコシルルチン、α－リポ酸、ホスホン酸塩、ホスフィン酸塩、亜硫酸塩、スルホキシル酸塩、亜ジチオン酸塩、チオ硫酸塩、二酸化チオ尿素等が例示できる。 Foam absorbers include ascorbic acids, erythorbic acids, α-tocopherol, catechins, synthetic polyphenols, kojic acid, alkylhydroxylamines, oxime derivatives, α-glucosylrutin, α-lipoic acid, phosphonates, phosphinates, Examples include sulfites, sulfoxylates, dithionites, thiosulfates, and thiourea dioxide.
　湿潤剤としては、還元または非還元デンプン加水分解物、トレハロース等の二糖類、オリゴ糖、ショ糖、サイクロデキストリン、ぶどう糖、デキストリン、ソルビット、マンニット、ピロリン酸ナトリウム等が例示できる。 Examples of wetting agents include reduced or non-reduced starch hydrolysates, disaccharides such as trehalose, oligosaccharides, sucrose, cyclodextrin, glucose, dextrin, sorbitol, mannitol, sodium pyrophosphate, and the like.
　本発明の実施形態によるインキ組成物がボールペンチップを備える筆記具（ボールペン）に収容される場合、インキ組成物には潤滑剤を配合させることもできる。 When the ink composition according to the embodiment of the present invention is stored in a writing instrument (ballpoint pen) equipped with a ballpoint pen tip, a lubricant can also be blended into the ink composition.
　潤滑剤は、チップ本体内部に設けられるボール受け座と、チップ本体の前端に備えられるボールとの潤滑性を向上させて、ボール受け座の摩耗を容易に防止することができ、筆記感を向上させることができるものである。 The lubricant improves the lubricity between the ball receiving seat provided inside the tip body and the ball provided at the front end of the tip body, making it easier to prevent wear on the ball receiving seat and improving the writing feel. It is something that can be done.
　潤滑剤としては、例えば、オレイン酸等の高級脂肪酸、長鎖アルキル基を有するノニオン系界面活性剤、ポリエーテル変性シリコーンオイル等を例示できる。 Examples of the lubricant include higher fatty acids such as oleic acid, nonionic surfactants having long-chain alkyl groups, and polyether-modified silicone oil.
　本発明の実施形態によるインキ組成物の製造方法は特に限定されるものではなく、従来公知の任意の方法を用いることができる。
　具体的には、上記の各成分を配合した混合物を、プロペラ攪拌、ホモディスパー、もしくはホモミキサー等の各種攪拌機で攪拌することにより、またはビーズミル等の各種分散機等で分散することにより、インキ組成物を製造することができる。 The method for producing the ink composition according to the embodiment of the present invention is not particularly limited, and any conventionally known method can be used.
Specifically, the ink composition is prepared by stirring a mixture of the above-mentioned components with various stirrers such as propeller stirring, homodisper, or homomixer, or by dispersing it with various dispersion machines such as bead mills. can manufacture things.
　本発明の実施形態によるインキ組成物において、粘度特性は特に限定されない。例えば、高剪断減粘性のインキ組成物（ゲルインキ）、低粘度で低剪断減粘性のインキ組成物、低粘度で非剪断減粘性のインキ組成物（ニュートニアンインキ）等の粘度特性を有するインキ組成物を用いることができる。本発明の実施形態に適用されるグアニン顔料は分散安定性に優れ、インキ組成物が低粘度であっても顔料が沈降し難いことから、本発明の実施形態によるインキ組成物としては、低粘度のインキ組成物が好適である。 In the ink composition according to the embodiment of the present invention, the viscosity characteristics are not particularly limited. For example, ink compositions with viscosity characteristics such as high shear thinning ink compositions (gel inks), low viscosity and low shear thinning ink compositions, and low viscosity non-shear thinning ink compositions (Newtonian inks). objects can be used. The guanine pigment applied to the embodiment of the present invention has excellent dispersion stability, and the pigment does not easily settle even if the ink composition has a low viscosity. The following ink compositions are suitable.
　本発明の実施形態によるインキ組成物がボールペンに用いられる場合、その粘度は、２０℃の環境下において、回転速度１ｒｐｍ（剪断速度３．８４ｓｅｃ－１）の条件で測定した場合、顔料の分散安定性をより安定させることができることから、以下の範囲が好ましい。詳細には、この場合のインキ組成物の粘度は、好ましくは１～２０００ｍＰａ・ｓ、より好ましくは１０～１５００ｍＰａ・ｓ、さらに好ましくは１００～１０００ｍＰａ・ｓの範囲である。
　また、２０℃の環境下において、回転速度１００ｒｐｍ（剪断速度３８４ｓｅｃ－１）の条件で測定した場合、ボールペンのペン先からのインキ吐出性を良好とすることができることから、粘度は、以下の範囲が好ましい。詳細には、この場合のインキ組成物の粘度は、好ましくは１～２００ｍＰａ・ｓ、より好ましくは１０～１００ｍＰａ・ｓ、さらに好ましくは２０～５０ｍＰａ・ｓの範囲である。
　インキ組成物の粘度が上記の範囲内にあることにより、顔料の分散安定性、およびボールペンの機構内におけるインキの易流動性を高いレベルで維持することができる。 When the ink composition according to the embodiment of the present invention is used for a ballpoint pen, its viscosity is determined by the dispersion stability of the pigment when measured at a rotation speed of 1 rpm (shear rate 3.84 sec -1 ) in an environment of 20°C. The following ranges are preferable because the properties can be more stabilized. Specifically, the viscosity of the ink composition in this case is preferably in the range of 1 to 2000 mPa·s, more preferably 10 to 1500 mPa·s, and still more preferably 100 to 1000 mPa·s.
In addition, when measured at a rotational speed of 100 rpm (shear rate 384 sec -1 ) in an environment of 20°C, the viscosity is within the following range because the ink ejection performance from the tip of a ballpoint pen can be made good. is preferred. Specifically, the viscosity of the ink composition in this case is preferably in the range of 1 to 200 mPa·s, more preferably 10 to 100 mPa·s, and even more preferably 20 to 50 mPa·s.
When the viscosity of the ink composition is within the above range, the dispersion stability of the pigment and the free flowability of the ink within the mechanism of the ballpoint pen can be maintained at a high level.
　なお、インキ組成物の粘度は、レオメーター〔ＴＡインスツルメンツ社製、製品名：Ｄｉｓｃｏｖｅｒｙ　ＨＲ－２、コーンプレート（直径４０ｍｍ、角度１°）〕を用いて、インキを２０℃の環境下に置いて、回転速度１ｒｐｍ（剪断速度３．８４ｓｅｃ－１）、または、回転速度１００ｒｐｍ（剪断速度３８４ｓｅｃ－１）の条件で測定した値である。 The viscosity of the ink composition was measured using a rheometer [manufactured by TA Instruments, product name: Discovery HR-2, cone plate (diameter 40 mm, angle 1°)] by placing the ink in an environment of 20°C. , a rotation speed of 1 rpm (shear rate 3.84 sec −1 ), or a rotation speed of 100 rpm (shear rate 384 sec −1 ).
　本発明の実施形態によるインキ組成物がマーキングペンに用いられる場合、その粘度は、２０℃の環境下において、回転数５０ｒｐｍの条件で測定した場合、インキの流動性と顔料の分散安定性を高いレベルで維持することができることから、以下の範囲が好ましい。詳細には、この場合のインキ組成物の粘度は、好ましくは１～３０ｍＰａ・ｓ、より好ましくは１～２０ｍＰａ・ｓ、さらに好ましくは１～１０ｍＰａ・ｓの範囲である。 When the ink composition according to the embodiment of the present invention is used for a marking pen, the viscosity thereof is determined to have a high fluidity of the ink and a high dispersion stability of the pigment when measured at a rotation speed of 50 rpm in an environment of 20°C. The following ranges are preferable because they can be maintained at the same level. Specifically, the viscosity of the ink composition in this case is preferably in the range of 1 to 30 mPa·s, more preferably 1 to 20 mPa·s, even more preferably 1 to 10 mPa·s.
　なお、インキ組成物の粘度は、Ｅ型回転粘度計〔東機産業（株）製、製品名：ＲＥ－８５Ｌ、コーン型ローター：標準型（１°３４′×Ｒ２４）〕を用いて、インキ組成物を２０℃の環境下に置いて測定した値である。 The viscosity of the ink composition was measured using an E-type rotational viscometer [manufactured by Toki Sangyo Co., Ltd., product name: RE-85L, cone rotor: standard type (1°34' x R24)]. This is a value measured with the composition placed in an environment at 20°C.
　本発明の実施形態によるインキ組成物がボールペンまたはマーキングペンに用いられる場合、そのｐＨは、好ましくは６～１０、より好ましくは７～９の範囲である。ｐＨが上記の範囲内にあることにより、インキ組成物の過度な高粘度化および変質を抑制することができる。 When the ink composition according to the embodiment of the present invention is used for a ballpoint pen or a marking pen, its pH is preferably in the range of 6 to 10, more preferably 7 to 9. When the pH is within the above range, excessive increase in viscosity and deterioration of the ink composition can be suppressed.
　なお、インキ組成物のｐＨは、ｐＨメーター〔東亜ディーケーケー（株）製、製品名：ＩＭ－４０Ｓ〕を用いて、インキを２０℃の環境下に置いて測定した値である。 Note that the pH of the ink composition is a value measured using a pH meter [manufactured by DKK Toa Co., Ltd., product name: IM-40S] with the ink placed in an environment of 20°C.
　本発明の実施形態によるインキ組成物がボールペンに用いられる場合、ボールペン自体の構造、形状は特に限定されるものではなく、例えば、ボールペンチップと、インキ充填機構とを備えたボールペンレフィルまたはボールペンに充填して用いられる。 When the ink composition according to the embodiment of the present invention is used in a ballpoint pen, the structure and shape of the ballpoint pen itself are not particularly limited. It is used as
　ボールペンチップは、チップ本体と、チップ本体の前端に備えられるボールとからなる。ボールペンチップは、例えば、金属製のパイプからなるチップ本体の先端近傍を外面より内方に押圧変形させたボール抱持部にボールを抱持してなるチップ、金属材料からなるチップ本体に、ドリル等による切削加工により形成したボール抱持部にボールを抱持してなるチップ、金属またはプラスチック製チップ本体の内部に樹脂製のボール受け座を設けたチップ、あるいは、上記チップに抱持するボールをバネ体により前方に付勢させたもの等を例示できる。 A ballpoint pen tip consists of a tip body and a ball provided at the front end of the tip body. For example, a ballpoint pen tip is a tip in which a ball is held in a ball holding part where the tip of the tip body made of a metal pipe is deformed by pressing inward from the outer surface, or a tip made of a metal pipe with a ball held in the tip body. A chip in which a ball is held in a ball holding part formed by cutting, etc., a chip in which a resin ball receiving seat is provided inside a metal or plastic chip body, or a ball held in the above-mentioned chip. An example is one in which a spring body urges forward.
　チップ本体およびボールの材質としては特に限定されるものではなく、例えば、超硬合金（超硬）、ステンレス鋼、ルビー、セラミック、樹脂、ゴム等を例示できる。さらに、ボールにはＤＬＣコート等の表面処理を施すこともできる。 The material of the chip body and the ball is not particularly limited, and examples thereof include cemented carbide (carbide), stainless steel, ruby, ceramic, resin, and rubber. Furthermore, the ball can also be subjected to surface treatment such as DLC coating.
　ボールの直径は、一般的には０．２～３ｍｍであり、好ましくは０．２～２ｍｍ、より好ましくは０．２～１．５ｍｍ、さらに好ましくは０．２～１ｍｍの範囲である。 The diameter of the ball is generally 0.2 to 3 mm, preferably 0.2 to 2 mm, more preferably 0.2 to 1.5 mm, and still more preferably 0.2 to 1 mm.
　インキ充填機構としては、例えば、インキを直に充填することのできるインキ収容体を例示できる。 An example of the ink filling mechanism is an ink container that can be directly filled with ink.
　インキ収容体としては、例えば、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート、ナイロン等の熱可塑性樹脂からなる成形体、または金属製管状体が用いられる。 As the ink container, for example, a molded body made of a thermoplastic resin such as polyethylene, polypropylene, polyethylene terephthalate, or nylon, or a metal tubular body is used.
　インキ収容体に、ボールペンチップを直接、または接続部材を介して連結させ、インキ収容体にインキを直接充填することにより、ボールペンレフィル（以下、「レフィル」と表すことがある）を形成することができる。このレフィルを軸筒内に収容することでボールペンを形成することができる。 A ballpoint pen refill (hereinafter sometimes referred to as "refill") can be formed by connecting a ballpoint pen tip to the ink container directly or via a connecting member and directly filling the ink container with ink. can. A ballpoint pen can be formed by housing this refill in the barrel.
　インキ収容体に充填されるインキの後端にはインキ逆流防止体が充填される。インキ逆流防止体としては、液栓または固体栓が挙げられる。 An ink backflow prevention body is filled at the rear end of the ink filled in the ink container. Examples of the ink backflow preventer include a liquid stopper or a solid stopper.
　液栓は不揮発性液体及び／又は難揮発性液体からなり、例えば、ワセリン、スピンドル油、ヒマシ油、オリーブ油、精製鉱油、流動パラフィン、ポリブテン、α－オレフィン、α－オレフィンのオリゴマーまたはコオリゴマー、ジメチルシリコーンオイル、メチルフェニルシリコーンオイル、アミノ変性シリコーンオイル、ポリエーテル変性シリコーンオイル、脂肪酸変性シリコーンオイル等を例示できる。 The liquid stopper consists of a non-volatile liquid and/or a slightly volatile liquid, such as vaseline, spindle oil, castor oil, olive oil, refined mineral oil, liquid paraffin, polybutene, α-olefin, oligomer or cooligomer of α-olefin, dimethyl Examples include silicone oil, methylphenyl silicone oil, amino-modified silicone oil, polyether-modified silicone oil, and fatty acid-modified silicone oil.
　不揮発性液体及び／又は難揮発性液体は一種、または二種以上を併用して用いることができる。 The non-volatile liquid and/or the hardly volatile liquid can be used alone or in combination of two or more.
　不揮発性液体及び／又は難揮発性液体には、増粘剤を添加して好適な粘度まで増粘させることが好ましい。 It is preferable to add a thickener to the non-volatile liquid and/or the slightly volatile liquid to thicken it to a suitable viscosity.
　増粘剤としては、例えば、表面を疎水処理したシリカ、表面をメチル化処理した微粒子シリカ、珪酸アルミニウム、膨潤性雲母、疎水処理を施したベントナイトおよびモンモリロナイト等の粘土系増粘剤；ステアリン酸マグネシウム、ステアリン酸カルシウム、ステアリン酸アルミニウム、ステアリン酸亜鉛等の脂肪酸金属石鹸；トリベンジリデンソルビトール、脂肪酸アマイド、アマイド変性ポリエチレンワックス、水添ひまし油、脂肪酸デキストリン等のデキストリン系化合物；セルロース系化合物等を例示できる。 Thickeners include, for example, silica with a hydrophobically treated surface, fine particle silica with a methylated surface, aluminum silicate, swelling mica, clay-based thickeners such as hydrophobically treated bentonite and montmorillonite; magnesium stearate. , fatty acid metal soaps such as calcium stearate, aluminum stearate, and zinc stearate; dextrin-based compounds such as tribenzylidene sorbitol, fatty acid amide, amide-modified polyethylene wax, hydrogenated castor oil, and fatty acid dextrin; and cellulose-based compounds.
　固体栓としては、例えば、ポリエチレン、ポリプロピレン、ポリメチルペンテン等からなる固体栓を例示できる。 Examples of solid plugs include solid plugs made of polyethylene, polypropylene, polymethylpentene, and the like.
　インキ逆流防止体として、上記した液栓と固体栓を併用して用いることもできる。 As the ink backflow preventer, the above-mentioned liquid plug and solid plug can also be used in combination.
　また、軸筒自体をインキ充填機構とし、軸筒内にインキを直接充填すると共に、軸筒の前端部にボールペンチップを装着することで、ボールペンチップと、インキ充填機構とを備えたボールペンを形成することもできる。 In addition, by using the barrel itself as an ink filling mechanism and filling ink directly into the barrel, and by attaching a ballpoint pen tip to the front end of the barrel, a ballpoint pen with a ballpoint pen tip and an ink filling mechanism is formed. You can also.
　インキ充填機構に充填されるインキが低粘度である場合、ボールペンチップと、インキ充填機構とを備えたボールペンは、さらに、インキ充填機構に充填されるインキをペン先に供給するためのインキ供給機構を備えていてもよい。 When the ink filled in the ink filling mechanism has a low viscosity, a ballpoint pen equipped with a ballpoint pen tip and an ink filling mechanism further includes an ink supply mechanism for supplying the ink filled in the ink filling mechanism to the pen tip. may be provided.
　インキ供給機構としては特に限定されるものではなく、例えば、（１）繊維束等からなるインキ誘導芯をインキ流量調節体として備え、これを介在させてインキをペン先に供給する機構、（２）櫛溝状のインキ流量調節体を備え、これを介在させてインキをペン先に供給する機構、（３）多数の円盤体が櫛溝状の間隔を開け並列配置され、円盤体を軸方向に縦貫するスリット状のインキ誘導溝および該溝より太幅の通気溝が設けられ、軸心にインキ充填機構からペン先へインキを誘導するためのインキ誘導芯が配置されてなるペン芯を介して、インキをペン先に供給する機構等が挙げられる。 The ink supply mechanism is not particularly limited, and includes, for example, (1) a mechanism that includes an ink guide core made of a fiber bundle or the like as an ink flow rate regulator and supplies ink to the pen tip through this intervening mechanism; ) A mechanism that includes a comb groove-shaped ink flow rate regulator and supplies ink to the pen tip through this intervening mechanism; (3) A large number of disc bodies are arranged in parallel with comb groove-shaped intervals, and the disc bodies are arranged in parallel in the axial direction. A slit-shaped ink guide groove running vertically through the pen core and a ventilation groove wider than the groove are provided, and an ink guide core for guiding ink from the ink filling mechanism to the pen tip is arranged at the axis of the pen core. Examples include a mechanism that supplies ink to the pen tip.
　ペン芯の材質としては、多数の円盤体を櫛溝状とした構造に射出成形できる合成樹脂であれば特に制限されるものではない。合成樹脂としては、例えば、汎用のポリカーボネート、ポリプロピレン、ポリエチレン、アクリロニトリル－ブタジエン－スチレン共重合体（ＡＢＳ樹脂）等を例示できる。特に、成形性が高く、ペン芯性能を得られ易いことから、アクリロニトリル－ブタジエン－スチレン共重合体（ＡＢＳ樹脂）が好適に用いられる。 The material of the pen core is not particularly limited as long as it is a synthetic resin that can be injection molded into a comb-like structure with a large number of discs. Examples of the synthetic resin include general-purpose polycarbonate, polypropylene, polyethylene, acrylonitrile-butadiene-styrene copolymer (ABS resin), and the like. In particular, acrylonitrile-butadiene-styrene copolymer (ABS resin) is preferably used because it has high moldability and can easily obtain pen core performance.
　ボールペンが上記のインキ供給機構を備えてなる場合、インキ充填機構としては、上記したインキ収容体および軸筒のほか、インキを充填できるインキ吸蔵体を用いることができる。 When the ballpoint pen is equipped with the above-mentioned ink supply mechanism, in addition to the above-described ink container and barrel, an ink storage body that can be filled with ink can be used as the ink filling mechanism.
　インキ吸蔵体は、捲縮状繊維を長手方向に集束させた繊維集束体であり、プラスチック筒体またはフィルム等の被覆体に内在させて、気孔率が概ね４０～９０％の範囲になるように調整して構成されたものである。 The ink storage body is a fiber bundle in which crimped fibers are bundled in the longitudinal direction.The ink storage body is a fiber bundle in which crimped fibers are bundled in the longitudinal direction, and is built into a plastic cylinder or a covering such as a film so that the porosity is in the range of approximately 40 to 90%. It is configured by adjusting.
　また、インキ収容体にインキを含浸させたインキ吸蔵体を収容し、インキ吸蔵体に接続するようにインキ供給機構が、インキ収容体の前端に備えられると共に、インキ供給機構に接続するようにボールペンチップを、直接または接続部材を介してインキ供給機構に連結させることにより、ボールペンチップと、インキ充填機構と、インキ供給機構とを備えたボールペンレフィルを形成することもできる。あるいは、インキ収容体にインキを含浸させたインキ吸蔵体を収容し、インキ吸蔵体に接続するようにインキ供給機構が、インキ収容体の内部に備えられると共に、インキ供給機構に接続するようにボールペンチップを、直接または接続部材を介してインキ収容体に連結させることによっても、ボールペンレフィルを形成することができる。 Further, an ink storage body impregnated with ink is housed in the ink storage body, and an ink supply mechanism is provided at the front end of the ink storage body so as to be connected to the ink storage body. A ballpoint pen refill including a ballpoint pen tip, an ink filling mechanism, and an ink supply mechanism can also be formed by connecting the tip to the ink supply mechanism directly or via a connecting member. Alternatively, the ink storage body houses an ink storage body impregnated with ink, and an ink supply mechanism is provided inside the ink storage body so as to be connected to the ink storage body, and a ballpoint pen is connected to the ink supply mechanism. A ballpoint pen refill can also be formed by connecting the tip to the ink container directly or via a connecting member.
　本発明の実施形態によるインキ組成物を収容するボールペンの構成として具体的には、（１）軸筒内に、インキを充填したインキ収容体を有し、インキ収容体には、直接または接続部材を介してボールペンチップが連結され、インキの端面にはインキ逆流防止体が充填されたボールペン、（２）軸筒内に直接インキが充填され、櫛溝状のインキ流量調節体、または繊維束等からなるインキ誘導芯をインキ流量調節体として介在させてインキをペン先に供給する機構が備えられるボールペン、（３）軸筒内に直接インキが充填され、上記のペン芯を介してインキをペン先に供給する機構が備えられるボールペン、（４）軸筒内に、インキを含浸させた繊維集束体からなるインキ吸蔵体が収容され、繊維束等からなるインキ誘導芯をインキ流量調節体として介在させてインキをペン先に供給する機構が備えられるボールペン等を例示できる。 Specifically, the structure of the ballpoint pen that accommodates the ink composition according to the embodiment of the present invention is as follows: (1) It has an ink container filled with ink in the barrel, and the ink container is provided with a direct or connecting member. (2) A ballpoint pen whose end face is filled with an ink backflow preventer; (2) A ballpoint pen whose barrel is directly filled with ink and a comb-shaped ink flow regulator, or a fiber bundle, etc. (3) A ballpoint pen that is equipped with a mechanism for supplying ink to the nib by interposing an ink guiding core as an ink flow rate regulator; A ballpoint pen equipped with a mechanism for supplying the ink first, (4) an ink storage body made of a fiber bundle impregnated with ink is housed in the barrel, and an ink guide core made of a fiber bundle etc. is interposed as an ink flow rate regulator. An example is a ballpoint pen, etc., which is equipped with a mechanism for supplying ink to the pen tip.
　本発明の実施形態によるインキ組成物がマーキングペンに用いられる場合、マーキングペン自体の構造、形状は特に限定されるものではなく、例えば、マーキングペンチップと、インキ充填機構とを備えたマーキングペンレフィルまたはマーキングペンに充填して用いられる。 When the ink composition according to the embodiment of the present invention is used in a marking pen, the structure and shape of the marking pen itself are not particularly limited. For example, a marking pen refill including a marking pen tip and an ink filling mechanism is used. Or it can be filled into a marking pen.
　マーキングペンチップとしては、例えば、繊維の樹脂加工体、熱溶融性繊維の融着加工体、フェルト体等の従来より汎用の気孔率が概ね３０～７０％の範囲から選ばれる連通気孔の多孔質部材、または、軸方向に延びる複数のインキ導出孔を有する合成樹脂の押出成形体等を例示でき、一端を砲弾形状、長方形状、チゼル形状等の目的に応じた形状に加工して実用に供される。 As a marking pen tip, for example, a porous material with continuous pores selected from a conventional general-purpose material with a porosity in the range of 30 to 70%, such as a resin-processed fiber, a fusion-processed heat-fusible fiber, a felt material, etc. An example is a member or a synthetic resin extrusion molded body having a plurality of ink outlet holes extending in the axial direction, and one end can be processed into a shape according to the purpose such as a bullet shape, a rectangular shape, a chisel shape, etc. and used for practical use. be done.
　インキ充填機構としては、例えば、インキを充填できるインキ吸蔵体を例示できる。
　インキ吸蔵体は、捲縮状繊維を長手方向に集束させた繊維集束体であり、プラスチック筒体またはフィルム等の被覆体に内在させて、気孔率が概ね４０～９０％の範囲に調整して構成される。 An example of the ink filling mechanism is an ink storage body that can be filled with ink.
The ink occlusion body is a fiber bundle in which crimped fibers are bundled in the longitudinal direction.The ink storage body is a fiber bundle in which crimped fibers are bundled in the longitudinal direction, and the porosity is adjusted to a range of approximately 40 to 90% by incorporating it into a plastic cylinder or a covering such as a film. configured.
　軸筒内に、インキを含浸させたインキ吸蔵体を収容し、インキ吸蔵体に接続するようにマーキングペンチップを、直接または接続部材を介して軸筒に連結させることにより、マーキングペンを形成することができる。 A marking pen is formed by accommodating an ink absorbing body impregnated with ink in the barrel, and connecting the marking pen tip to the barrel directly or through a connecting member so as to be connected to the ink absorbing body. be able to.
　また、インキ収容体にインキを含浸させたインキ吸蔵体を収容し、インキ吸蔵体に接続するようにマーキングペンチップを、直接または接続部材を介してインキ収容体に連結させることにより、マーキングペンレフィル（以下、「レフィル」と表すことがある）を形成することができる。このレフィルを軸筒に収容することでマーキングペンを形成することができる。 In addition, the marking pen refill can be made by accommodating an ink storage body impregnated with ink in the ink storage body, and connecting the marking pen tip to the ink storage body directly or through a connecting member. (hereinafter sometimes referred to as a "refill") can be formed. A marking pen can be formed by housing this refill in a barrel.
　インキ収容体としては、例えば、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート、ナイロン等の熱可塑性樹脂からなる成形体、または金属製管状体が用いられる。 As the ink container, for example, a molded body made of a thermoplastic resin such as polyethylene, polypropylene, polyethylene terephthalate, or nylon, or a metal tubular body is used.
　マーキングペンチップと、インキ充填機構とを備えたマーキングペンは、さらに、インキ充填機構に充填されるインキ組成物をペン先に供給するためのインキ供給機構を備えていてもよい。 The marking pen equipped with a marking pen tip and an ink filling mechanism may further include an ink supply mechanism for supplying the ink composition to be filled in the ink filling mechanism to the pen tip.
　インキ供給機構としては特に限定されるものではなく、例えば、上記したボールペンに備えられるインキ供給機構に加えて、（４）弁機構によるインキ流量調節体を備え、開弁によりインキをペン先に供給する機構等が挙げられる。 The ink supply mechanism is not particularly limited, and for example, in addition to the ink supply mechanism included in the ballpoint pen described above, it may include (4) an ink flow rate regulator using a valve mechanism, and ink is supplied to the pen tip by opening the valve. Examples include mechanisms for
　弁機構は、チップの押圧により開放する、従来より汎用のポンピング式形態が使用でき、筆圧により押圧開放可能なバネ圧に設定したものが好適である。 The valve mechanism can be a conventionally general-purpose pumping type that opens by pressing the tip, and preferably has a spring pressure that allows the valve to be opened by pressure from a pen.
　マーキングペンがインキ供給機構を備えてなる場合、インキ充填機構としては、上記したインキ吸蔵体のほか、インキを直接充填できるインキ収容体を用いることができる。また、軸筒自体をインキ充填機構として、インキを直接充填してもよい。 When the marking pen is equipped with an ink supply mechanism, in addition to the above-mentioned ink storage body, an ink storage body that can be directly filled with ink can be used as the ink filling mechanism. Alternatively, the barrel itself may be used as an ink filling mechanism to directly fill ink.
　また、インキ収容体にインキを含浸させたインキ吸蔵体を収容し、インキ吸蔵体に接続するようにインキ供給機構が、インキ収容体の前端に備えられると共に、インキ供給機構に接続するようにマーキングペンチップを、直接または接続部材を介してインキ供給機構に連結させることにより、マーキングペンチップと、インキ充填機構と、インキ供給機構とを備えたマーキングペンレフィルを形成することもできる。あるいは、インキ収容体にインキを含浸させたインキ吸蔵体を収容し、インキ吸蔵体に接続するようにインキ供給機構が、インキ収容体の内部に備えられると共に、インキ供給機構に接続するようにマーキングペンチップを、直接または接続部材を介してインキ収容体に連結させることによっても、マーキングペンレフィルを形成することができる。 Further, the ink storage body houses an ink storage body impregnated with ink, and an ink supply mechanism is provided at the front end of the ink storage body so as to be connected to the ink storage body, and markings are provided so as to connect to the ink supply mechanism. A marking pen refill including a marking pen tip, an ink filling mechanism, and an ink supply mechanism can also be formed by connecting the pen tip to the ink supply mechanism directly or via a connecting member. Alternatively, an ink storage body impregnated with ink is housed in the ink storage body, and an ink supply mechanism is provided inside the ink storage body so as to be connected to the ink storage body, and markings are provided so as to be connected to the ink supply mechanism. A marking pen refill can also be formed by connecting the pen tip to the ink reservoir directly or via a connecting member.
　本発明の実施形態によるインキ組成物を収容するマーキングペンの構成として具体的には、（１）軸筒内に、インキを含浸させた繊維集束体からなるインキ吸蔵体が収容され、毛細間隙が形成された、繊維加工体または樹脂成形体からなるマーキングペンチップが、インキ吸蔵体とチップが接続するように、直接または接続部材を介して軸筒に連結されたマーキングペン、（２）軸筒内に直接インキが充填され、櫛溝状のインキ流量調節体または繊維束等からなるインキ誘導芯をインキ流量調節体として介在させてインキをペン先に供給する機構が備えられるマーキングペン、（３）軸筒内に直接インキが充填され、上記のペン芯を介してインキをペン先に供給する機構が備えられるマーキングペン、（４）チップの押圧により開弁する弁機構を介してチップとインキ収容体とが備えられ、インキ収容体に直接インキが充填されるマーキングペン、（５）軸筒内に、インキを含浸させた繊維集束体からなるインキ吸蔵体を収容したインキ収容体を有し、毛細間隙が形成された、繊維加工体または樹脂成形体からなるマーキングペンチップが、インキ吸蔵体とチップが接続するように、直接または接続部材を介してインキ収容体に連結されたマーキングペン等を例示できる。 Specifically, the configuration of the marking pen that accommodates the ink composition according to the embodiment of the present invention is as follows: (1) An ink storage body made of a fiber bundle impregnated with ink is housed in the barrel, and capillary gaps are formed. (2) A marking pen in which a marking pen tip made of a fiber processed body or a resin molded body is connected to a barrel directly or through a connecting member so that the ink storage body and the tip are connected to the barrel; (2) a barrel; A marking pen, which is directly filled with ink and is equipped with a mechanism for supplying ink to the pen tip by interposing an ink guide core made of a comb-shaped ink flow rate regulator or a fiber bundle as an ink flow rate regulator, (3 ) A marking pen with a mechanism in which the barrel is directly filled with ink and a mechanism for supplying ink to the nib via the above-mentioned pen core; (4) A marking pen that is equipped with a mechanism that supplies ink to the nib via the above-mentioned pen core; (5) a marking pen having an ink container in which the ink storage body is directly filled with ink; , a marking pen, etc., in which a marking pen tip made of a fiber processed body or a resin molded body in which capillary gaps are formed is connected to an ink storage body directly or through a connecting member so that the ink storage body and the tip are connected. can be exemplified.
　本発明の実施形態によるボールペンまたはマーキングペンがインキを直接充填するものである場合、顔料の再分散を容易とするために、インキが充填されるインキ収容体または軸筒に、インキを攪拌する攪拌ボール等の攪拌体を内蔵させることもできる。攪拌体の形状としては、球状体、棒状体等が挙げられる。攪拌体の材質としては特に限定されるものではなく、例えば、金属、セラミック、樹脂、硝子等を例示できる。 When the ballpoint pen or marking pen according to the embodiment of the present invention is one that is directly filled with ink, stirring is performed to stir the ink in the ink container or barrel filled with the ink in order to facilitate redispersion of the pigment. It is also possible to incorporate a stirring body such as a ball. Examples of the shape of the stirring body include a spherical body and a rod-shaped body. The material of the stirring body is not particularly limited, and examples include metal, ceramic, resin, and glass.
　本発明の実施形態によるボールペンまたはマーキングペン等の筆記具は、着脱可能な構造としてインキカートリッジ形態とすることもできる。この場合、筆記具のインキカートリッジに収容されるインキを使い切った後に、新たなインキカートリッジと取り替えることで、再び筆記具を使用することができる。 A writing instrument such as a ballpoint pen or a marking pen according to an embodiment of the present invention can also be in the form of an ink cartridge as a removable structure. In this case, after the ink stored in the ink cartridge of the writing instrument is used up, the writing instrument can be used again by replacing it with a new ink cartridge.
　インキカートリッジとしては、筆記具本体に接続することで筆記具を構成する軸筒を兼ねたもの、または筆記具本体に接続した後に軸筒（後軸）を被覆して保護するものが用いられる。なお、後者においては、インキカートリッジ単体で用いるほか、使用前の筆記具において、筆記具本体とインキカートリッジが接続されているもの、および筆記具のユーザーが使用時に軸筒内のインキカートリッジを接続して使用を開始するように非接続状態で軸筒内に収容したもののいずれであってもよい。 The ink cartridge used is one that doubles as a barrel that constitutes the writing instrument by being connected to the writing instrument body, or one that covers and protects the barrel (rear barrel) after being connected to the writing instrument body. In addition to using the ink cartridge alone, the latter can also be used with writing instruments in which the writing instrument body and ink cartridge are connected before use, and with the user of the writing instrument connecting the ink cartridge inside the barrel during use. It may be any of those that are housed in the shaft cylinder in an unconnected state so as to start.
　本発明の実施形態によるボールペンまたはマーキングペン等の筆記具には、ペン先（筆記先端部）を覆うように装着されるキャップを設けてキャップ式筆記具とすることにより、ペン先が乾燥して筆記できなくなること、および筆記先端部が汚染・破損されることを防ぐことができる。 A writing instrument such as a ballpoint pen or a marking pen according to an embodiment of the present invention is provided with a cap that is attached to cover the pen tip (writing tip) to make it a cap-type writing instrument, so that the pen tip dries and prevents writing. It is possible to prevent the writing tip from being lost and the writing tip from being contaminated or damaged.
　また、軸筒内にレフィルが収容されるボールペンまたはマーキングペン等の筆記具には、軸筒内に、軸筒から筆記先端部を出没可能とする出没機構を設けて出没式筆記具とすることができ、筆記先端部が汚染・破損されることを防ぐことができる。 In addition, a writing instrument such as a ballpoint pen or a marking pen in which a refill is stored in the barrel can be made into a retractable writing instrument by providing a retractable mechanism in the barrel that allows the writing tip to retract from the barrel. , it is possible to prevent the writing tip from being contaminated or damaged.
　出没式筆記具は、筆記先端部が外気に晒された状態で軸筒内に収容されており、出没機構の作動によって軸筒開口部から筆記先端部が突出する構造であれば全て用いることができる。
　また、軸筒内に複数のレフィルを収容してなり、出没機構の作動によっていずれかのレフィルの筆記先端部を軸筒開口部から出没させる複合タイプの出没式筆記具とすることもできる。 Any retractable writing instrument can be used as long as the writing tip is housed in the barrel with the writing tip exposed to the outside air, and the writing tip protrudes from the barrel opening by the operation of the retractable mechanism. .
Further, it is also possible to provide a composite type retractable writing instrument in which a plurality of refills are housed in a barrel, and the writing tip of one of the refills is moved out and retracted from the opening of the barrel by the operation of a retractable mechanism.
　出没機構としては、例えば、（１）軸筒の後部側壁より前後方向に移動可能な操作部（クリップ）を径方向外方に突設させ、操作部を前方にスライド操作することにより軸筒前端開口部から筆記先端部を出没させるサイドスライド式の出没機構、（２）軸筒後端に設けた操作部を前方に押圧することにより軸筒前端開口部から筆記先端部を出没させる後端ノック式の出没機構、（３）軸筒側壁外面より突出する操作部を径方向内方に押圧することにより軸筒前端開口部から筆記先端部を出没させるサイドノック式の出没機構、（４）軸筒後部の操作部を回転操作することにより軸筒前端開口部から筆記先端部を出没させる回転式の出没機構等を例示できる。 For example, (1) an operating section (clip) that can be moved in the front-rear direction from the rear side wall of the barrel is protruded radially outward, and by sliding the operating section forward, the front end of the barrel can be moved. (2) A rear end knock that makes the writing tip come out and go out from the opening at the front end of the barrel by pushing forward the operating section provided at the rear end of the barrel. (3) A side-knock-type ejection mechanism that causes the writing tip to protrude and retract from the front end opening of the barrel by pressing an operating part protruding from the outer surface of the side wall of the barrel in the radial direction; (4) a shaft; An example is a rotary ejection mechanism that causes the writing tip to protrude and retract from the front end opening of the barrel by rotating an operating section at the rear of the barrel.
　ボールペンおよびマーキングペンの形態は上記した構成に限らず、相異なる形態のチップを装着させたり、相異なる色調あるいは色相のインキを導出させるチップを装着させたりするほか、相異なる形態のチップを装着させると共に、各チップから導出されるインキの色調あるいは色相が相異なる複合式筆記具（両頭式またはペン先繰り出し式等）であってもよい。 Ballpoint pens and marking pens are not limited to the configurations described above; they may be equipped with tips of different shapes, tips that produce ink of different tones or hues, or tips of different shapes. Additionally, it may be a composite writing instrument (double-ended type, pen-tip type, etc.) in which the tone or hue of the ink derived from each tip is different.
　着色剤として、可逆熱変色性組成物、可逆熱変色性マイクロカプセル顔料、または可逆熱変色性樹脂粒子等を用いる場合、本発明の実施形態によるインキ組成物を収容した筆記具を用いて被筆記面に形成される筆跡は、指による擦過、加熱具または冷却具により変色させることができる。 When a reversible thermochromic composition, a reversible thermochromic microcapsule pigment, a reversible thermochromic resin particle, or the like is used as a coloring agent, a writing instrument containing an ink composition according to an embodiment of the present invention is used to coat the writing surface. The handwriting formed can be discolored by rubbing with a finger or by using a heating or cooling tool.
　加熱具としては、ＰＴＣ素子等の抵抗発熱体を装備した通電加熱変色具、温水等の媒体を充填した加熱変色具、スチームまたはレーザー光等を用いた加熱変色具、ヘアドライヤーの適用等が挙げられるが、簡便な方法により変色させることができることから、摩擦部材および摩擦体が好ましい。 Examples of heating tools include electrical heating discoloration tools equipped with a resistance heating element such as a PTC element, heat discoloration tools filled with a medium such as hot water, heat discoloration tools using steam or laser light, hair dryers, etc. However, friction members and friction bodies are preferable because they can be changed in color by a simple method.
　冷却具としては、ペルチエ素子を用いた通電冷熱変色具、冷水及び／又は氷片等の冷媒を充填した冷熱変色具、畜冷剤、冷蔵庫および冷凍庫の適用等が挙げられる。 Examples of the cooling device include an energized cold/heat discoloration device using a Peltier element, a cold/heat discoloration device filled with a refrigerant such as cold water and/or ice chips, a cold storage agent, and applications for refrigerators and freezers.
　摩擦部材および摩擦体としては、弾性感に富み、擦過時に適度な摩擦を生じて摩擦熱を発生させることのできるエラストマー、プラスチック発泡体等の弾性体が好ましいが、プラスチック成形体、石材、木材、金属、布帛等を用いることもできる。 As the friction member and friction body, it is preferable to use an elastic body such as an elastomer or plastic foam, which has a rich elastic feel and can generate appropriate friction and generate frictional heat during rubbing, but plastic molded bodies, stone, wood, etc. Metal, cloth, etc. can also be used.
　なお、鉛筆による筆跡を消去するために用いられる一般的な消しゴムを使用して、筆跡を擦過してもよいが、擦過時に消しカスが発生するため、消しカスが殆ど発生しない上記の摩擦部材および摩擦体が好適に用いられる。 Note that the handwriting may be rubbed using a general eraser used for erasing pencil handwriting, but since eraser scum is generated during rubbing, the above-mentioned friction member that hardly generates eraser scum and A friction body is preferably used.
　摩擦部材および摩擦体の材質としては、例えば、シリコーン樹脂、スチレン－エチレン－ブタジエン－スチレンブロック共重合体（ＳＥＢＳ樹脂）等を例示できる。シリコーン樹脂は擦過により消去した部分に樹脂が付着し易く、繰り返し筆記した際に筆跡がはじかれる傾向にあるため、ＳＥＢＳ樹脂がより好適に用いられる。 Examples of the material for the friction member and the friction body include silicone resin, styrene-ethylene-butadiene-styrene block copolymer (SEBS resin), and the like. SEBS resin is more preferably used because silicone resin tends to adhere to areas erased by rubbing and handwriting tends to be repelled when written repeatedly.
　上記の摩擦部材または摩擦体は、筆記具とは別体の任意形状の部材であってもよいが、筆記具に設けることにより携帯性に優れるものとすることができる。また、筆記具と、筆記具とは別体の任意形状の摩擦部材または摩擦体とを組み合わせて、筆記具セットを得ることもできる。 The above-mentioned friction member or friction body may be a member of any shape separate from the writing instrument, but by providing it on the writing instrument, it can be made highly portable. Further, a writing instrument set can also be obtained by combining a writing instrument and a friction member or friction body of an arbitrary shape that is separate from the writing instrument.
　キャップを備える筆記具の場合、摩擦部材または摩擦体を設ける箇所は特に限定されるものではなく、例えば、キャップ自体を摩擦部材により形成したり、軸筒自体を摩擦部材により形成したり、クリップを設ける場合には、クリップ自体を摩擦部材により形成したり、キャップ先端部（頂部）あるいは軸筒後端部（筆記先端部を設けていない部分）等に摩擦部材または摩擦体を設けることができる。 In the case of a writing instrument equipped with a cap, the friction member or the location where the friction body is provided is not particularly limited. For example, the cap itself may be formed from a friction member, the barrel itself may be formed from a friction member, or a clip may be provided. In some cases, the clip itself may be formed of a friction member, or a friction member or a friction body may be provided at the tip (top) of the cap, the rear end of the barrel (the portion where the writing tip is not provided), or the like.
　出没機構を備える筆記具の場合、摩擦部材または摩擦体を設ける箇所は特に限定されるものではなく、例えば、軸筒自体を摩擦部材により形成したり、さらにクリップを設ける場合には、クリップ自体を摩擦部材により形成したり、軸筒開口部近傍、軸筒後端部（筆記先端部を設けていない部分）、あるいはノック部に摩擦部材または摩擦体を設けることができる。 In the case of a writing instrument equipped with a retractable mechanism, the friction member or the location where the friction body is provided is not particularly limited. For example, if the barrel itself is formed of a friction member, or if a clip is further provided, the clip itself is A friction member or a friction body may be provided in the vicinity of the opening of the barrel, at the rear end of the barrel (the part where the writing tip is not provided), or in the knock portion.
　本発明の実施形態によるインキ組成物は筆記具用途以外にも利用することができる。例えば、スクリーン印刷、オフセット印刷、プロセス印刷、グラビヤ印刷、コーター、タンポ印刷等に用いられる印刷用インキ；刷毛塗り、スプレー塗装、静電塗装、電着塗装、流し塗り、ローラー塗り、浸漬塗装等に用いられる塗料；インクジェット用インキ；紫外線硬化型インキ；塗布具用インキ；スタンプ用インキ；絵具；化粧料；繊維用着色液として利用することができる。 The ink composition according to the embodiment of the present invention can be used for purposes other than writing instruments. For example, printing ink used for screen printing, offset printing, process printing, gravure printing, coater, tampo printing, etc.; for brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, dip coating, etc. It can be used as a paint; an inkjet ink; an ultraviolet curable ink; an ink for applicators; an ink for stamps; a paint; a cosmetic; and a coloring liquid for textiles.
　以下に実施例を示すが、本発明の実施形態はこれに限定されるものではない。なお、特に断らない限り実施例中の「部」および「％」はそれぞれ、「質量部」および「質量％」を示す。 Examples are shown below, but the embodiments of the present invention are not limited thereto. In addition, unless otherwise specified, "parts" and "%" in the examples indicate "parts by mass" and "% by mass", respectively.
　実施例１
　顔料分散体の調製
　グアニン〔東京化成工業（株）製〕１０部と、分散剤〔東亞合成（株）製、製品名：アロンＡ－１２ＳＬ（固形分：４０％）〕２．５部と、水８７．５部とを混合した。そして、メディアとして直径１．４～１．６ｍｍのジルコニアビーズを２００部加え、ビーズミルにより６時間、粉砕分散処理を行い、顔料分散体（グアニン顔料分散液）を調製した。なお、顔料分散体の総質量に対する分散剤の含有率は１％であり、グアニン顔料に対する分散剤の含有率は１０％である。また、上述の方法により、顔料分散体中に分散するグアニン顔料の平均粒子径を測定した結果、０．３５μｍであった。 Example 1
Preparation of pigment dispersion 10 parts of guanine [manufactured by Tokyo Chemical Industry Co., Ltd.], 2.5 parts of a dispersant [manufactured by Toagosei Co., Ltd., product name: Aron A-12SL (solid content: 40%)], 87.5 parts of water were mixed. Then, 200 parts of zirconia beads with a diameter of 1.4 to 1.6 mm were added as a media, and pulverization and dispersion treatment was performed using a bead mill for 6 hours to prepare a pigment dispersion (guanine pigment dispersion). Note that the content of the dispersant with respect to the total mass of the pigment dispersion was 1%, and the content of the dispersant with respect to the guanine pigment was 10%. Furthermore, the average particle diameter of the guanine pigment dispersed in the pigment dispersion was measured by the above method and was found to be 0.35 μm.
　実施例２～４
　顔料分散体の調製
　実施例２～４の各顔料分散体は、配合する材料の種類と配合量を以下の表１に記載のものに変更した以外は、実施例１と同様にして調製した。顔料分散体の総質量に対する分散剤の含有率、グアニン顔料に対する分散剤の含有率、顔料分散体中に分散するグアニン顔料の平均粒子径を、以下の表１に示した。 Examples 2-4
Preparation of Pigment Dispersion Each of the pigment dispersions of Examples 2 to 4 was prepared in the same manner as in Example 1, except that the types and amounts of the materials to be blended were changed to those listed in Table 1 below. The content ratio of the dispersant to the total mass of the pigment dispersion, the content ratio of the dispersant to the guanine pigment, and the average particle diameter of the guanine pigment dispersed in the pigment dispersion are shown in Table 1 below.
　比較例１
　顔料分散体の調製
　酸化チタン〔テイカ（株）製、製品名：ＪＲ－７０７〕１０部と、分散剤〔ビックケミー・ジャパン（株）製、製品名：ＤＩＳＰＥＲ　ＢＹＫ－１９０（固形分：４０％）〕２．５部と、水８７．５部とを混合した。そして、メディアとして直径２．０ｍｍのガラスビーズを１００部加え、ビーズミルにより１時間、粉砕分散処理を行い、顔料分散体（酸化チタン分散液）を調製した。なお、顔料分散体の総質量に対する分散剤の含有率は１％であり、酸化チタンに対する分散剤の含有率は１０％である。顔料分散体中に分散する酸化チタンの平均粒子径は０．３μｍであった。 Comparative example 1
Preparation of pigment dispersion 10 parts of titanium oxide [manufactured by Teika Co., Ltd., product name: JR-707] and a dispersant [manufactured by BYK Chemie Japan Co., Ltd., product name: DISPER BYK-190 (solid content: 40%) ] and 87.5 parts of water were mixed. Then, 100 parts of glass beads with a diameter of 2.0 mm were added as a media, and pulverization and dispersion treatment was performed using a bead mill for 1 hour to prepare a pigment dispersion (titanium oxide dispersion). Note that the content of the dispersant with respect to the total mass of the pigment dispersion was 1%, and the content of the dispersant with respect to titanium oxide was 10%. The average particle diameter of titanium oxide dispersed in the pigment dispersion was 0.3 μm.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１中の材料の内容を、注番号に沿って説明する。
　（１）東京化成工業（株）製
　（２）テイカ（株）製、製品名：ＪＲ－７０７
　（３）未中和型アクリル－スルホン酸系共重合体〔東亞合成（株）製、製品名：アロンＡ－１２ＳＬ（固形分：４０％）〕
　（４）カルボキシ基含有ポリマー変性物の２－アミノ－２－メチル－１－プロパノール塩〔共栄社化学（株）製、製品名：フローレンＧ－７００ＡＭＰ（固形分：４５％）〕
　（５）コントロール重合のアクリル系共重合物〔ビックケミー・ジャパン（株）製、製品名：ＤＩＳＰＥＲ　ＢＹＫ－２０１０（固形分：４０％）〕
　（６）顔料に親和性のあるブロック共重合体〔ビックケミー・ジャパン（株）製、製品名：ＤＩＳＰＥＲ　ＢＹＫ－１９０（固形分：４０％）〕 The contents of the materials in Table 1 will be explained according to the note numbers.
(1) Manufactured by Tokyo Chemical Industry Co., Ltd. (2) Manufactured by Teika Co., Ltd., product name: JR-707
(3) Unneutralized acrylic-sulfonic acid copolymer [manufactured by Toagosei Co., Ltd., product name: Aron A-12SL (solid content: 40%)]
(4) 2-amino-2-methyl-1-propanol salt of modified polymer containing carboxyl group [manufactured by Kyoeisha Chemical Co., Ltd., product name: Floren G-700AMP (solid content: 45%)]
(5) Controlled polymerization acrylic copolymer [manufactured by BYK Chemie Japan Co., Ltd., product name: DISPER BYK-2010 (solid content: 40%)]
(6) Block copolymer with affinity for pigments [manufactured by BYK Chemie Japan Co., Ltd., product name: DISPER BYK-190 (solid content: 40%)]
［分散性評価］
　実施例１～４、ならびに、比較例１の各顔料分散体を、光学顕微鏡〔オリンパス（株）製、製品名：システム生物顕微鏡ＢＸ５３、１００倍〕にて確認し、下記基準で分散性を評価した。評価結果を、以下の表２に示した。なお、評価「Ａ」および「Ｂ」を合格とした。
Ａ：顔料が均一に分散している様相が視認された。
Ｂ：顔料の一次粒子が凝集している様相が、僅かに視認された。
Ｃ：顔料が著しく凝集している様相が視認された。 [Dispersibility evaluation]
Each pigment dispersion of Examples 1 to 4 and Comparative Example 1 was confirmed with an optical microscope [manufactured by Olympus Corporation, product name: System Biological Microscope BX53, 100 times], and the dispersibility was evaluated according to the following criteria. did. The evaluation results are shown in Table 2 below. Note that evaluations of "A" and "B" were considered to be passed.
A: It was observed that the pigment was uniformly dispersed.
B: A slight amount of agglomeration of the primary pigment particles was visually recognized.
C: Significant agglomeration of the pigment was visually observed.
［分散安定性評価］
　実施例１～４、ならびに、比較例１の各顔料分散体を、スクリュー管瓶（Ｎｏ．７）に４０ｇ入れ、室温（２５℃）環境下で７日間静置させた。７日間経過後に、各顔料分散体を目視にて確認し、下記基準で分散安定性を評価した。評価結果を、以下の表２に示した。なお、評価「Ａ」および「Ｂ」を合格とした。
Ａ：顔料は分散状態を保持しており、顔料分散体は均一な白色であった。
Ｂ：顔料はやや沈降し、顔料分散体の上部に淡い白色の層が視認された（顔料分散体に白色の濃淡が生じていた）。
Ｃ：顔料の多くが沈降し、顔料分散体に上澄み（水層）が視認され、完全に二層に分離していた。 [Dispersion stability evaluation]
40 g of each of the pigment dispersions of Examples 1 to 4 and Comparative Example 1 was placed in a screw tube bottle (No. 7) and allowed to stand at room temperature (25° C.) for 7 days. After 7 days had passed, each pigment dispersion was visually confirmed, and the dispersion stability was evaluated using the following criteria. The evaluation results are shown in Table 2 below. Note that evaluations of "A" and "B" were considered to be passed.
A: The pigment maintained a dispersed state, and the pigment dispersion was uniformly white.
B: The pigment was slightly sedimented, and a pale white layer was visible on the top of the pigment dispersion (the pigment dispersion had white shading).
C: Most of the pigment had settled, a supernatant (aqueous layer) was visible in the pigment dispersion, and the pigment was completely separated into two layers.
［隠蔽性試験］
　実施例１～４、ならびに、比較例１の各顔料分散体を、バーコーター（＃２）を用いて黒紙上質紙〔中厚、（株）活英社製〕に均一に塗工し、乾燥させて試験試料を得た。試験試料における塗工箇所の濃度を目視にて確認し、下記基準で隠蔽性を評価した。評価結果を、以下の表２に示した。なお、評価「Ａ」および「Ｂ」を合格とした。
Ａ：塗工箇所は明瞭な白色であり、十分な隠蔽性を有していた。
Ｂ：塗工箇所はやや薄い白色であったが、隠蔽性を有しており、実用上問題のないレベルであった。
Ｃ：塗工箇所は顕著に薄い白色であり、塗工箇所を通して紙の黒色がはっきりと視認され、隠蔽性は不十分であった。 [Concealability test]
Each pigment dispersion of Examples 1 to 4 and Comparative Example 1 was uniformly coated on black high-quality paper (medium thickness, manufactured by Katsueisha Co., Ltd.) using a bar coater (#2), A test sample was obtained by drying. The concentration of the coated area in the test sample was visually confirmed, and the hiding performance was evaluated using the following criteria. The evaluation results are shown in Table 2 below. Note that evaluations of "A" and "B" were considered to be passed.
A: The coated area was clear white and had sufficient hiding properties.
B: The coated area was a slightly pale white color, but it had hiding properties and was at a level that caused no practical problems.
C: The coated area was noticeably pale white, the black color of the paper was clearly visible through the coated area, and the hiding power was insufficient.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　実施例５
　筆記具用水性インキ組成物の調製
　グアニン〔東京化成工業（株）製〕２０部と、分散剤〔東亞合成（株）製、製品名：アロンＡ－１２ＳＬ（固形分：４０％）〕７．５部と、水７２．５部とを混合した。そして、メディアとして直径１．４～１．６ｍｍのジルコニアビーズを２００部加え、ビーズミルにより５時間、粉砕分散処理を行い、筆記具用水性インキ組成物を調製した。なお、インキ組成物の総質量に対する分散剤の含有率は３％であり、グアニン顔料に対する分散剤の含有率は１５％である。 Example 5
Preparation of water-based ink composition for writing instruments 20 parts of guanine [manufactured by Tokyo Chemical Industry Co., Ltd.] and a dispersant [manufactured by Toagosei Co., Ltd., product name: Aron A-12SL (solid content: 40%)] 7.5 1 part and 72.5 parts of water were mixed. Then, 200 parts of zirconia beads with a diameter of 1.4 to 1.6 mm were added as a media, and pulverization and dispersion treatment was performed using a bead mill for 5 hours to prepare a water-based ink composition for writing instruments. Note that the content of the dispersant with respect to the total mass of the ink composition was 3%, and the content of the dispersant with respect to the guanine pigment was 15%.
　筆記具の作製
　ポリエステルスライバーを合成樹脂フィルムで被覆したインキ吸蔵体内に上記の筆記具用水性インキ組成物を含浸させ、ポリプロピレン樹脂からなる軸筒内に収容し、軸筒先端部にポリエステル繊維の樹脂加工ペン体（砲弾型）を、樹脂製のホルダーを介して接続状態に組み立て、キャップを装着して中詰式筆記具（マーキングペン）を作製した。 Preparation of writing instrument: The ink storage body made of polyester sliver covered with a synthetic resin film is impregnated with the above water-based ink composition for writing instruments, and the result is housed in a barrel made of polypropylene resin, and a resin-treated pen made of polyester fiber is attached to the tip of the barrel. The body (shell-shaped) was assembled in a connected state via a resin holder, and a cap was attached to produce a filling-type writing instrument (marking pen).
　比較例２
　筆記具用水性インキ組成物の調製
　酸化チタン〔テイカ（株）製、製品名：ＪＲ－７０７〕２０部と、分散剤〔ビックケミー・ジャパン（株）製、製品名：ＤＩＳＰＥＲ　ＢＹＫ－１９０（固形分：４０％）〕７．５部と、水７２．５部とを混合した。そして、メディアとして直径２．０ｍｍのガラスビーズを１００部加え、ビーズミルにより１時間、粉砕分散処理を行い、筆記具用水性インキ組成物を調製した。なお、インキ組成物の総質量に対する分散剤の含有率は３％であり、酸化チタンに対する分散剤の含有率は１５％である。 Comparative example 2
Preparation of water-based ink composition for writing instruments 20 parts of titanium oxide [manufactured by Teika Co., Ltd., product name: JR-707] and a dispersant [manufactured by BYK Chemie Japan Co., Ltd., product name: DISPER BYK-190 (solid content: 40%)] and 72.5 parts of water were mixed. Then, 100 parts of glass beads with a diameter of 2.0 mm were added as a media, and pulverization and dispersion treatment was performed using a bead mill for 1 hour to prepare a water-based ink composition for writing instruments. Note that the content of the dispersant with respect to the total mass of the ink composition was 3%, and the content of the dispersant with respect to titanium oxide was 15%.
　筆記具の作製
　比較例２の筆記具（マーキングペン）は、実施例５と同様にして作製した。 Production of Writing Instrument A writing instrument (marking pen) of Comparative Example 2 was produced in the same manner as in Example 5.
［筆記試験］
　実施例５および比較例２で作製した各筆記具を用いて、室温（２０℃）環境下で、黒紙上質紙〔中厚、（株）活英社製〕に手書きで、文字「永」を筆記した。筆跡の状態を目視にて確認し、下記基準で筆跡の隠蔽性を評価した。評価結果を、以下の表３に示した。なお、評価「Ａ」を合格とした。
Ａ：筆跡は白色を呈し、隠蔽性を有していた。
Ｂ：筆跡は顕著に薄い白色を呈し、筆跡が透けて紙の黒色がはっきりと視認され、隠蔽性は不十分であった。 [Written test]
Using each of the writing instruments produced in Example 5 and Comparative Example 2, write the character "ei" by hand on black high-quality paper (medium weight, manufactured by Katsueisha Co., Ltd.) at room temperature (20°C). I wrote it down. The condition of the handwriting was visually confirmed, and the concealability of the handwriting was evaluated according to the following criteria. The evaluation results are shown in Table 3 below. Note that an evaluation of "A" was considered a pass.
A: The handwriting was white and had concealment properties.
B: The handwriting was noticeably pale white, the black of the paper was clearly visible through the handwriting, and the concealment was insufficient.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
［経時後の筆記試験］
　上述の筆記試験を行った各筆記具を、室温（２０℃）環境下で３日間、ペン先が上向きの状態（正立状態）で静置させた。３日経過後に、室温（２０℃）環境下で、黒紙上質紙〔中厚、（株）活英社製〕に手書きで、文字「永」を筆記した。筆跡の状態を目視にて確認し、下記基準で経時後の筆跡の隠蔽性を評価した。評価結果を、以下の表４に示した。なお、評価「Ａ」および「Ｂ」を合格とした。
Ａ：筆跡の白色は初期と同じあるいは同等レベルであり、隠蔽性を有していた。
Ｂ：筆跡の白色は初期の筆跡に比べてやや淡色化したが、実用上問題のないレベルの隠蔽性を有していた
Ｃ：筆跡の色は初期の筆跡に比べて淡色化し、隠蔽性は不十分であった。あるいは筆記不能であった。 [Written test after time]
Each of the writing instruments subjected to the above-mentioned writing test was allowed to stand still in a room temperature (20° C.) environment for 3 days with the pen tip facing upward (erect state). After 3 days, the character "Ei" was written by hand on black high-quality paper (medium thickness, manufactured by Katsueisha Co., Ltd.) at room temperature (20° C.). The condition of the handwriting was visually confirmed, and the concealability of the handwriting after time was evaluated based on the following criteria. The evaluation results are shown in Table 4 below. Note that evaluations of "A" and "B" were considered to be passed.
A: The whiteness of the handwriting was the same or at the same level as the initial level, and it had concealment properties.
B: The white color of the handwriting was slightly lighter than the initial handwriting, but it had a level of concealment that was not a problem in practical use. C: The color of the handwriting was lighter than the initial handwriting, and the concealability was low. It was insufficient. Or it was impossible to write.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　実施例６
　筆記具用水性インキ組成物の調製
　グアニン〔東京化成工業（株）製〕２０部と、分散剤〔ビックケミー・ジャパン（株）製、製品名：ＤＩＳＰＥＲ　ＢＹＫ－２０１０（固形分：４０％）〕７．５部と、水７２．５部とを混合した。そして、メディアとして直径１．４～１．６ｍｍのジルコニアビーズを２００部加え、ビーズミルにより５時間、粉砕分散処理を行い、顔料分散体（グアニン顔料分散液）を調製した。 Example 6
Preparation of water-based ink composition for writing instruments 20 parts of guanine [manufactured by Tokyo Kasei Kogyo Co., Ltd.] and a dispersant [manufactured by BYK Chemie Japan Co., Ltd., product name: DISPER BYK-2010 (solid content: 40%)]7. 5 parts and 72.5 parts of water were mixed. Then, 200 parts of zirconia beads with a diameter of 1.4 to 1.6 mm were added as a media, and pulverization and dispersion treatment was performed using a bead mill for 5 hours to prepare a pigment dispersion (guanine pigment dispersion).
　上記の顔料分散体８８部と、剪断減粘性付与剤（サクシノグリカン）〔三晶（株）製、製品名：レオザン〕０．２部と、リン酸エステル系界面活性剤〔第一工業製薬（株）製、製品名：プライサーフＡＬ〕１部と、ｐＨ調整剤（トリエタノールアミン）１部と、防腐剤〔ロンザジャパン（株）製、製品名：プロキセルＸＬ－２（Ｓ）〕０．１部と、水９．７部とを混合して、筆記具用水性インキ組成物を調製した。なお、インキ組成物の総質量に対する分散剤（すなわち「ＤＩＳＰＥＲ　ＢＹＫ－２０１０」および「プライサーフＡＬ」の合計）の含有率は３．６％であり、グアニン顔料に対する分散剤（すなわち「ＤＩＳＰＥＲ　ＢＹＫ－２０１０」および「プライサーフＡＬ」の合計）の含有率は２１％である。 88 parts of the above pigment dispersion, 0.2 part of shear thinning agent (succinoglycan) [manufactured by Sansho Co., Ltd., product name: Reosan], and a phosphate ester surfactant [Daiichi Kogyo Seiyaku Co., Ltd.] Co., Ltd., product name: PRICELURF AL] 1 part, pH adjuster (triethanolamine) 1 part, preservative [Lonza Japan Co., Ltd., product name: Proxel XL-2 (S)] 0 .1 part and 9.7 parts of water were mixed to prepare a water-based ink composition for writing instruments. The content of the dispersant (i.e., the total of "DISPER BYK-2010" and "Plysurf AL") with respect to the total mass of the ink composition is 3.6%, and the content of the dispersant for the guanine pigment (i.e., "DISPER BYK-2010") is 3.6%. 2010" and "Plysurf AL") is 21%.
　筆記具の作製
　上記の筆記具用水性インキ組成物を、ポリプロピレン製パイプからなるインキ収容体に吸引充填した後、樹脂製ホルダーを介して、直径０．５ｍｍの超硬製のボールを先端に抱持したボールペンチップと連結させた。次いで、インキ収容体の後端より、ポリブテンを主成分とする粘弾性を有するインキ逆流防止体（液栓）を充填し、さらに尾栓をパイプの後部に嵌合させ、遠心により脱気処理を行い、ボールペンレフィルを得た。
　次いで、上記のレフィルを軸筒内に組み込み、筆記具（出没式ボールペン）を作製した。
　上記のボールペンは、ボールペンレフィルに設けられたチップが外気に晒された状態で軸筒内に収納されており、軸筒の後端に設けられた操作部を前方に押圧することによって軸筒前端開口部からチップが突出する、後端ノック式の出没構造が設けられる。 Preparation of writing instrument After the above water-based ink composition for writing instruments was suction-filled into an ink container made of a polypropylene pipe, a carbide ball with a diameter of 0.5 mm was held at the tip via a resin holder. Connected to ballpoint pen tip. Next, a viscoelastic ink backflow preventer (liquid plug) containing polybutene as a main component is filled from the rear end of the ink container, and a tail plug is fitted to the rear of the pipe, and deaeration is performed by centrifugation. I did so and got a ballpoint pen refill.
Next, the above-mentioned refill was assembled into a barrel to produce a writing instrument (retractable ballpoint pen).
In the above ballpoint pen, the tip provided in the ballpoint pen refill is stored in the barrel while being exposed to the outside air, and the front end of the barrel is pushed forward by the operating section provided at the rear end of the barrel. A rear end knock-type retractable structure is provided in which the tip protrudes from the opening.
　実施例６のボールペンを用いて、室温（２０℃）環境下で、黒色上質紙〔中厚、（株）活英社製〕に手書きで筆記したところ、カスレおよび線飛び等の筆記不良がなく、明瞭な白色の筆跡が形成された。また、この筆跡は筆記面を隠蔽しており、隠蔽性に富む良好な筆跡であった。 When the ballpoint pen of Example 6 was used to write by hand on black high-quality paper (medium thickness, manufactured by Katsueisha Co., Ltd.) at room temperature (20°C), there were no writing defects such as blurring or line skipping. , a clear white handwriting was formed. In addition, this handwriting concealed the writing surface and was a good handwriting with excellent concealment properties.
　実施例７
　顔料分散体の調製
　グアニン〔東京化成工業（株）製〕１０部と、分散剤〔東亞合成（株）製、製品名：アロンＡ－１２ＳＬ（固形分：４０％）〕２．５部と、水８７．５部とを混合した。そして、メディアとして直径１．４～１．６ｍｍのジルコニアビーズを２００部加え、ビーズミルにより６時間、粉砕分散処理を行い、顔料分散体（グアニン顔料分散液）を調製した。なお、顔料分散体の総質量に対する分散剤の含有率は１％であり、グアニン顔料に対する分散剤の含有率は１０％である。また、上述の方法により、顔料分散体中に分散するグアニン顔料の平均粒子径を測定した結果、０．３５μｍであった。 Example 7
Preparation of pigment dispersion 10 parts of guanine [manufactured by Tokyo Chemical Industry Co., Ltd.], 2.5 parts of a dispersant [manufactured by Toagosei Co., Ltd., product name: Aron A-12SL (solid content: 40%)], 87.5 parts of water were mixed. Then, 200 parts of zirconia beads with a diameter of 1.4 to 1.6 mm were added as a media, and pulverization and dispersion treatment was performed using a bead mill for 6 hours to prepare a pigment dispersion (guanine pigment dispersion). Note that the content of the dispersant with respect to the total mass of the pigment dispersion was 1%, and the content of the dispersant with respect to the guanine pigment was 10%. Furthermore, the average particle diameter of the guanine pigment dispersed in the pigment dispersion was measured by the above method and was found to be 0.35 μm.
　実施例８～１３
　顔料分散体の調製
　実施例８～１３の各顔料分散体は、配合する材料の種類と配合量を以下の表５に記載のものに変更した以外は、実施例７と同様にして調製した。顔料分散体の総質量に対する分散剤の含有率、グアニン顔料に対する分散剤の含有率、顔料分散体中に分散するグアニン顔料の平均粒子径を、以下の表５に示した。 Examples 8-13
Preparation of Pigment Dispersion Each of the pigment dispersions of Examples 8 to 13 was prepared in the same manner as Example 7, except that the types and amounts of the materials to be blended were changed to those listed in Table 5 below. The content ratio of the dispersant to the total mass of the pigment dispersion, the content ratio of the dispersant to the guanine pigment, and the average particle diameter of the guanine pigment dispersed in the pigment dispersion are shown in Table 5 below.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　表５中の材料の内容を、注番号に沿って説明する。
　（７）東京化成工業（株）製
　（８）未中和型アクリル－スルホン酸系共重合体〔東亞合成（株）製、製品名：アロンＡ－１２ＳＬ（固形分：４０％）〕
　（９）カルボキシ基含有ポリマー変性物の２－アミノ－２－メチル－１－プロパノール塩〔共栄社化学（株）製、製品名：フローレンＧ－７００ＡＭＰ（固形分：４５％）、酸価：２５ｍｇＫＯＨ／ｇ、アミン価：２５ｍｇＫＯＨ／ｇ〕
　（１０）コントロール重合のアクリル系共重合物〔ビックケミー・ジャパン（株）製、製品名：ＤＩＳＰＥＲ　ＢＹＫ－２０１０（固形分：４０％）、酸価：２０ｍｇＫＯＨ／ｇ、アミン価：２０ｍｇＫＯＨ／ｇ〕
　（１１）酸性基を有するコポリマー〔ビックケミー・ジャパン（株）製、製品名：ＤＩＳＰＥＲ　ＢＹＫ－１０２（固形分：９９％）、酸価：１０１ｍｇＫＯＨ／ｇ〕
　（１２）カルボキシ基含有スチレン－アクリル共重合体〔ＢＡＳＦジャパン（株）製、製品名：ジョンクリル５７Ｊ（固形分：３７％）、酸価：２１５ｍｇＫＯＨ／ｇ〕
　（１３）酸性基含有櫛型高分子分散剤〔日本ルーブリゾール（株）製、製品名：ソルスパース４６０００（固形分：５０％）、酸価：１２±２ｍｇＫＯＨ／ｇ〕
　（１４）酸性基含有櫛型高分子分散剤〔日本ルーブリゾール（株）製、製品名：ソルスパース４７０００（固形分：４０％）、酸価：８±１．５ｍｇＫＯＨ／ｇ〕 The contents of the materials in Table 5 will be explained according to the note numbers.
(7) Manufactured by Tokyo Kasei Kogyo Co., Ltd. (8) Unneutralized acrylic-sulfonic acid copolymer [manufactured by Toagosei Co., Ltd., product name: Aron A-12SL (solid content: 40%)]
(9) 2-Amino-2-methyl-1-propanol salt of modified polymer containing carboxyl group [manufactured by Kyoeisha Kagaku Co., Ltd., product name: Floren G-700AMP (solid content: 45%), acid value: 25 mgKOH/ g, amine value: 25mgKOH/g]
(10) Controlled polymerization acrylic copolymer [manufactured by BYK Chemie Japan Co., Ltd., product name: DISPER BYK-2010 (solid content: 40%), acid value: 20 mgKOH/g, amine value: 20 mgKOH/g]
(11) Copolymer with acidic group [manufactured by BYK Chemie Japan Co., Ltd., product name: DISPER BYK-102 (solid content: 99%), acid value: 101 mgKOH/g]
(12) Carboxy group-containing styrene-acrylic copolymer [manufactured by BASF Japan Ltd., product name: Joncryl 57J (solid content: 37%), acid value: 215 mgKOH/g]
(13) Acidic group-containing comb-shaped polymer dispersant [manufactured by Nippon Lubrizol Co., Ltd., product name: Solsperse 46000 (solid content: 50%), acid value: 12 ± 2 mgKOH/g]
(14) Acidic group-containing comb-shaped polymer dispersant [manufactured by Nippon Lubrizol Co., Ltd., product name: Solsperse 47000 (solid content: 40%), acid value: 8 ± 1.5 mgKOH/g]
［分散安定性評価］
　実施例７～１３の各顔料分散体を、上記実施例１～４、ならびに、比較例１と同様の方法で分散安定性を評価した。評価結果を、以下の表６に示す。 [Dispersion stability evaluation]
The dispersion stability of each of the pigment dispersions of Examples 7 to 13 was evaluated in the same manner as in Examples 1 to 4 and Comparative Example 1 above. The evaluation results are shown in Table 6 below.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　応用例１
　液状組成物の調製
　グアニン〔東京化成工業（株）製〕２０部と、分散剤〔東亞合成（株）製、製品名：アロンＡ－１２ＳＬ（固形分：４０％）〕７．５部と、水７２．５部とを混合した。そして、メディアとして直径１．４～１．６ｍｍのジルコニアビーズを２００部加え、ビーズミルにより５時間、粉砕分散処理を行い、スクリーン印刷に用いられる印刷用インキである液状組成物を調製した。 Application example 1
Preparation of liquid composition 20 parts of guanine [manufactured by Tokyo Chemical Industry Co., Ltd.], 7.5 parts of a dispersant [manufactured by Toagosei Co., Ltd., product name: Aron A-12SL (solid content: 40%)], 72.5 parts of water were mixed. Then, 200 parts of zirconia beads with a diameter of 1.4 to 1.6 mm were added as a media, and pulverization and dispersion treatment was performed using a bead mill for 5 hours to prepare a liquid composition that is a printing ink used in screen printing.
　積層体の作製
　黒色上質紙〔中厚、（株）活英社製〕の表面に、上記の印刷用インキを用いて、スクリーン印刷によりベタ柄を印刷し、乾燥して硬化させて着色層を設けて、積層体を得た。 Preparation of laminate A solid pattern is printed on the surface of black high-quality paper (medium weight, manufactured by Katsueisha Co., Ltd.) using the above printing ink by screen printing, and then dried and hardened to form a colored layer. A laminate was obtained.
　応用例１の積層体は、着色層が明瞭な白色であると共に良好な隠蔽性を有し、着色層を通して下層の紙の黒色が視認されなかった。また、液状組成物中におけるグアニン顔料の分散性に優れるため、着色層の濃度が均一であると共に、外観が良好であった。 In the laminate of Application Example 1, the colored layer was clearly white and had good hiding properties, and the black color of the underlying paper was not visible through the colored layer. Furthermore, since the guanine pigment had excellent dispersibility in the liquid composition, the colored layer had a uniform concentration and a good appearance.
　本出願は、出願日が２０２２年６月２９日である日本国特許出願、特願第２０２２－１０５０１１号を基礎出願とする優先権主張を伴う。特願第２０２２－１０５０１１号は参照することにより本明細書に取り込まれる。 This application claims priority to the Japanese patent application, Japanese Patent Application No. 2022-105011, whose filing date is June 29, 2022, as the basic application. Japanese Patent Application No. 2022-105011 is incorporated herein by reference.

Claims (7)

  1. 　少なくとも、グアニン顔料を含む顔料と、水とを含んでなる、筆記具用水性インキ組成物。 A water-based ink composition for writing instruments, comprising at least a pigment containing a guanine pigment and water.
  2. 　分散剤をさらに含んでなる、請求項１記載のインキ組成物。 The ink composition according to claim 1, further comprising a dispersant.
  3. 　前記分散剤は、酸性基及び／又は酸性基の塩を有する、請求項２に記載のインキ組成物。 The ink composition according to claim 2, wherein the dispersant has an acidic group and/or a salt of an acidic group.
  4. 　前記グアニン顔料の平均粒子径が０．１～１μｍである、請求項１乃至３のいずれか一項に記載のインキ組成物。 The ink composition according to any one of claims 1 to 3, wherein the guanine pigment has an average particle diameter of 0.1 to 1 μm.
  5. 　前記インキ組成物の総質量に対する前記グアニン顔料の含有率が、１～５０質量％である、請求項１乃至４のいずれか一項に記載のインキ組成物。 The ink composition according to any one of claims 1 to 4, wherein the content of the guanine pigment with respect to the total mass of the ink composition is 1 to 50% by mass.
  6. 　着色剤をさらに含んでなる、請求項１乃至５のいずれか一項に記載のインキ組成物。 The ink composition according to any one of claims 1 to 5, further comprising a colorant.
  7. 　請求項１乃至６のいずれか一項に記載のインキ組成物を収容してなる、筆記具。 A writing instrument containing the ink composition according to any one of claims 1 to 6.
PCT/JP2023/023934 2022-06-29 2023-06-28 Aqueous ink composition for writing utensil and writing utensil housing same WO2024005056A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5566978A (en) * 1978-11-15 1980-05-20 Shion Kagaku Kogyo Kk Ink for writing utensil
JP2004502822A (en) * 2000-07-03 2004-01-29 ベロル・コーポレイション Pearl ink, writing utensils, and methods
US20050257718A1 (en) * 2004-05-22 2005-11-24 Engelhard Corporation Natural Pearl in Butylene Glycol

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5566978A (en) * 1978-11-15 1980-05-20 Shion Kagaku Kogyo Kk Ink for writing utensil
JP2004502822A (en) * 2000-07-03 2004-01-29 ベロル・コーポレイション Pearl ink, writing utensils, and methods
US20050257718A1 (en) * 2004-05-22 2005-11-24 Engelhard Corporation Natural Pearl in Butylene Glycol

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