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WO2016163291A1 - Dispersion liquide de microparticules de résine de couleur pour encre aqueuse, et composition d'encre aqueuse pour instrument d'écriture mettant en œuvre celle-ci - Google Patents

Dispersion liquide de microparticules de résine de couleur pour encre aqueuse, et composition d'encre aqueuse pour instrument d'écriture mettant en œuvre celle-ci Download PDF

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Publication number
WO2016163291A1
WO2016163291A1 PCT/JP2016/060603 JP2016060603W WO2016163291A1 WO 2016163291 A1 WO2016163291 A1 WO 2016163291A1 JP 2016060603 W JP2016060603 W JP 2016060603W WO 2016163291 A1 WO2016163291 A1 WO 2016163291A1
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Prior art keywords
water
fine particles
resin fine
colored resin
dispersion
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PCT/JP2016/060603
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English (en)
Japanese (ja)
Inventor
久人 羽賀
岩佐　敦
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Mitsubishi Pencil Co Ltd
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Mitsubishi Pencil Co Ltd
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Priority claimed from JP2015155221A external-priority patent/JP6563731B2/ja
Application filed by Mitsubishi Pencil Co Ltd filed Critical Mitsubishi Pencil Co Ltd
Priority to US15/564,598 priority Critical patent/US20180079920A1/en
Priority to CN201680019809.6A priority patent/CN107429092A/zh
Priority to EP16776458.8A priority patent/EP3281992B1/fr
Publication of WO2016163291A1 publication Critical patent/WO2016163291A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/16—Writing inks

Definitions

  • the present invention relates to a dispersion of colored resin fine particles for water-based ink, which has the property of improving drawing dryness in addition to functions as color materials such as color developability, weather resistance, and stability, and sign pens and marking pens using the same
  • the present invention relates to a water-based ink composition for a writing instrument suitable for a writing instrument such as a ballpoint pen.
  • An aqueous dispersion of colored resin fine particles for aqueous ink prepared by emulsion polymerization of a vinyl monomer having an acidic functional group in which a water-soluble basic dye is dissolved in the presence of a polymerizable surfactant for example, patents) Reference 1
  • 2) Aqueous dispersion of colored resin fine particles for ink obtained by heat-treating a solution obtained by dissolving a water-soluble dye in an emulsion polymerization solution obtained by emulsion polymerization of a vinyl monomer in the presence of a polymerizable surfactant for example, patents) Reference 1
  • Aqueous dispersion of colored resin fine particles for ink obtained by heat-treating a solution obtained by dissolving a water-soluble dye in an emulsion polymerization solution obtained by emulsion polymerization of a vinyl monomer in the presence of a polymerizable surfactant.
  • Patent Document 2 A mixed vinyl monomer containing a vinyl monomer having an acidic functional group in which a water-soluble basic dye is dissolved and a vinyl monomer having a cyano group is emulsified in the presence of a polymerizable surfactant.
  • Polymerized colored fine resin particle aqueous dispersion for example, see Patent Document 3
  • Dye-dyed cyano group-containing vinyl monomer (A), and vinyl represented by the specific formula Nomar (B) and an aqueous ink characterized by containing the resin particles made of a copolymer comprising one or both of the vinyl monomer (C) as constituent monomers e.g., see Patent Document 4
  • each of the color materials described in Patent Documents 1 to 4 exhibits excellent effects in color development, weather resistance, stability, and the like, but there is no knowledge of adding other functions.
  • coloring materials such as color developability, weather resistance, and stability
  • colored resin fine particles for water-based inks having further functions are currently desired.
  • JP-A-10-259337 (Claims, Examples, etc.) JP-A-10-77435 (Claims, Examples, etc.) JP-A-10-77436 (Claims, Examples, etc.) Japanese Patent Laid-Open No. 2001-181544 (Claims, Examples, etc.)
  • the present invention is to solve this in view of the current state of the prior art described above, and in addition to functions as a coloring material such as color developability, weather resistance, and stability, it has the property of improving the drawing dryness. It is an object of the present invention to provide a dispersion of colored resin fine particles for water-based ink, and a water-based ink composition for writing tools suitable for writing tools such as sign pens, marking pens, and ballpoint pens using the same.
  • the present inventors have at least a carboxyl group-containing vinyl monomer (A) having a solubility in water as an acidic functional group of a specific value or less, and acrylic acid or methacrylic acid.
  • a dispersion in which colored resin fine particles composed of an ester monomer (B) of an acid and a linear or cyclic alcohol having a specific number of carbon atoms and a basic dye or an oil-soluble dye are dispersed in water.
  • the present invention resides in the following (1) to (6).
  • At least an ester monomer of a carboxyl group-containing vinyl monomer (A) having an acid functional group solubility in water of 10% by mass or less and acrylic acid or methacrylic acid and a linear or cyclic alcohol having 2 to 18 carbon atoms A dispersion of colored resin fine particles for water-based inks, wherein colored resin fine particles composed of (B) and a basic dye or an oil-soluble dye are dispersed in water.
  • the total content of the carboxyl group-containing vinyl monomer (A) and the ester monomer (B) among the polymer components constituting the colored resin fine particles for water-based ink is 60% by mass or more.
  • the content of the carboxyl group-containing vinyl monomer (A) is 40% by mass or more, and the content of the ester monomer (B) is 20% by mass or more
  • a water-based ink composition for a writing instrument suitable for a writing instrument such as a marking pen and a ballpoint pen is provided. Furthermore, in the case of using the dicyclopenta (te) nyl (meth) acrylate monomer (C), in addition to the above effects, a dispersion of colored resin fine particles for aqueous ink that is less likely to lose stability even when moisture is volatilized, and aqueous for writing instruments An ink composition will be obtained.
  • the dispersion of the colored resin fine particles for aqueous ink of the present invention comprises at least a carboxyl group-containing vinyl monomer (A) having an acid functional group solubility in water of 10% by mass or less, acrylic acid or methacrylic acid, and a carbon number of 2 to Colored resin fine particles composed of an ester monomer (B) with 18 linear or cyclic alcohols and a basic dye or oil-soluble dye are dispersed in water.
  • A carboxyl group-containing vinyl monomer having an acid functional group solubility in water of 10% by mass or less, acrylic acid or methacrylic acid, and a carbon number of 2 to
  • Colored resin fine particles composed of an ester monomer (B) with 18 linear or cyclic alcohols and a basic dye or oil-soluble dye are dispersed in water.
  • the carboxyl group-containing vinyl monomer having a solubility in water of 10% by mass or less as the acidic functional group to be used as the component (A) used in the present invention is a coloring monomer and has a solubility in water of 10% by mass or less.
  • the vinyl monomer having an acidic functional group of carboxyl group is not particularly limited.
  • succinic acid-2-methacryloyloxyethyl manufactured by Mitsubishi Rayon Co., Ltd., acrylic ester SA, solubility in water: 1.
  • the proportion of the acidic monomer in the mixed monomer with the component (B) can be increased.
  • the amount of the oil-soluble dye that can be mixed with the vinyl monomer becomes very large, and as a result, colored resin fine particles having a deep color and excellent color developability can be obtained.
  • the solubility in water exceeds 10% by mass, or using a vinyl monomer having only an acidic functional group such as a sulfone group other than a carboxyl group as a main component, the effect of the present invention cannot be exhibited. Become.
  • the ester monomer of acrylic acid or methacrylic acid and linear or cyclic alcohol having 2 to 18 carbon atoms used as the component (B) used in the present invention is a skeleton monomer, and acrylic acid or methacrylic acid and carbon number 2
  • (meth) acrylic acid represents “acrylic acid and / or methacrylic acid”. It is particularly preferable to use n-butyl (meth) acrylate, lauryl methacrylate, or cyclohexyl methacrylate, which further improves the drawn line drying property. Since the component (B) used is an ester monomer of acrylic acid or methacrylic acid and a linear or cyclic alcohol having 2 to 18 carbon atoms, methyl (meth) acrylate cannot exert the effects of the present invention. .
  • Examples of the basic dye used in the present invention include di- and triarylmethane-based dyes; azine-based (including nigrosine), oxazine-based and thiazine-based quinoneimine-based dyes; xanthene-based dyes; triazole azo-based dyes; Benzothiazole azo dyes; azo dyes; methine dyes such as polymethine, azomethine, and azamethine dyes; anthraquinone dyes; and basic dyes such as phthalocyanine dyes. Water-soluble basic dyes are desirable. Specific examples of yellow basic dyes that can be used include C.I. I.
  • yellow basic dyes include AIZEN CATHILLON YELLOW GPLH (trade name manufactured by Hodogaya Chemical Co., Ltd.).
  • orange basic dyes include C.I. I.
  • COLORs such as Basic Orange-1, -2, -7, -14, -15, -21, -22, -23, -24, -25, -30, -32, -33, -34, etc.
  • dyes described in INDEX examples include C.I. I.
  • Examples of purple basic dyes include C.I. I. Basic Violet-1, -2, -3, -4, -5, -6, -7, -8, -10, -11, -11: 1, -12, -13, -14, -15, -16, -18, -21, -23, -24, -25, -26, -27, -28, -29, -33, -39, etc. It is done.
  • Examples of blue basic dyes include C.I. I.
  • green basic dyes include C.I. I.
  • examples thereof include dyes described in COLOR INDEX such as Basic Green-1, -4, -6, and -10.
  • examples of commercially available green basic dyes include Diacryl Supra Brilliant Green 2GL (trade name, manufactured by Mitsubishi Chemical Corporation).
  • brown basic dyes include C.I. I. Examples thereof include dyes described in COLOR INDEX of Basic Brown-1, -2, -4, -5, -7, -11, -12, -13, and -15.
  • brown basic dyes examples include Janus Brown R (trade name, manufactured by Nippon Kagaku Co., Ltd.), AIZEN CATILON BROWN GH (trade name, manufactured by Hodogaya Chemical Co., Ltd.), and the like.
  • black basic dyes examples include C.I. I. Examples thereof include dyes described in COLOR INDEX such as Basic Black-1, -2, -3, -7, -8, and nigrosine basic dyes.
  • oil-soluble dye used in the present invention examples include commercially available monoazo, disazo, metal complex type monoazo, anthraquinone, phthalocyanine, triarylmethane and the like. Further, a salt-forming oil-soluble dye in which a functional group such as an acid / basic dye is substituted with a hydrophobic group can also be used. Examples of yellow type include C.I. I. Solvent yellow 114, 116; I. Solvent Orange 67; I. Solvent Red 122, 146; I. Solvent Blue 5, 36, 44, 63, 70, 83, 105, 111; I.
  • Solvent Black 3, 7, 27, 29 Specific commercially available oil-soluble dyes include blue dye SBN blue 701 (Hodogaya Chemical Co., Ltd.), blue dye oil blue 650 (Orient Chemical Co., Ltd.), red dye SOC-1-0100 (Orient Chemical Co., Ltd.) ), Oil black 860 (manufactured by Orient Chemical Co., Ltd.) and the like.
  • the dispersion of the colored resin fine particles for water-based ink of the present invention comprises at least a carboxyl group-containing vinyl monomer having a solubility in water of 10% by mass or less as the acidic functional group of the component (A) and the acrylic of the component (B).
  • Colored resin fine particles composed of an ester monomer of acid or methacrylic acid and a linear or cyclic alcohol having 2 to 18 carbon atoms and a basic dye or oil-soluble dye are dispersed in water, and the production thereof
  • a basic dye or oil-soluble dye is dissolved in a mixed monomer containing an ester monomer with a linear or cyclic alcohol, and ammonium persulfate or persulfate potassium is dissolved.
  • a polymerization initiator such as hydrogen peroxide
  • a reducing agent further combination with the polymerization initiator can be prepared such as by emulsion polymerization using a further polymerizable surfactant as needed.
  • staining was performed simultaneously with superposition
  • the component (A) and the component (B) are further mixed with a dicyclopenta (te) nyl (meth) acrylate monomer as the component (C) to perform emulsion polymerization. Also good.
  • dicyclopenta (te) nyl (meth) acrylate monomer is further mixed and emulsion polymerized. Even if the water in the dispersion is volatilized, the stability of the polymer is less likely to be lost. This is because an aqueous dispersion of colored resin fine particles for water-based inks and a water-based ink composition for writing tools can be obtained.
  • the dicyclopenta (te) nyl (meth) acrylate monomer includes dicyclopentanyl acrylate monomer, dicyclopentenyl acrylate, dicyclopentanyl methacrylate monomer, and dicyclopentenyl methacrylate.
  • other hydrophobic vinyl monomers may be mixed to perform the emulsion polymerization.
  • the hydrophobic vinyl monomer that can be used is not particularly limited, and examples thereof include styrenes such as styrene and methylstyrene.
  • a monomer having a reactive crosslinking group such as an epoxy group, a hydroxymethylamide group or an isocyanate group, or a polyfunctional monomer having two or more vinyl groups may be blended and crosslinked.
  • the total content of the carboxyl group-containing vinyl monomer (A) and the ester monomer (B) is the color developing property and weather resistance.
  • it is preferably 60% by mass or more, more preferably 70% by mass in the polymer composition, from the viewpoint of improving drawn line drying and further exerting the effects of the present invention. It is desirable that the content is not less than 100% by mass.
  • the content of the carboxyl group-containing vinyl monomer of the component (A) is 40% by mass or more, and the content of the ester monomer (B) of the component (B) is 20% by mass or more. Is desirable.
  • the dicyclopenta (te) nyl (meth) acrylate monomer (C) is further used, from the viewpoint of stability and further improvement of ink performance.
  • the content is preferably 1 to 25% by mass, more preferably 5 to 15% by mass.
  • the content of the basic dye or oil-soluble dye is preferably 0.2 to 50 with respect to the total amount of monomers from the viewpoint of functions as a coloring material such as color developability, weather resistance, and stability. It is desirable that the content be 0.5% by mass, more preferably 0.5 to 10% by mass.
  • the polymerizable surfactant that can be used as necessary is not particularly limited as long as it is a polymerizable surfactant that is usually used in the emulsion polymerization.
  • the polymerizable surfactant may be an anionic surfactant.
  • a nonionic polymerizable surfactant Adeka Soap NE-10, NE-20, NE-30, NE-40, SE-40, SE-10N manufactured by Adeka Co., Ltd., manufactured by Kao Corporation Latemul S-180, S-180A, S-120A, Elemiol JS-20 manufactured by Sanyo Chemical Industries, Ltd., and the like.
  • the amount of these polymerizable surfactants used is 0 to 50% by mass, preferably 0.1 to 50% by mass, based on the total amount of the monomers.
  • the preferred embodiment specifically, a mixed monomer containing at least 40% by mass of the carboxyl group-containing vinyl monomer of the component (A) and 20% by mass or more of the ester monomer of the component (B), Dyeing by dissolving a basic dye or oil-soluble dye as described above and emulsion polymerization, or at least dissolving the basic dye or oil-soluble dye after the polymerization of the component (A) and the component (B).
  • a dispersion of colored resin fine particles for water-based ink in which 20 to 50% by weight of colored resin fine particles as a resin solid content is dispersed in water is obtained.
  • the resulting dispersion of the colored resin fine particles has a property of improving the line drawing dryness, which has not been achieved in the past, in addition to functions as a coloring material such as color developability, weather resistance, and stability. It is useful as a coloring material for a water-based ink composition for a writing instrument suitable for a writing instrument such as a ballpoint pen.
  • dicyclopenta (te) nyl (meth) acrylate monomer (C) that is, the carboxyl group-containing vinyl monomer of the component (A), the ester monomer of the component (B), and the (C)
  • a basic dye or an oil-soluble dye is dissolved in a mixed monomer containing the component dicyclopenta (te) nyl (meth) acrylate monomer, and emulsion polymerization is performed, or at least the component (A) and Water-based ink in which 20-50 mass% of colored resin fine particles are dispersed in water by dissolving a basic dye or an oil-soluble dye after polymerization of component (B) and component (C)
  • a dispersion of colored resin fine particles for use is obtained.
  • the colored resin fine particles obtained by further polymerizing the component (C) are dispersed in water, and the dispersion improves the unprecedented dryness of drawn lines in addition to the functions as a coloring material such as color development, weather resistance and stability.
  • a dispersion of colored resin fine particles for water-based inks that is less likely to lose stability even if moisture evaporates is obtained.
  • the average particle diameter of the colored resin fine particles in the dispersion of the colored resin fine particles for water-based ink obtained varies depending on each monomer type, content, polymerization conditions at the time of polymerization, etc.
  • the “average particle diameter” defined in the present invention is a value of D50 measured with a particle size distribution measuring apparatus [FPAR1000 (manufactured by Otsuka Electronics)].
  • the water-based ink composition for a writing instrument according to the present invention is characterized by containing a dispersion of colored resin fine particles having the above-described configuration, a water-soluble organic solvent, and water.
  • water-soluble organic solvents that can be used include ethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, and 1,2-butane.
  • alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, hexyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, benzyl alcohol, dimethylformamide
  • Water-soluble solvents such as amides such as diethylacetamide and ketones such as acetone can also be mixed.
  • the content of these water-soluble organic solvents varies depending on the type of writing instrument such as sign pens, marking pens and ballpoint pens, and is 1 to 40% by mass with respect to the total amount of the ink composition. Therefore, the ink composition is particularly effective for an ink composition of 10% by mass or less, more preferably 3 to 8% by mass.
  • the content of water is preferably 30 to 90% by mass, more preferably 40 to 60% by mass, based on the total amount of the ink composition. is there.
  • a preservative or antifungal agent in the water-based ink composition for a writing instrument of the present invention, a preservative or antifungal agent, a pH adjuster, an antifoaming agent, and the like can be appropriately selected and used as necessary within a range not impairing the effects of the present invention.
  • pH adjusters ammonia, urea, monoethanolamine, diethanolamine, triethanolamine, aminomethylpropanol, sodium tripolynate, sodium carbonate and other alkali metal salts of carbonic acid and phosphoric acid, and alkali metal water such as sodium hydroxide
  • alkali metal water such as sodium hydroxide
  • alkali metal water such as sodium hydroxide
  • at least one kind such as an oxide.
  • preservatives or antifungal agents examples include phenol, sodium omadin, sodium pentachlorophenol, 1,2-benzisothiazolin-3-one, 2,3,5,6-tetrachloro-4 (methylsulfonyl) pyridine, benzoic acid, Examples thereof include at least one of sorbic acid, alkali metal salts of dehydroacetic acid, benzimidazole compounds, and the like.
  • Lubricants such as phosphate esters, polyalkylene glycol derivatives such as polyoxyethylene lauryl ether, fatty acid alkali salts, nonionic surfactants, fluorosurfactants such as perfluoroalkyl phosphate esters, dimethylpolysiloxane polyethylene glycol
  • Lubricants such as phosphate esters, polyalkylene glycol derivatives such as polyoxyethylene lauryl ether, fatty acid alkali salts, nonionic surfactants, fluorosurfactants such as perfluoroalkyl phosphate esters, dimethylpolysiloxane polyethylene glycol
  • examples include at least one of polyether-modified silicone such as an adduct.
  • the colored resin for water-based ink has the property of improving the drawn line drying property. Since the fine particle dispersion is contained, a water-based ink composition for a writing instrument suitable for a writing instrument such as a sign pen, a marking pen, and a ballpoint pen can be obtained. Furthermore, in the case of using the dicyclopenta (te) nyl (meth) acrylate monomer (C), in addition to the functions as color materials such as the color development property, weather resistance, stability, etc., it improves the unprecedented drawing dryness. In addition to the properties, a water-based ink composition for a writing instrument is obtained in which the stability is not easily impaired even if moisture evaporates.
  • Example 1 Dispersions of colored resin fine particles for each water-based ink of Examples 1 to 17 and Comparative Examples 1 to 4 were prepared by the following preparation method.
  • Example 1 A 2 liter flask was equipped with a stirrer, reflux condenser, thermometer, nitrogen gas inlet tube, 1000 ml separatory funnel for monomer introduction, set in a hot water tank, 500 g of distilled water, polymerizable surfactant [manufactured by ADEKA , “Adekaria Soap SE-10N”] and 3 g of ammonium persulfate were charged, and the internal temperature was raised to 50 ° C. while introducing nitrogen gas.
  • phthalic acid-2-methacryloyloxyethyl phthalate manufactured by Mitsubishi Rayon Co., Ltd., acrylic ester PA, solubility in water: 0.08% by mass
  • component (A) component (B)
  • component (B) component (B)
  • n-butyl methacrylate A liquid was prepared by mixing 40 g of a water-soluble basic dye [manufactured by Hodogaya Chemical Co., Ltd., “AIZEN CATHILOON RED BLH 200%”] in 500 g of a mixed monomer composed of 200 g.
  • This preparation solution was added from the separatory funnel to the flask maintained at a temperature of about 50 ° C. over 3 hours with stirring to carry out emulsion polymerization.
  • the polymerization was completed after aging for 5 hours to obtain a dispersion of colored resin fine particles for aqueous ink.
  • Example 2 A dispersion of colored resin fine particles for aqueous ink was obtained in the same manner as in Example 1 except that 150 g of n-butyl acrylate was used as the component (B) in Example 1 above.
  • Example 3 In Example 1 above, a dispersion of colored resin fine particles for aqueous ink was obtained in the same manner as in Example 1 except that 150 g of lauryl methacrylate was used as the component (B).
  • Example 4 In Example 1 above, a dispersion of colored resin fine particles for aqueous ink was obtained in the same manner as in Example 1 except that 150 g of myristyl acrylate was used as the component (B).
  • Example 5 A dispersion of colored resin fine particles for aqueous ink was obtained in the same manner as in Example 1 except that 150 g of cyclohexyl methacrylate was used as the component (B) in Example 1 above.
  • Example 6 In Example 1 above, except that 200 g of 2-methacryloyloxyethyl succinate (manufactured by Mitsubishi Rayon Co., Ltd., acrylic ester SA, solubility in water: 1.86% by mass) was used as component (A). In the same manner as in Example 1, a dispersion of colored resin fine particles for aqueous ink was obtained.
  • 2-methacryloyloxyethyl succinate manufactured by Mitsubishi Rayon Co., Ltd., acrylic ester SA, solubility in water: 1.86% by mass
  • Example 7 a dispersion of colored resin fine particles for aqueous ink was obtained in the same manner as in Example 6 except that 150 g of myristyl acrylate was used as the component (B).
  • Example 6 a dispersion liquid of colored resin fine particles for aqueous ink was obtained in the same manner as in Example 6 except that 150 g of cyclohexyl methacrylate was used as the component (B).
  • Example 9 In Example 2 above, except that 200 g of hexahydrophthalic acid-2-methacryloyloxyethyl [manufactured by Mitsubishi Rayon Co., Ltd., acrylic ester HH, solubility in water: 3.40 mass%] was used as component (A). In the same manner as in Example 2, a dispersion of colored resin fine particles for aqueous ink was obtained.
  • Example 10 a dispersion of colored resin fine particles for aqueous ink was obtained in the same manner as in Example 9 except that 150 g of cyclohexyl methacrylate was used as the component (B).
  • Example 11 In Example 3 above, except that 150 g of 2-methacryloyloxyethyl maleate [manufactured by Mitsubishi Rayon Co., Ltd., acrylic ester ML, solubility in water: 9.17% by mass] was used as component (A). In the same manner as in Example 3, a dispersion of colored resin fine particles for aqueous ink was obtained.
  • Example 12 In Example 1 described above, instead of 40 g of water-soluble basic dye [Hozenya Chemical Industry Co., Ltd., “AIZEN CATILON RED BLH 200%”], an oil-soluble dye, VALIFAST BLACK 3830, manufactured by Orient Chemical Co., Ltd. In the same manner as in Example 1, a dispersion of colored resin fine particles for aqueous ink was obtained.
  • water-soluble basic dye Hozenya Chemical Industry Co., Ltd., “AIZEN CATILON RED BLH 200%”
  • VALIFAST BLACK 3830 an oil-soluble dye
  • Example 13 In Example 1 above, 40 g of water-soluble basic dye [Hodogaya Chemical Co., Ltd., “AIZEN CATHILON RED BLH 200%”] was not added, and the water-soluble basic dye was added after polymerization to produce an aqueous ink. A dispersion of colored resin fine particles was obtained.
  • Example 14 A 2 liter flask was equipped with a stirrer, reflux condenser, thermometer, nitrogen gas inlet tube, 1000 ml separatory funnel for monomer addition, set in a hot water tank, 420 g of distilled water, polymerizable surfactant [manufactured by ADEKA , “Adekaria Soap SE-10N”] and 3 g of ammonium persulfate were charged, and the internal temperature was raised to 50 ° C. while introducing nitrogen gas.
  • phthalic acid-2-methacryloyloxyethyl phthalate manufactured by Mitsubishi Rayon Co., Ltd., acrylic ester PA, solubility in water: 0.08% by mass
  • component (A) 300 g of phthalate, n-methacrylic acid as component (B)
  • component (C) 40 g of a water-soluble basic dye [manufactured by Hodogaya Chemical Co., Ltd., “AIZEN CATHILON RED BLH 200%”] was mixed with 580 g of a mixed monomer composed of 80 g of dicyclopentanyl methacrylate.
  • a liquid was prepared.
  • This preparation solution was added from the separatory funnel to the flask maintained at a temperature of about 50 ° C. over 3 hours with stirring to carry out emulsion polymerization.
  • the polymerization was completed after aging for 5 hours to obtain a dispersion of colored fine particles for aqueous ink.
  • Example 15 In Example 14 above, instead of 40 g of a water-soluble basic dye [Hozenya Chemical Co., Ltd., “AIZEN CATILON RED BLH 200%”], VALIFAST BLACK 3830 manufactured by Orient Chemical Co., Ltd. was used as an oil-soluble dye. In the same manner as in Example 14, a dispersion of colored fine particles for aqueous ink was obtained.
  • a water-soluble basic dye Hozenya Chemical Co., Ltd., “AIZEN CATILON RED BLH 200%”
  • VALIFAST BLACK 3830 manufactured by Orient Chemical Co., Ltd.
  • Example 16 A dispersion liquid of colored fine particles for aqueous ink was obtained in the same manner as in Example 14 except that dicyclopentanyl acrylate was used in place of dicyclopentanyl methacrylate.
  • Example 17 In Example 16 above, instead of 40 g of a water-soluble basic dye (“AIZEN CATHILON RED BLH 200%” manufactured by Hodogaya Chemical Co., Ltd.), VALIFAST BLACK 3830 manufactured by Orient Chemical Co., Ltd. was used as an oil-soluble dye. In the same manner as in Example 14, a dispersion of colored fine particles for aqueous ink was obtained.
  • a water-soluble basic dye (“AIZEN CATHILON RED BLH 200%” manufactured by Hodogaya Chemical Co., Ltd.
  • VALIFAST BLACK 3830 manufactured by Orient Chemical Co., Ltd.
  • Example 1 A dispersion of colored resin fine particles for aqueous ink was obtained in the same manner as in Example 1 except that 150 g of methyl methacrylate was used as the component (B) in Example 1.
  • Example 2 In Example 6 above, a dispersion of colored resin fine particles for aqueous ink was obtained in the same manner as in Example 6 except that 150 g of methyl methacrylate was used as the component (B).
  • Example 9 a dispersion of colored resin fine particles for aqueous ink was obtained in the same manner as in Example 9 except that 150 g of methyl methacrylate was used as the component (B).
  • Example 4 a dispersion of colored resin fine particles for aqueous ink was obtained in the same manner as in Example 11 except that 150 g of methyl methacrylate was used as the component (B).
  • Examples 1 to 13 which are within the scope of the present invention, are for water-based inks having the property of improving the line drawing dryness in addition to the functions as color materials such as color developability, weather resistance, and stability. It turned out that it becomes the aqueous
  • a dispersion of colored resin fine particles for aqueous ink suitable for writing instruments such as sign pens, marking pens and ballpoint pens, and an aqueous ink composition for writing instruments using the same are obtained.

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  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

L'invention fournit une dispersion liquide de microparticules de résine de couleur pour encre aqueuse qui en plus de fonctions en tant que matériau colorant telles que des propriétés chromogènes, une résistance aux intempéries, une stabilité, ou similaire, possède des caractéristiques améliorant les propriétés de séchage de trait tracé. L'invention fournit également une composition d'encre aqueuse pour instrument d'écriture mettant en œuvre cette dispersion liquide. Cette dispersion liquide de microparticules de résine de couleur pour encre aqueuse est caractéristique en ce qu'elle présente une dispersion dans l'eau de microparticules de résine de couleur qui sont configurées au moins par : un monomère de vinyle comprenant un groupe carboxy (A) dont la solubilité dans l'eau est inférieure ou égale à 10% en masse en tant que groupe fonctionnel acide ; un monomère d'ester (B) d'un acide acrylique ou d'un acide méthacrylique et d'un alcool à chaîne droite ou cyclique de 2 à 18 atomes de carbones ; et un colorant basique ou un colorant à l'huile. Enfin, la composition d'encre aqueuse pour instrument d'écriture est caractéristique en ce qu'elle comprend la dispersion liquide de microparticules de résine de couleur pour encre aqueuse dont la composition est susmentionnée, un solvant organique hydrosoluble, et une eau.
PCT/JP2016/060603 2015-04-06 2016-03-31 Dispersion liquide de microparticules de résine de couleur pour encre aqueuse, et composition d'encre aqueuse pour instrument d'écriture mettant en œuvre celle-ci Ceased WO2016163291A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US15/564,598 US20180079920A1 (en) 2015-04-06 2016-03-31 Dispersion of colored resin fine particles for aqueous ink, and aqueous ink composition for writing instruments prepared by using the same
CN201680019809.6A CN107429092A (zh) 2015-04-06 2016-03-31 水性墨用着色树脂细颗粒的分散液、及使用其制备的书写工具用水性墨组合物
EP16776458.8A EP3281992B1 (fr) 2015-04-06 2016-03-31 Dispersion liquide de fines particules de résine colorées pour encres aqueuses et composition d´encre aqueuse pour instruments d´écriture utilisant celle-ci

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2015-077779 2015-04-06
JP2015077779 2015-04-06
JP2015155221A JP6563731B2 (ja) 2015-04-06 2015-08-05 筆記具用水性インク組成物
JP2015-155221 2015-08-05

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WO2016163291A1 true WO2016163291A1 (fr) 2016-10-13

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019112561A (ja) * 2017-12-25 2019-07-11 三菱鉛筆株式会社 水性インク用着色樹脂微粒子の分散液、これを用いた筆記具用水性インク組成物
EP3933001A4 (fr) * 2019-02-28 2022-04-20 FUJIFILM Corporation Dispersion de particules de résine colorée, encre, ensemble d'encres et procédé d'impression par jet d'encre

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10259337A (ja) * 1996-09-02 1998-09-29 Mitsubishi Pencil Co Ltd 水性インキ用着色樹脂微粒子水性分散液
JP2002053788A (ja) * 2000-08-09 2002-02-19 Mitsubishi Pencil Co Ltd 水性ボールペン用インキ組成物
JP2002356602A (ja) * 2000-07-28 2002-12-13 Sekisui Chem Co Ltd 着色樹脂エマルジョン、インクジェット印刷用インク、電着液及びカラーフィルター
JP2004075818A (ja) * 2002-08-15 2004-03-11 Fuji Photo Film Co Ltd インク組成物及びインクジェット記録方法
WO2004092285A1 (fr) * 2003-04-11 2004-10-28 Seiko Epson Corporation Dispersion de pigments, et composition d'encre et jeu d'encre contenant tous deux cette dispersion de pigments

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10259337A (ja) * 1996-09-02 1998-09-29 Mitsubishi Pencil Co Ltd 水性インキ用着色樹脂微粒子水性分散液
JP2002356602A (ja) * 2000-07-28 2002-12-13 Sekisui Chem Co Ltd 着色樹脂エマルジョン、インクジェット印刷用インク、電着液及びカラーフィルター
JP2002053788A (ja) * 2000-08-09 2002-02-19 Mitsubishi Pencil Co Ltd 水性ボールペン用インキ組成物
JP2004075818A (ja) * 2002-08-15 2004-03-11 Fuji Photo Film Co Ltd インク組成物及びインクジェット記録方法
WO2004092285A1 (fr) * 2003-04-11 2004-10-28 Seiko Epson Corporation Dispersion de pigments, et composition d'encre et jeu d'encre contenant tous deux cette dispersion de pigments

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019112561A (ja) * 2017-12-25 2019-07-11 三菱鉛筆株式会社 水性インク用着色樹脂微粒子の分散液、これを用いた筆記具用水性インク組成物
EP3733789A4 (fr) * 2017-12-25 2021-09-29 Mitsubishi Pencil Company, Limited Dispersion de fines particules de résine colorée pour encre aqueuse, et composition d'encre aqueuse employant celle-ci, à utiliser dans des instruments d'écriture
JP7042610B2 (ja) 2017-12-25 2022-03-28 三菱鉛筆株式会社 筆記具用水性インク組成物
US11560489B2 (en) 2017-12-25 2023-01-24 Mitsubishi Pencil Company, Limited Dispersion liquid of colored resin fine particles for aqueous ink, and aqueous ink composition for writing instruments using same
EP3933001A4 (fr) * 2019-02-28 2022-04-20 FUJIFILM Corporation Dispersion de particules de résine colorée, encre, ensemble d'encres et procédé d'impression par jet d'encre
US12049569B2 (en) 2019-02-28 2024-07-30 Fujifilm Corporation Colored resin particle dispersion, ink, ink set, and inkjet printing method

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