WO2016163291A1 - Dispersion liquid of colored resin fine particles for aqueous inks, and aqueous ink composition for writing utensils using same - Google Patents
Dispersion liquid of colored resin fine particles for aqueous inks, and aqueous ink composition for writing utensils using same Download PDFInfo
- 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
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- water
- fine particles
- resin fine
- colored resin
- dispersion
- Prior art date
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- 239000000976 ink Substances 0.000 title claims abstract description 101
- 239000011347 resin Substances 0.000 title claims abstract description 83
- 229920005989 resin Polymers 0.000 title claims abstract description 83
- 239000010419 fine particle Substances 0.000 title claims abstract description 81
- 239000006185 dispersion Substances 0.000 title claims abstract description 67
- 239000000203 mixture Substances 0.000 title claims abstract description 35
- 239000007788 liquid Substances 0.000 title abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 94
- 239000000178 monomer Substances 0.000 claims abstract description 77
- 239000000981 basic dye Substances 0.000 claims abstract description 40
- 239000000975 dye Substances 0.000 claims abstract description 35
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- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 30
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 19
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- 125000000524 functional group Chemical group 0.000 claims abstract description 13
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- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- AQNSVANSEBPSMK-UHFFFAOYSA-N dicyclopentenyl methacrylate Chemical compound C12CC=CC2C2CC(OC(=O)C(=C)C)C1C2.C12C=CCC2C2CC(OC(=O)C(=C)C)C1C2 AQNSVANSEBPSMK-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- XYXCXCJKZRDVPU-UHFFFAOYSA-N hexane-1,2,3-triol Chemical compound CCCC(O)C(O)CO XYXCXCJKZRDVPU-UHFFFAOYSA-N 0.000 description 1
- OHMBHFSEKCCCBW-UHFFFAOYSA-N hexane-2,5-diol Chemical compound CC(O)CCC(C)O OHMBHFSEKCCCBW-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SYGRIMFNUFCHJC-UHFFFAOYSA-N hydron;4-methyl-6-phenyldiazenylbenzene-1,3-diamine;chloride Chemical compound Cl.C1=C(N)C(C)=CC(N=NC=2C=CC=CC=2)=C1N SYGRIMFNUFCHJC-UHFFFAOYSA-N 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical group NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LUCXVPAZUDVVBT-UHFFFAOYSA-N methyl-[3-(2-methylphenoxy)-3-phenylpropyl]azanium;chloride Chemical compound Cl.C=1C=CC=CC=1C(CCNC)OC1=CC=CC=C1C LUCXVPAZUDVVBT-UHFFFAOYSA-N 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 150000004060 quinone imines Chemical class 0.000 description 1
- 235000012739 red 2G Nutrition 0.000 description 1
- 239000004180 red 2G Substances 0.000 description 1
- 239000001044 red dye Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- HCJLVWUMMKIQIM-UHFFFAOYSA-M sodium;2,3,4,5,6-pentachlorophenolate Chemical compound [Na+].[O-]C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl HCJLVWUMMKIQIM-UHFFFAOYSA-M 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- JADVWWSKYZXRGX-UHFFFAOYSA-M thioflavine T Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C1=[N+](C)C2=CC=C(C)C=C2S1 JADVWWSKYZXRGX-UHFFFAOYSA-M 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
Classifications
-
- 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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Abstract
Provided are: a dispersion liquid of colored resin fine particles for aqueous inks, which has a property for improving drawn line dryability in addition to colorant functions such as color developability, weather resistance and stability; and an aqueous ink composition for writing utensils, which uses this dispersion liquid of colored resin fine particles for aqueous inks.
This dispersion liquid of colored resin fine particles for aqueous inks is characterized by being obtained by dispersing colored resin fine particles in water, said colored resin fine particles being configured at least of (A) a vinyl monomer that contains a carboxyl group as an acidic functional group and has a solubility in water of 10% by mass or less, (B) an ester monomer of an acrylic acid or methacrylic acid and a linear or cyclic alcohol having 2-18 carbon atoms, and a basic dye or an oil-soluble dye.
In addition, this aqueous ink composition for writing utensils is characterized by containing: a dispersion liquid of colored resin fine particles for aqueous inks having the above-described composition; a water-soluble organic solvent; and water.
Description
本発明は、発色性、耐候性、安定性などの色材としての機能に加えて、描線乾燥性を向上させる性質を有する水性インク用着色樹脂微粒子の分散液、これを用いたサインペンやマーキングペン、ボールペンなどの筆記具に好適な筆記具用水性インク組成物に関する。
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.
従来より、特定のポリマー構成を有する樹脂エマルションを染料で染色して、疑似顔料とも呼ばれる色材として利用することが知られている。
Conventionally, it is known that a resin emulsion having a specific polymer structure is dyed with a dye and used as a coloring material called a pseudo pigment.
例えば、１）重合性界面活性剤の存在下で水溶性塩基性染料が溶解された酸性官能基を有するビニルモノマーを乳化重合して調製された水性インク用着色樹脂微粒子水性分散液（例えば、特許文献１参照）、２）重合性界面活性剤の存在下でビニルモノマーを乳化重合して得られる乳化重合液に水溶性染料を溶解した液を加熱処理してなるインク用着色樹脂微粒子水性分散液（例えば、特許文献２参照）、３）水溶性塩基性染料を溶解した酸性官能基を有するビニルモノマーとシアノ基を有するビニルモノマーを含む混合ビニルモノマーを重合性界面活性剤の存在下で乳化共重合してなる着色樹脂微粒子水性分散液（例えば、特許文献３参照）、４）染料で染色された、シアノ基含有ビニルモノマー（Ａ）、及び、特定式に示されるビニルモノマー（Ｂ）及びビニルモノマー（Ｃ）の一方または両方を構成モノマーとして含む共重合体からなる樹脂粒子を含有することを特徴とする水性インク（例えば、特許文献４参照）が知られている。
For example, 1) 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. (See, for example, Patent Document 2) 3) 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), 4) 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) is known.
しかしながら、上記特許文献１～４に記載の各色材は、発色性、耐候性、安定性などに優れた効果を発揮するものの、それ以外の機能を付加するという知見は存在しないものである。
水性インク用等として、発色性、耐候性、安定性などの色材としての機能に加えて、更なる機能を有する水性インク用着色樹脂微粒子などが切望されているのが現状である。 However, 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.
For water-based inks and the like, in addition to functions as coloring materials such as color developability, weather resistance, and stability, colored resin fine particles for water-based inks having further functions are currently desired.
水性インク用等として、発色性、耐候性、安定性などの色材としての機能に加えて、更なる機能を有する水性インク用着色樹脂微粒子などが切望されているのが現状である。 However, 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.
For water-based inks and the like, in addition to functions as coloring materials such as color developability, weather resistance, and stability, colored resin fine particles for water-based inks having further functions are currently desired.
本発明は、上記従来技術の現状等に鑑み、これを解消しようとするものであり、発色性、耐候性、安定性などの色材としての機能に加えて、描線乾燥性を向上させる性質を有する水性インク用着色樹脂微粒子の分散液、これを用いたサインペンやマーキングペン、ボールペンなどの筆記具に好適な筆記具用水性インク組成物を提供することを目的とする。
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.
本発明者らは、上記従来の課題等に鑑み、鋭意研究を行った結果、少なくとも、酸性官能基として水への溶解度が特定値以下のカルボキシル基含有ビニルモノマー（Ａ）と、アクリル酸又はメタクリル酸と炭素数が特定範囲となる直鎖若しくは環状アルコールとのエステルモノマー（Ｂ）と、塩基性染料又は油溶性染料とで構成される着色樹脂微粒子が水に分散されている分散液とすることなどにより、上記目的の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が得られることを見出し、本発明を完成するに至ったのである。
As a result of intensive studies in view of the above-described conventional problems, 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 As a result, the inventors have found that the above-described dispersion of colored resin fine particles for water-based ink and a water-based ink composition for writing instruments using the same can be obtained, and the present invention has been completed.
すなわち、本発明は、次の（１）～（６）に存する。
（１） 少なくとも、酸性官能基として水への溶解度が１０質量％以下のカルボキシル基含有ビニルモノマー（Ａ）と、アクリル酸又はメタクリル酸と炭素数２～１８の直鎖若しくは環状アルコールとのエステルモノマー（Ｂ）と、塩基性染料又は油溶性染料とで構成される着色樹脂微粒子が水に分散されていることを特徴とする水性インク用着色樹脂微粒子の分散液。
（２） 前記水性インク用着色樹脂微粒子を構成するポリマー成分のうち、前記カルボキシル基含有ビニルモノマー（Ａ）と、前記エステルモノマー（Ｂ）の合計含有量が６０質量％以上であることを特徴とする上記（１）記載の水性インク用着色樹脂微粒子の分散液。
（３） 前記カルボキシル基含有ビニルモノマー（Ａ）の含有量が、４０質量％以上であり、前記エステルモノマー（Ｂ）の含有量が、２０質量％以上であることを特徴とする上記（２）記載の水性インク用着色樹脂微粒子の分散液。
（４） 更に、ジシクロペンタ（テ）ニル（メタ）アクリレートモノマー（Ｃ）を有することを特徴とする上記（１）～（３）の何れか１項記載の水性インク用着色樹脂微粒子の分散液。
（５） 前記水性インク用着色樹脂微粒子を構成するポリマー成分のうち、前記ジシクロペンタ（テ）ニル（メタ）アクリレートモノマー（Ｃ）の含有量が１～２５質量％であることを特徴とする上記（４）記載の水性インク用着色樹脂微粒子の分散液。
（６） 上記（１）～（５）の何れか１項記載の水性インク用着色樹脂微粒子の分散液と、水溶性有機溶剤と、水とを含有することを特徴とする筆記具用水性インク組成物。 That is, the present invention resides in the following (1) to (6).
(1) 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.
(2) 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. A dispersion of colored resin fine particles for water-based ink as described in (1) above.
(3) 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 (2) A dispersion of colored resin fine particles for water-based ink as described.
(4) The dispersion of colored resin fine particles for aqueous ink according to any one of (1) to (3) above, further comprising dicyclopenta (te) nyl (meth) acrylate monomer (C).
(5) The polymer component constituting the colored resin fine particles for water-based ink, wherein the content of the dicyclopenta (te) nyl (meth) acrylate monomer (C) is 1 to 25% by mass ( 4) A dispersion of colored resin fine particles for water-based inks.
(6) A water-based ink composition for writing instruments, comprising a dispersion of colored resin fine particles for water-based ink according to any one of (1) to (5), a water-soluble organic solvent, and water. object.
（１） 少なくとも、酸性官能基として水への溶解度が１０質量％以下のカルボキシル基含有ビニルモノマー（Ａ）と、アクリル酸又はメタクリル酸と炭素数２～１８の直鎖若しくは環状アルコールとのエステルモノマー（Ｂ）と、塩基性染料又は油溶性染料とで構成される着色樹脂微粒子が水に分散されていることを特徴とする水性インク用着色樹脂微粒子の分散液。
（２） 前記水性インク用着色樹脂微粒子を構成するポリマー成分のうち、前記カルボキシル基含有ビニルモノマー（Ａ）と、前記エステルモノマー（Ｂ）の合計含有量が６０質量％以上であることを特徴とする上記（１）記載の水性インク用着色樹脂微粒子の分散液。
（３） 前記カルボキシル基含有ビニルモノマー（Ａ）の含有量が、４０質量％以上であり、前記エステルモノマー（Ｂ）の含有量が、２０質量％以上であることを特徴とする上記（２）記載の水性インク用着色樹脂微粒子の分散液。
（４） 更に、ジシクロペンタ（テ）ニル（メタ）アクリレートモノマー（Ｃ）を有することを特徴とする上記（１）～（３）の何れか１項記載の水性インク用着色樹脂微粒子の分散液。
（５） 前記水性インク用着色樹脂微粒子を構成するポリマー成分のうち、前記ジシクロペンタ（テ）ニル（メタ）アクリレートモノマー（Ｃ）の含有量が１～２５質量％であることを特徴とする上記（４）記載の水性インク用着色樹脂微粒子の分散液。
（６） 上記（１）～（５）の何れか１項記載の水性インク用着色樹脂微粒子の分散液と、水溶性有機溶剤と、水とを含有することを特徴とする筆記具用水性インク組成物。 That is, the present invention resides in the following (1) to (6).
(1) 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.
(2) 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. A dispersion of colored resin fine particles for water-based ink as described in (1) above.
(3) 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 (2) A dispersion of colored resin fine particles for water-based ink as described.
(4) The dispersion of colored resin fine particles for aqueous ink according to any one of (1) to (3) above, further comprising dicyclopenta (te) nyl (meth) acrylate monomer (C).
(5) The polymer component constituting the colored resin fine particles for water-based ink, wherein the content of the dicyclopenta (te) nyl (meth) acrylate monomer (C) is 1 to 25% by mass ( 4) A dispersion of colored resin fine particles for water-based inks.
(6) A water-based ink composition for writing instruments, comprising a dispersion of colored resin fine particles for water-based ink according to any one of (1) to (5), a water-soluble organic solvent, and water. object.
本発明によれば、発色性、耐候性、安定性などの色材としての機能に加えて、描線乾燥性を向上させる性質を有する水性インク用着色樹脂微粒子の分散液、これを用いたサインペンやマーキングペン、ボールペンなどの筆記具に好適な筆記具用水性インク組成物が提供される。
更に、ジシクロペンタ（テ）ニル（メタ）アクリレートモノマー（Ｃ）を用いたものでは、上記効果と共に、水分が揮発したとしても安定性が損なわれにくい水性インク用着色樹脂微粒子の分散液、筆記具用水性インク組成物が得られることとなる。 According to the present invention, in addition to functions as a colorant such as color developability, weather resistance, and stability, a dispersion of colored resin fine particles for aqueous ink having a property of improving drawing dryness, a sign pen using the same, 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.
更に、ジシクロペンタ（テ）ニル（メタ）アクリレートモノマー（Ｃ）を用いたものでは、上記効果と共に、水分が揮発したとしても安定性が損なわれにくい水性インク用着色樹脂微粒子の分散液、筆記具用水性インク組成物が得られることとなる。 According to the present invention, in addition to functions as a colorant such as color developability, weather resistance, and stability, a dispersion of colored resin fine particles for aqueous ink having a property of improving drawing dryness, a sign pen using the same, 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.
以下に、本発明の実施形態を詳しく説明する。
本発明の水性インク用着色樹脂微粒子の分散液は、少なくとも、酸性官能基として水への溶解度が１０質量％以下のカルボキシル基含有ビニルモノマー（Ａ）と、アクリル酸又はメタクリル酸と炭素数２～１８の直鎖若しくは環状アルコールとのエステルモノマー（Ｂ）と、塩基性染料又は油溶性染料とで構成される着色樹脂微粒子が水に分散されていることを特徴とするものである。 Hereinafter, embodiments of the present invention will be described in detail.
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.
本発明の水性インク用着色樹脂微粒子の分散液は、少なくとも、酸性官能基として水への溶解度が１０質量％以下のカルボキシル基含有ビニルモノマー（Ａ）と、アクリル酸又はメタクリル酸と炭素数２～１８の直鎖若しくは環状アルコールとのエステルモノマー（Ｂ）と、塩基性染料又は油溶性染料とで構成される着色樹脂微粒子が水に分散されていることを特徴とするものである。 Hereinafter, embodiments of the present invention will be described in detail.
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.
本発明に用いる（Ａ）成分となる酸性官能基として水への溶解度が１０質量％以下のカルボキシル基含有ビニルモノマーは、発色モノマーとなるものであり、水への溶解度が１０質量％以下であり、カルボキシル基の酸性官能基を有するビニルモノマーであれば特に制限はなく、例えば、例えば、コハク酸－２－メタクリロイルオキシエチル〔三菱レイヨン（株）製、アクリルエステルＳＡ、水への溶解度：１．８６質量％〕、マレイン酸－２－メタクリロイルオキシエチル〔三菱レイヨン（株）製、アクリルエステルＭＬ、水への溶解度：９．１７質量％〕、フタル酸－２－メタクリロイルオキシエチル〔三菱レイヨン（株）製、アクリルエステルＰＡ、水への溶解度：０．０８質量％〕、ヘキサヒドロフタル酸－２－メタクリロイルオキシエチル〔三菱レイヨン（株）製、アクリルエステルＨＨ、水への溶解度：３．４０質量％〕などの少なくとも１種（各単独又は二種以上の混合、以下同様）が挙げられる。
特に好ましくは、十分な発色性を付与する点から、フタル酸－２－メタクリロイルオキシエチルの使用が望ましい。 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. For example, succinic acid-2-methacryloyloxyethyl [manufactured by Mitsubishi Rayon Co., Ltd., acrylic ester SA, solubility in water: 1. 86 mass%], 2-methacryloyloxyethyl maleate [Made by Mitsubishi Rayon Co., Ltd., acrylic ester ML, solubility in water: 9.17 mass%], 2-methacryloyloxyethyl phthalate [Mitsubishi Rayon Co., Ltd. Acrylic ester PA, water solubility: 0.08% by mass], hexahydrophthalic acid-2-methacryloyloxy Ethyl [Mitsubishi Rayon Co., Ltd., an acrylic ester HH, solubility in water: 3.40 wt%] at least one such (mixing of the singly or, hereinafter the same) and the like.
It is particularly preferable to use 2-methacryloyloxyethyl phthalate from the viewpoint of imparting sufficient color developability.
特に好ましくは、十分な発色性を付与する点から、フタル酸－２－メタクリロイルオキシエチルの使用が望ましい。 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. For example, succinic acid-2-methacryloyloxyethyl [manufactured by Mitsubishi Rayon Co., Ltd., acrylic ester SA, solubility in water: 1. 86 mass%], 2-methacryloyloxyethyl maleate [Made by Mitsubishi Rayon Co., Ltd., acrylic ester ML, solubility in water: 9.17 mass%], 2-methacryloyloxyethyl phthalate [Mitsubishi Rayon Co., Ltd. Acrylic ester PA, water solubility: 0.08% by mass], hexahydrophthalic acid-2-methacryloyloxy Ethyl [Mitsubishi Rayon Co., Ltd., an acrylic ester HH, solubility in water: 3.40 wt%] at least one such (mixing of the singly or, hereinafter the same) and the like.
It is particularly preferable to use 2-methacryloyloxyethyl phthalate from the viewpoint of imparting sufficient color developability.
本発明において、水への溶解度が１０質量％以下となるカルボキシル基含有ビニルモノマーを用いると、（Ｂ）成分との混合モノマー中の酸性モノマーの割合を高めることができ、従って、塩基性染料又は油溶性染料のビニルモノマーへ混和できる量が非常に多くなり、その結果、色の濃い発色性に優れる着色樹脂微粒子を得ることができる。
なお、水への溶解度が１０質量％超過のもの、また、カルボキシル基以外のスルフォン基などの酸性官能基のみを有するビニルモノマーを主成分として使用するものでは、本発明の効果を発揮できないものとなる。 In the present invention, when a carboxyl group-containing vinyl monomer having a solubility in water of 10% by mass or less can be used, 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.
It should be noted that, when 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.
なお、水への溶解度が１０質量％超過のもの、また、カルボキシル基以外のスルフォン基などの酸性官能基のみを有するビニルモノマーを主成分として使用するものでは、本発明の効果を発揮できないものとなる。 In the present invention, when a carboxyl group-containing vinyl monomer having a solubility in water of 10% by mass or less can be used, 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.
It should be noted that, when 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.
本発明に用いる（Ｂ）成分となるアクリル酸又はメタクリル酸と炭素数２～１８の直鎖若しくは環状アルコールとのエステルモノマーは、骨格モノマーとなるものであり、アクリル酸又はメタクリル酸と炭素数２～１８の直鎖若しくは環状アルコールとのエステルであり、具体的には、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｔ－ブチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸オクチル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸パルミチル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸ベヘニル等の少なくとも１種を好適に示すことができる。なお、上記「（メタ）アクリル酸」の表記は、「アクリル酸及び／又はメタクリル酸」を表す。
特に好ましくは、描線乾燥性を更に向上させる（メタ）アクリル酸ｎ－ブチル、メタクリル酸ラウリル、メタクリル酸シクロヘキシルの使用が望ましい。
用いる（Ｂ）成分は、アクリル酸又はメタクリル酸と炭素数２～１８の直鎖若しくは環状アルコールとのエステルモノマーであるので、（メタ）アクリル酸メチルでは、本発明の効果を発揮できないものである。 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 To 18 linear or cyclic alcohols, specifically, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, ( Isobutyl acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic acid Lauryl, palmitic acid (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic acid Can be suitably represents at least one such Genil. In addition, the notation of “(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. .
特に好ましくは、描線乾燥性を更に向上させる（メタ）アクリル酸ｎ－ブチル、メタクリル酸ラウリル、メタクリル酸シクロヘキシルの使用が望ましい。
用いる（Ｂ）成分は、アクリル酸又はメタクリル酸と炭素数２～１８の直鎖若しくは環状アルコールとのエステルモノマーであるので、（メタ）アクリル酸メチルでは、本発明の効果を発揮できないものである。 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 To 18 linear or cyclic alcohols, specifically, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, ( Isobutyl acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic acid Lauryl, palmitic acid (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic acid Can be suitably represents at least one such Genil. In addition, the notation of “(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. .
本発明に用いる塩基性染料としては、例えば、ジ及びトリアリールメタン系染料；アジン系（ニグロシンを含む）、オキサジン系、チアジン系等のキノンイミン系染料；キサンテン系染料；トリアゾールアゾ系染料；チアゾールアゾ系染料；ベンゾチアゾールアゾ系染料；アゾ系染料；ポリメチン系、アゾメチン系、アザメチン系等のメチン系染料；アントラキノン系染料；フタロシアニン系染料等の塩基性染料などの少なくとも１種が挙げられ、好ましくは、水溶性の塩基性染料が望ましい。
用いることができる具体的な黄色塩基性染料の例としては、Ｃ．Ｉ．ベーシックイエロー（Ｂａｓｉｃ Ｙｅｌｌｏｗ）－１、－２、－９、－１１、－１２、－１３、－１４、－１５、－１９、－２１、－２３、－２４、－２５、－２８、－２９、－３２、－３３、－３４、－３５、－３６、－４０、－４１、－５１、－６３、－７３、－８０等のＣＯＬＯＲ ＩＮＤＥＸに記載されている染料が挙げられる。また、市販されている黄色塩基性染料としては、ＡＩＺＥＮ ＣＡＴＨＩＬＯＮ ＹＥＬＬＯＷ ＧＰＬＨ（保土谷化学工業社製の商品名）等が挙げられる。
橙色塩基性染料の例としては、Ｃ．Ｉ．ベーシックオレンジ（Ｂａｓｉｃ Ｏｒａｎｇｅ）－１、－２、－７、－１４、－１５、－２１、－２２、－２３、－２４、－２５、－３０、－３２、－３３、－３４等のＣＯＬＯＲ ＩＮＤＥＸに記載されている染料が挙げられる。
赤色塩基性染料の例としては、Ｃ．Ｉ．ベーシックレッド（Ｂａｓｉｃ Ｒｅｄ）－１、－２、－３、－４、－８、－９、－１２、－１３、－１４、－１５、－１６、－１７、－１８、－２２、－２３、－２４、－２５、－２６、－２７、－２９、－３０、－３２、－３４、－３５、－３６、－３７、－３８、－３９、－４０、－４１、－４２、－４３、－４６、－４９、－５０、－５１、－５２、－５３等のＣＯＬＯＲ ＩＮＤＥＸに記載されている染料が挙げられる。また、市販されている赤色塩基性染料としては、ＡＩＺＥＮ ＣＡＴＨＩＬＯＮ ＲＥＤ ＢＬＨ、ＡＩＺＥＮ ＣＡＴＨＩＬＯＮ ＲＥＤ ＲＨなど（以上、保土谷化学工業社製の商品名）、Ｄｉａｃｒｙｌ Ｓｕｐｒａ Ｂｒｉｌｌｉａｎｔ Ｒｅｄ ２Ｇなど（三菱化学社製の商品名）、Ｓｕｍｉａｃｒｙｌ Ｒｅｄ Ｂ（住友化学社製の商品名）等が挙げられる。 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. Basic Yellow -1, -2, -9, -11, -12, -13, -14, -15, -19, -21, -23, -24, -25, -28, -29 , -32, -33, -34, -35, -36, -40, -41, -51, -63, -73, -80, and the like. Examples of commercially available yellow basic dyes include AIZEN CATHILLON YELLOW GPLH (trade name manufactured by Hodogaya Chemical Co., Ltd.).
Examples of 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. And dyes described in INDEX.
Examples of red basic dyes include C.I. I. Basic Red-1, -2, -3, -4, -8, -9, -12, -13, -14, -15, -16, -17, -18, -22, -23 , -24, -25, -26, -27, -29, -30, -32, -34, -35, -36, -37, -38, -39, -40, -41, -42,- And dyes described in COLOR INDEX such as 43, -46, -49, -50, -51, -52, and -53. In addition, examples of commercially available red basic dyes include AIZEN CATHILON RED BLH, AIZEN CATHILON RED RH, etc. (above, product names manufactured by Hodogaya Chemical Co., Ltd.), Diacryl Supra Brilliant Red 2G, etc. (products manufactured by Mitsubishi Chemical Corporation). Name), Sumiacryl Red B (trade name, manufactured by Sumitomo Chemical Co., Ltd.), and the like.
用いることができる具体的な黄色塩基性染料の例としては、Ｃ．Ｉ．ベーシックイエロー（Ｂａｓｉｃ Ｙｅｌｌｏｗ）－１、－２、－９、－１１、－１２、－１３、－１４、－１５、－１９、－２１、－２３、－２４、－２５、－２８、－２９、－３２、－３３、－３４、－３５、－３６、－４０、－４１、－５１、－６３、－７３、－８０等のＣＯＬＯＲ ＩＮＤＥＸに記載されている染料が挙げられる。また、市販されている黄色塩基性染料としては、ＡＩＺＥＮ ＣＡＴＨＩＬＯＮ ＹＥＬＬＯＷ ＧＰＬＨ（保土谷化学工業社製の商品名）等が挙げられる。
橙色塩基性染料の例としては、Ｃ．Ｉ．ベーシックオレンジ（Ｂａｓｉｃ Ｏｒａｎｇｅ）－１、－２、－７、－１４、－１５、－２１、－２２、－２３、－２４、－２５、－３０、－３２、－３３、－３４等のＣＯＬＯＲ ＩＮＤＥＸに記載されている染料が挙げられる。
赤色塩基性染料の例としては、Ｃ．Ｉ．ベーシックレッド（Ｂａｓｉｃ Ｒｅｄ）－１、－２、－３、－４、－８、－９、－１２、－１３、－１４、－１５、－１６、－１７、－１８、－２２、－２３、－２４、－２５、－２６、－２７、－２９、－３０、－３２、－３４、－３５、－３６、－３７、－３８、－３９、－４０、－４１、－４２、－４３、－４６、－４９、－５０、－５１、－５２、－５３等のＣＯＬＯＲ ＩＮＤＥＸに記載されている染料が挙げられる。また、市販されている赤色塩基性染料としては、ＡＩＺＥＮ ＣＡＴＨＩＬＯＮ ＲＥＤ ＢＬＨ、ＡＩＺＥＮ ＣＡＴＨＩＬＯＮ ＲＥＤ ＲＨなど（以上、保土谷化学工業社製の商品名）、Ｄｉａｃｒｙｌ Ｓｕｐｒａ Ｂｒｉｌｌｉａｎｔ Ｒｅｄ ２Ｇなど（三菱化学社製の商品名）、Ｓｕｍｉａｃｒｙｌ Ｒｅｄ Ｂ（住友化学社製の商品名）等が挙げられる。 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. Basic Yellow -1, -2, -9, -11, -12, -13, -14, -15, -19, -21, -23, -24, -25, -28, -29 , -32, -33, -34, -35, -36, -40, -41, -51, -63, -73, -80, and the like. Examples of commercially available yellow basic dyes include AIZEN CATHILLON YELLOW GPLH (trade name manufactured by Hodogaya Chemical Co., Ltd.).
Examples of 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. And dyes described in INDEX.
Examples of red basic dyes include C.I. I. Basic Red-1, -2, -3, -4, -8, -9, -12, -13, -14, -15, -16, -17, -18, -22, -23 , -24, -25, -26, -27, -29, -30, -32, -34, -35, -36, -37, -38, -39, -40, -41, -42,- And dyes described in COLOR INDEX such as 43, -46, -49, -50, -51, -52, and -53. In addition, examples of commercially available red basic dyes include AIZEN CATHILON RED BLH, AIZEN CATHILON RED RH, etc. (above, product names manufactured by Hodogaya Chemical Co., Ltd.), Diacryl Supra Brilliant Red 2G, etc. (products manufactured by Mitsubishi Chemical Corporation). Name), Sumiacryl Red B (trade name, manufactured by Sumitomo Chemical Co., Ltd.), and the like.
紫色塩基性染料の例としては、Ｃ．Ｉ．ベーシックバイオレット（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等のＣＯＬＯＲ ＩＮＤＥＸに記載されている染料が挙げられる。
青色塩基性染料の例としては、Ｃ．Ｉ．ベーシックブルー（Ｂａｓｉｃ Ｂｌｕｅ）－１、－２、－３、－５、－６、－７、－８、－９、－１５、－１８、－１９、－２０、－２１、－２２、－２４、－２５、－２６、－２８、－２９、－３３、－３５、－３７、－４０、－４１、－４２、－４４、－４５、－４６、－４７、－４９、－５０、－５３、－５４、－５８、－５９、－６０、－６２、－６３、－６４、－６５、－６６、－６７、－６８、－６９、－７０、－７１、－７５、－７７、－７８、－７９、－８２、－８３、－８７、－８８、等のＣＯＬＯＲ ＩＮＤＥＸに記載されている染料が挙げられる。また、市販されている青色塩基性染料としては、ＡＩＺＥＮ ＣＡＴＨＩＬＯＮ ＴＵＲＱＵＯＩＳＥ ＢＬＵＥ ＬＨ（保土谷化学工業社製の商品名）等が挙げられる。
緑色塩基性染料の例としては、Ｃ．Ｉ．ベーシックグリーン（Ｂａｓｉｃ Ｇｒｅｅｎ）－１、－４、－６、－１０等のＣＯＬＯＲ ＩＮＤＥＸに記載されている染料が挙げられる。また、市販されている緑色塩基性染料としては、Ｄｉａｃｒｙｌ Ｓｕｐｒａ Ｂｒｉｌｌｉａｎｔ Ｇｒｅｅｎ ２ＧＬ（三菱化学社製の商品名）等が挙げられる。
茶色塩基性染料の例としては、Ｃ．Ｉ．ベーシックブラウン（Ｂａｓｉｃ Ｂｒｏｗｎ）－１、－２、－４、－５、－７、－１１、－１２、－１３、－１５のＣＯＬＯＲ ＩＮＤＥＸに記載されている染料が挙げられる。また、市販されている茶色塩基性染料としては、Ｊａｎｕｓ Ｂｒｏｗｎ Ｒ（日本化学社製の商品名）、ＡＩＺＥＮ ＣＡＴＨＩＬＯＮ ＢＲＯＷＮ ＧＨ（保土谷化学工業社製の商品名）等が挙げられる。
黒色塩基性染料の例としては、Ｃ．Ｉ．ベーシックブラック（Ｂａｓｉｃ Ｂｌａｃｋ）－１、－２、－３、－７、－８等のＣＯＬＯＲ ＩＮＤＥＸに記載されている染料或いはニグロシン系塩基性染料が挙げられる。 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. Basic Blue-1, -2, -3, -5, -6, -7, -8, -9, -15, -18, -19, -20, -21, -22, -24 , -25, -26, -28, -29, -33, -35, -37, -40, -41, -42, -44, -45, -46, -47, -49, -50,- 53, -54, -58, -59, -60, -62, -63, -64, -65, -66, -67, -68, -69, -70, -71, -75, -77, Examples include dyes described in COLOR INDEX such as -78, -79, -82, -83, -87, and -88. Moreover, as a blue basic dye marketed, AIZEN CATHILON TURQUIOISE BLUE LH (brand name by Hodogaya Chemical Co., Ltd.) etc. are mentioned.
Examples of 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).
Examples of 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. Examples of commercially available brown basic dyes 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.
Examples of black basic dyes 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.
青色塩基性染料の例としては、Ｃ．Ｉ．ベーシックブルー（Ｂａｓｉｃ Ｂｌｕｅ）－１、－２、－３、－５、－６、－７、－８、－９、－１５、－１８、－１９、－２０、－２１、－２２、－２４、－２５、－２６、－２８、－２９、－３３、－３５、－３７、－４０、－４１、－４２、－４４、－４５、－４６、－４７、－４９、－５０、－５３、－５４、－５８、－５９、－６０、－６２、－６３、－６４、－６５、－６６、－６７、－６８、－６９、－７０、－７１、－７５、－７７、－７８、－７９、－８２、－８３、－８７、－８８、等のＣＯＬＯＲ ＩＮＤＥＸに記載されている染料が挙げられる。また、市販されている青色塩基性染料としては、ＡＩＺＥＮ ＣＡＴＨＩＬＯＮ ＴＵＲＱＵＯＩＳＥ ＢＬＵＥ ＬＨ（保土谷化学工業社製の商品名）等が挙げられる。
緑色塩基性染料の例としては、Ｃ．Ｉ．ベーシックグリーン（Ｂａｓｉｃ Ｇｒｅｅｎ）－１、－４、－６、－１０等のＣＯＬＯＲ ＩＮＤＥＸに記載されている染料が挙げられる。また、市販されている緑色塩基性染料としては、Ｄｉａｃｒｙｌ Ｓｕｐｒａ Ｂｒｉｌｌｉａｎｔ Ｇｒｅｅｎ ２ＧＬ（三菱化学社製の商品名）等が挙げられる。
茶色塩基性染料の例としては、Ｃ．Ｉ．ベーシックブラウン（Ｂａｓｉｃ Ｂｒｏｗｎ）－１、－２、－４、－５、－７、－１１、－１２、－１３、－１５のＣＯＬＯＲ ＩＮＤＥＸに記載されている染料が挙げられる。また、市販されている茶色塩基性染料としては、Ｊａｎｕｓ Ｂｒｏｗｎ Ｒ（日本化学社製の商品名）、ＡＩＺＥＮ ＣＡＴＨＩＬＯＮ ＢＲＯＷＮ ＧＨ（保土谷化学工業社製の商品名）等が挙げられる。
黒色塩基性染料の例としては、Ｃ．Ｉ．ベーシックブラック（Ｂａｓｉｃ Ｂｌａｃｋ）－１、－２、－３、－７、－８等のＣＯＬＯＲ ＩＮＤＥＸに記載されている染料或いはニグロシン系塩基性染料が挙げられる。 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. Basic Blue-1, -2, -3, -5, -6, -7, -8, -9, -15, -18, -19, -20, -21, -22, -24 , -25, -26, -28, -29, -33, -35, -37, -40, -41, -42, -44, -45, -46, -47, -49, -50,- 53, -54, -58, -59, -60, -62, -63, -64, -65, -66, -67, -68, -69, -70, -71, -75, -77, Examples include dyes described in COLOR INDEX such as -78, -79, -82, -83, -87, and -88. Moreover, as a blue basic dye marketed, AIZEN CATHILON TURQUIOISE BLUE LH (brand name by Hodogaya Chemical Co., Ltd.) etc. are mentioned.
Examples of 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).
Examples of 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. Examples of commercially available brown basic dyes 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.
Examples of black basic dyes 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.
本発明に用いる油溶性染料としては、一般に市販されているモノアゾ、ジスアゾ、金属錯塩型モノアゾ、アントラキノン、フタロシアニン、トリアリールメタン等が挙げられる。また、酸・塩基性染料等の官能基を疎水基で置換した造塩タイプ油溶性染料も使用することができる。
黄色系としては、Ｃ．Ｉ．ソルベントイエロー１１４、１１６；オレンジ系としては、Ｃ．Ｉ．ソルベントオレンジ６７；赤色系としては、Ｃ．Ｉ．ソルベントレッド１２２、１４６；青色系としては、Ｃ．Ｉ．ソルベントブルー５、３６、４４、６３、７０、８３、１０５、１１１；黒色系としては、Ｃ．Ｉ．ソルベントブラック３、７、２７、２９；等がそれぞれ挙げられる。
具体的な市販油溶性染料としては、青染料ＳＢＮブルー７０１（保土谷化学工業社製）、青染料オイルブルー６５０（オリエント化学工業社製）、赤染料ＳＯＣ－１－０１００（オリエント化学工業社製）、オイルブラック８６０（オリエント化学工業社製）等を挙げることができる。 Examples of the oil-soluble dye used in the present invention 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.
黄色系としては、Ｃ．Ｉ．ソルベントイエロー１１４、１１６；オレンジ系としては、Ｃ．Ｉ．ソルベントオレンジ６７；赤色系としては、Ｃ．Ｉ．ソルベントレッド１２２、１４６；青色系としては、Ｃ．Ｉ．ソルベントブルー５、３６、４４、６３、７０、８３、１０５、１１１；黒色系としては、Ｃ．Ｉ．ソルベントブラック３、７、２７、２９；等がそれぞれ挙げられる。
具体的な市販油溶性染料としては、青染料ＳＢＮブルー７０１（保土谷化学工業社製）、青染料オイルブルー６５０（オリエント化学工業社製）、赤染料ＳＯＣ－１－０１００（オリエント化学工業社製）、オイルブラック８６０（オリエント化学工業社製）等を挙げることができる。 Examples of the oil-soluble dye used in the present invention 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.
本発明の水性インク用着色樹脂微粒子の分散液は、少なくとも、上記（Ａ）成分の酸性官能基として水への溶解度が１０質量％以下のカルボキシル基含有ビニルモノマーと、上記（Ｂ）成分のアクリル酸又はメタクリル酸と炭素数２～１８の直鎖若しくは環状アルコールとのエステルモノマーと、塩基性染料又は油溶性染料とで構成される着色樹脂微粒子が水に分散されているものであり、その製造としては、例えば、上記（Ａ）成分の酸性官能基として水への溶解度が１０質量％以下のカルボキシル基含有ビニルモノマーと、上記（Ｂ）成分のアクリル酸又はメタクリル酸と炭素数２～１８の直鎖若しくは環状アルコールとのエステルモノマーとを含む混合モノマーに塩基性染料又は油溶性染料を溶解し、過硫酸アンモニウム、過硫酸カリウム、過酸化水素などを重合開始剤として、また還元剤を更に併用した重合開始剤とし、更に必要に応じて重合性界面活性剤を用いて乳化重合することなどにより製造することができる。また、上記染色は重合と同時に行ったが、重合後に塩基性染料又は油溶性染料を溶解して染色を行っても良い。
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 As, for example, a carboxyl group-containing vinyl monomer having a solubility in water of 10% by mass or less as an acidic functional group of the component (A), an acrylic acid or methacrylic acid of the component (B), and a carbon number of 2 to 18 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. Um, as a polymerization initiator such as hydrogen peroxide, also a reducing agent further combination with the polymerization initiator can be prepared such as by emulsion polymerization using a further polymerizable surfactant as needed. Moreover, although the said dyeing | staining was performed simultaneously with superposition | polymerization, you may dye | stain by dissolving a basic dye or an oil-soluble dye after superposition | polymerization.
本発明において、上記乳化重合の際には、上記（Ａ）成分、（Ｂ）成分に、更に（Ｃ）成分として、ジシクロペンタ（テ）ニル（メタ）アクリレートモノマーを混合して乳化重合を行ってもよい。上記（Ｃ）成分として、ジシクロペンタ（テ）ニル（メタ）アクリレートモノマーを更に、混合して乳化重合したものポリマーは、分散液中の水分が揮発したとしても安定性が損なわれにくく、更に安定性に優れた水性インク用着色樹脂微粒子の分散液、筆記具用水性インク組成物が得られるものとなるからである。
なお、ジシクロペンタ（テ）ニル（メタ）アクリレートモノマーには、ジシクロペンタニルアクリレートモノマー、ジシクロペンテニルアクリレート、ジシクロペンタニルメタクリレートモノマー、ジシクロペンテニルメタクリレートを含むものである。
また、本発明において、上記乳化重合の際には、上記（Ａ）成分、（Ｂ）成分、更に用いる（Ｃ）成分以外に、他の疎水性ビニルモノマーを混合して乳化重合を行ってもよい。用いることができる疎水性ビニルモノマーとしては、特に制限することはなく、例えば、スチレン、メチルスチレンなどのスチレン類などが挙げられる。また、該乳化重合において、エポキシ基、ヒドロキシメチルアミド基、イソシアネート基などの反応性架橋基を有するモノマーや２つ以上のビニル基を有する多官能性モノマーを配合して架橋してもよい。 In the present invention, at the time of the emulsion polymerization, 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. As a component (C), 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.
In the present invention, in the emulsion polymerization, in addition to the component (A), the component (B), and the component (C) to be used, other hydrophobic vinyl monomers may be mixed to perform the emulsion polymerization. Good. The hydrophobic vinyl monomer that can be used is not particularly limited, and examples thereof include styrenes such as styrene and methylstyrene. In the emulsion polymerization, 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.
なお、ジシクロペンタ（テ）ニル（メタ）アクリレートモノマーには、ジシクロペンタニルアクリレートモノマー、ジシクロペンテニルアクリレート、ジシクロペンタニルメタクリレートモノマー、ジシクロペンテニルメタクリレートを含むものである。
また、本発明において、上記乳化重合の際には、上記（Ａ）成分、（Ｂ）成分、更に用いる（Ｃ）成分以外に、他の疎水性ビニルモノマーを混合して乳化重合を行ってもよい。用いることができる疎水性ビニルモノマーとしては、特に制限することはなく、例えば、スチレン、メチルスチレンなどのスチレン類などが挙げられる。また、該乳化重合において、エポキシ基、ヒドロキシメチルアミド基、イソシアネート基などの反応性架橋基を有するモノマーや２つ以上のビニル基を有する多官能性モノマーを配合して架橋してもよい。 In the present invention, at the time of the emulsion polymerization, 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. As a component (C), 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.
In the present invention, in the emulsion polymerization, in addition to the component (A), the component (B), and the component (C) to be used, other hydrophobic vinyl monomers may be mixed to perform the emulsion polymerization. Good. The hydrophobic vinyl monomer that can be used is not particularly limited, and examples thereof include styrenes such as styrene and methylstyrene. In the emulsion polymerization, 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.
本発明において、前記水性インク用着色樹脂微粒子を構成するポリマー成分のうち、上記（Ａ）成分のカルボキシル基含有ビニルモノマーと、上記（Ｂ）成分のエステルモノマーの合計含有量は、発色性、耐候性、安定性などの色材としての機能に加えて、描線乾燥性を向上させ本発明の効果を更に発揮せしめる点から、ポリマー構成中６０質量％以上であることが好ましく、更に好ましくは、７０質量％以上～１００質量％が望ましい。
特に好ましくは、上記（Ａ）成分のカルボキシル基含有ビニルモノマーの含有量は、４０質量％以上であり、上記（Ｂ）成分のエステルモノマー（Ｂ）の含有量が、２０質量％以上であることが望ましい。
上記水性インク用着色樹脂微粒子を構成するポリマー成分のうち、更に、前記ジシクロペンタ（テ）ニル（メタ）アクリレートモノマー（Ｃ）を用いる場合は、安定性の点、インク性能の更なる向上の点から、その含有量は１～２５質量％、更に好ましくは、５～１５質量％であることが望ましい。 In the present invention, among the polymer components constituting the colored resin fine particles for water-based ink, the total content of the carboxyl group-containing vinyl monomer (A) and the ester monomer (B) is the color developing property and weather resistance. In addition to the functions as a colorant such as properties and stability, 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.
Particularly preferably, 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.
Among the polymer components constituting the colored resin fine particles for water-based ink, when 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.
特に好ましくは、上記（Ａ）成分のカルボキシル基含有ビニルモノマーの含有量は、４０質量％以上であり、上記（Ｂ）成分のエステルモノマー（Ｂ）の含有量が、２０質量％以上であることが望ましい。
上記水性インク用着色樹脂微粒子を構成するポリマー成分のうち、更に、前記ジシクロペンタ（テ）ニル（メタ）アクリレートモノマー（Ｃ）を用いる場合は、安定性の点、インク性能の更なる向上の点から、その含有量は１～２５質量％、更に好ましくは、５～１５質量％であることが望ましい。 In the present invention, among the polymer components constituting the colored resin fine particles for water-based ink, the total content of the carboxyl group-containing vinyl monomer (A) and the ester monomer (B) is the color developing property and weather resistance. In addition to the functions as a colorant such as properties and stability, 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.
Particularly preferably, 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.
Among the polymer components constituting the colored resin fine particles for water-based ink, when 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.
本発明において、上記塩基性染料又は油溶性染料の含有量は、発色性、耐候性、安定性などの色材としての機能の点から、モノマー全量に対して、好ましくは、０．２～５０質量％、更に好ましくは、０．５～１０質量％とすることが望ましい。
In the present invention, 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.
上記必要に応じて用いることができる重合性界面活性剤としては、上記乳化重合に通常用いられる重合性界面活性剤であれば特に制限はないが、例えば、重合性界面活性剤としては、アニオン系またはノニオン系の重合性界面活性剤であり、アデカ（株）製のアデカリアソープＮＥ－１０、同ＮＥ－２０、同ＮＥ－３０、同ＮＥ－４０、同ＳＥ－１０Ｎ、花王（株）製のラテムルＳ－１８０、同Ｓ－１８０Ａ、同Ｓ－１２０Ａ、三洋化成工業（株）製のエレミノールＪＳ－２０などの少なくとも１種が挙げられる。これらの重合性界面活性剤の使用量は、上記モノマー全量に対して、０～５０質量％、好ましくは、０．１～５０質量％が望ましい。
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. For example, the polymerizable surfactant may be an anionic surfactant. Or, 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.
本発明において、上記好ましい態様、具体的には、少なくとも、上記（Ａ）成分のカルボキシル基含有ビニルモノマー４０質量％以上と、上記（Ｂ）成分のエステルモノマー２０質量％以上と含む混合モノマーに、上述の如く塩基性染料又は油溶性染料を溶解し、乳化重合することにより、または、少なくとも、上記（Ａ）成分と（Ｂ）成分との重合後に塩基性染料又は油溶性染料を溶解して染色することにより、樹脂固形分として２０～５０質量％の着色樹脂微粒子が水に分散されている水性インク用着色樹脂微粒子の分散液が得られることとなる。
得られる上記着色樹脂微粒子の分散液は、発色性、耐候性、安定性などの色材としての機能に加えて、従来にない描線乾燥性を向上させる性質を有するものとなり、サインペンやマーキングペン、ボールペンなどの筆記具に好適な筆記具用水性インク組成物の色材として有用となるものである。
更に、前記ジシクロペンタ（テ）ニル（メタ）アクリレートモノマー（Ｃ）を用いる場合、すなわち、上記上記（Ａ）成分のカルボキシル基含有ビニルモノマーと、上記（Ｂ）成分のエステルモノマーと、当該（Ｃ）成分のジシクロペンタ（テ）ニル（メタ）アクリレートモノマーとを含む混合モノマーに、上述の如く、塩基性染料又は油溶性染料を溶解し、乳化重合することにより、または、少なくとも、上記（Ａ）成分と（Ｂ）成分と（Ｃ）成分の重合後に塩基性染料又は油溶性染料を溶解して染色することにより、樹脂固形分として２０～５０質量％の着色樹脂微粒子が水に分散されている水性インク用着色樹脂微粒子の分散液が得られることとなる。この（Ｃ）成分を更に重合した着色樹脂微粒子が水に分散され分散液は、上記発色性、耐候性、安定性などの色材としての機能に加えて、従来にない描線乾燥性を向上させる性質と共に、水分が揮発したとしても安定性が損なわれにくい水性インク用着色樹脂微粒子の分散液が得られることとなる。
また、本発明において、得られる水性インク用着色樹脂微粒子の分散液における着色樹脂微粒子の平均粒子径は、各モノマー種、含有量、重合の際の重合条件等により変動するものであるが、０．８μｍ以下となるものであり、サインペンやマーキングペン、ボールペンなどの筆記具のペン芯において目詰まりすることなく、また、保存安定性などに優れたものとなる。なお、本発明で規定する「平均粒子径」は、粒度分布測定装置〔FPAR１０００（大塚電子製）〕にて、測定したＤ５０の値である。 In the present invention, 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). By doing so, 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.
Further, when the dicyclopenta (te) nyl (meth) acrylate monomer (C) is used, that is, the carboxyl group-containing vinyl monomer of the component (A), the ester monomer of the component (B), and the (C) As described above, 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) Thus, 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. In addition to the properties, a dispersion of colored resin fine particles for water-based inks that is less likely to lose stability even if moisture evaporates is obtained.
In the present invention, 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. .8 μm or less, and it is excellent in storage stability without clogging in a pen core of a writing instrument such as a sign pen, a marking pen, and a ballpoint pen. 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)].
得られる上記着色樹脂微粒子の分散液は、発色性、耐候性、安定性などの色材としての機能に加えて、従来にない描線乾燥性を向上させる性質を有するものとなり、サインペンやマーキングペン、ボールペンなどの筆記具に好適な筆記具用水性インク組成物の色材として有用となるものである。
更に、前記ジシクロペンタ（テ）ニル（メタ）アクリレートモノマー（Ｃ）を用いる場合、すなわち、上記上記（Ａ）成分のカルボキシル基含有ビニルモノマーと、上記（Ｂ）成分のエステルモノマーと、当該（Ｃ）成分のジシクロペンタ（テ）ニル（メタ）アクリレートモノマーとを含む混合モノマーに、上述の如く、塩基性染料又は油溶性染料を溶解し、乳化重合することにより、または、少なくとも、上記（Ａ）成分と（Ｂ）成分と（Ｃ）成分の重合後に塩基性染料又は油溶性染料を溶解して染色することにより、樹脂固形分として２０～５０質量％の着色樹脂微粒子が水に分散されている水性インク用着色樹脂微粒子の分散液が得られることとなる。この（Ｃ）成分を更に重合した着色樹脂微粒子が水に分散され分散液は、上記発色性、耐候性、安定性などの色材としての機能に加えて、従来にない描線乾燥性を向上させる性質と共に、水分が揮発したとしても安定性が損なわれにくい水性インク用着色樹脂微粒子の分散液が得られることとなる。
また、本発明において、得られる水性インク用着色樹脂微粒子の分散液における着色樹脂微粒子の平均粒子径は、各モノマー種、含有量、重合の際の重合条件等により変動するものであるが、０．８μｍ以下となるものであり、サインペンやマーキングペン、ボールペンなどの筆記具のペン芯において目詰まりすることなく、また、保存安定性などに優れたものとなる。なお、本発明で規定する「平均粒子径」は、粒度分布測定装置〔FPAR１０００（大塚電子製）〕にて、測定したＤ５０の値である。 In the present invention, 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). By doing so, 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.
Further, when the dicyclopenta (te) nyl (meth) acrylate monomer (C) is used, that is, the carboxyl group-containing vinyl monomer of the component (A), the ester monomer of the component (B), and the (C) As described above, 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) Thus, 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. In addition to the properties, a dispersion of colored resin fine particles for water-based inks that is less likely to lose stability even if moisture evaporates is obtained.
In the present invention, 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. .8 μm or less, and it is excellent in storage stability without clogging in a pen core of a writing instrument such as a sign pen, a marking pen, and a ballpoint pen. 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)].
本発明の筆記具用水性インク組成物は、上記構成の着色樹脂微粒子の分散液と、水溶性有機溶剤と、水とを含有することを特徴とするものである。
用いることができる水溶性有機溶剤としては、例えば、エチレングリコール、トリエチレングリコール、テトラエチレングリコール、プロピレングリコール、ジプロピレングリコール、１，２－プロパンジオール、１，３－プロパンジオール、１，２－ブタンジオール、２，３－ブタンジオール、１，３－ブタンジオール、１，４－ブタンジオール、１，２－ペンタンジオール、１，５－ペンタンジオール、２，５－ヘキサンジオール、３－メチル１，３－ブタンジオール、２メチルペンタン －２，４－ジオール、３－メチルペンタン－１，３，５トリオール、１，２，３－ヘキサントリオールなどのアルキレングリコール類、ポリエチレングリコール、ポリプロピレングリコールなどのポリアルキレングリコール類、グリセロール、ジグリセロール、トリグリセロールなどのグリセロール類、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、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－ｎ－ブチルエーテルなどのグリコールの低級アルキルエーテル、Ｎ－メチル－２－ピロリドン、１，３－ジメチル－２－イミダリジノンなどの少なくとも１種が挙げられる。 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.
Examples of 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. Diol, 2,3-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 2,5-hexanediol, 3-methyl 1,3 -Butanediol, 2-methylpentane-2,4-diol, alkylene glycols such as 3-methylpentane-1,3,5 triol, 1,2,3-hexanetriol, and polyalkylene glycols such as polyethylene glycol and polypropylene glycol Glycerol, digly Glycerols such as serol and triglycerol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, lower alkyl ethers of glycols such as diethylene glycol mono-n-butyl ether, N-methyl-2-pyrrolidone , 1,3-dimethyl-2-imidazolidinone and the like.
用いることができる水溶性有機溶剤としては、例えば、エチレングリコール、トリエチレングリコール、テトラエチレングリコール、プロピレングリコール、ジプロピレングリコール、１，２－プロパンジオール、１，３－プロパンジオール、１，２－ブタンジオール、２，３－ブタンジオール、１，３－ブタンジオール、１，４－ブタンジオール、１，２－ペンタンジオール、１，５－ペンタンジオール、２，５－ヘキサンジオール、３－メチル１，３－ブタンジオール、２メチルペンタン －２，４－ジオール、３－メチルペンタン－１，３，５トリオール、１，２，３－ヘキサントリオールなどのアルキレングリコール類、ポリエチレングリコール、ポリプロピレングリコールなどのポリアルキレングリコール類、グリセロール、ジグリセロール、トリグリセロールなどのグリセロール類、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、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－ｎ－ブチルエーテルなどのグリコールの低級アルキルエーテル、Ｎ－メチル－２－ピロリドン、１，３－ジメチル－２－イミダリジノンなどの少なくとも１種が挙げられる。 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.
Examples of 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. Diol, 2,3-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 2,5-hexanediol, 3-methyl 1,3 -Butanediol, 2-methylpentane-2,4-diol, alkylene glycols such as 3-methylpentane-1,3,5 triol, 1,2,3-hexanetriol, and polyalkylene glycols such as polyethylene glycol and polypropylene glycol Glycerol, digly Glycerols such as serol and triglycerol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, lower alkyl ethers of glycols such as diethylene glycol mono-n-butyl ether, N-methyl-2-pyrrolidone , 1,3-dimethyl-2-imidazolidinone and the like.
その他にも、例えば、メチルアルコール、エチルアルコール、イソプロピルアルコール、ｎ－ブチルアルコール、tert－ブチルアルコール、イソブチルアルコール、ヘキシルアルコール、オクチルアルコール、ノニルアルコール、デシルアルコール、ベンジルアルコールなどのアルコール類、ジメチルホルムアミド、ジエチルアセトアミドなどのアミド類、アセトンなどのケトン類などの水溶性溶剤を混合することもできる。
これらの水溶性有機溶剤の含有量は、サインペンやマーキングペン、ボールペンなどの筆記具種により変動するものであり、インク組成物全量に対して、１～４０質量％、描線乾燥性を更に向上させる点から、１０質量％以下としたインク組成に対して特に有効であり、より好ましくは、３～８質量％とすることが望ましい。 In addition, for example, 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.
これらの水溶性有機溶剤の含有量は、サインペンやマーキングペン、ボールペンなどの筆記具種により変動するものであり、インク組成物全量に対して、１～４０質量％、描線乾燥性を更に向上させる点から、１０質量％以下としたインク組成に対して特に有効であり、より好ましくは、３～８質量％とすることが望ましい。 In addition, for example, 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.
また、水（水道水、精製水、イオン交換水、蒸留水、純水など）の含有量は、インク組成物全量に対して３０～９０質量％が好ましく、より好ましくは４０～６０質量％である。
The content of water (tap water, purified water, ion-exchanged water, distilled water, pure water, etc.) 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.
本発明の筆記具用水性インク組成物では、本発明の効果を損なわない範囲で、必要に応じて防腐剤もしくは防黴剤、ｐＨ調整剤、消泡剤などを適宜選択して使用することができる。
例えば、ｐＨ調整剤として、アンモニア、尿素、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、アミノメチルプロパノール、トリポリン酸ナトリウム、炭酸ナトリウムなど炭酸やリン酸のアルカリ金属塩、水酸化ナトリウムなどのアルカリ金属の水酸化物などの少なくとも１種が挙げられる。
防腐剤もしくは防黴剤として、フェノール、ナトリウムオマジン、ペンタクロロフェノールナトリウム、１，２－ベンズイソチアゾリン３－オン、２，３，５，６－テトラクロロ－４（メチルスルホニル）ピリジン、安息香酸やソルビン酸やデヒドロ酢酸のアルカリ金属塩、ベンズイミダゾール系化合物などの少なくとも１種が挙げられる。
潤滑剤としてリン酸エステル類、ポリオキシエチレンラウリルエーテルなどのポリアルキレングリコール誘導体、脂肪酸アルカリ塩、ノニオン系界面活性剤、パーフルオロアルキルリン酸エステルなどのフッ素系界面活性剤、ジメチルポリシロキサンのポリエチレングリコール付加物などのポリエーテル変性シリコーンなどの少なくとも１種が挙げられる。 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. .
For example, as 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 There may be mentioned at least one kind such as an oxide.
Examples of preservatives or antifungal agents 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 Examples include at least one of polyether-modified silicone such as an adduct.
例えば、ｐＨ調整剤として、アンモニア、尿素、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、アミノメチルプロパノール、トリポリン酸ナトリウム、炭酸ナトリウムなど炭酸やリン酸のアルカリ金属塩、水酸化ナトリウムなどのアルカリ金属の水酸化物などの少なくとも１種が挙げられる。
防腐剤もしくは防黴剤として、フェノール、ナトリウムオマジン、ペンタクロロフェノールナトリウム、１，２－ベンズイソチアゾリン３－オン、２，３，５，６－テトラクロロ－４（メチルスルホニル）ピリジン、安息香酸やソルビン酸やデヒドロ酢酸のアルカリ金属塩、ベンズイミダゾール系化合物などの少なくとも１種が挙げられる。
潤滑剤としてリン酸エステル類、ポリオキシエチレンラウリルエーテルなどのポリアルキレングリコール誘導体、脂肪酸アルカリ塩、ノニオン系界面活性剤、パーフルオロアルキルリン酸エステルなどのフッ素系界面活性剤、ジメチルポリシロキサンのポリエチレングリコール付加物などのポリエーテル変性シリコーンなどの少なくとも１種が挙げられる。 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. .
For example, as 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 There may be mentioned at least one kind such as an oxide.
Examples of preservatives or antifungal agents 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 Examples include at least one of polyether-modified silicone such as an adduct.
このように構成される本発明の筆記具用水性インク組成物では、発色性、耐候性、安定性などの色材としての機能に加えて、描線乾燥性を向上させる性質を有する水性インク用着色樹脂微粒子の分散液を含有するので、サインペンやマーキングペン、ボールペンなどの筆記具に好適な筆記具用水性インク組成物が得られることとなる。
更に、ジシクロペンタ（テ）ニル（メタ）アクリレートモノマー（Ｃ）を用いたものでは、上記発色性、耐候性、安定性などの色材としての機能に加えて、従来にない描線乾燥性を向上させる性質に加えて水分が揮発したとしても安定性が損なわれにくい筆記具用水性インク組成物が得られることとなる。 In the water-based ink composition for a writing instrument of the present invention configured as described above, in addition to functions as a coloring material such as color developability, weather resistance, and stability, 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.
更に、ジシクロペンタ（テ）ニル（メタ）アクリレートモノマー（Ｃ）を用いたものでは、上記発色性、耐候性、安定性などの色材としての機能に加えて、従来にない描線乾燥性を向上させる性質に加えて水分が揮発したとしても安定性が損なわれにくい筆記具用水性インク組成物が得られることとなる。 In the water-based ink composition for a writing instrument of the present invention configured as described above, in addition to functions as a coloring material such as color developability, weather resistance, and stability, 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.
次に、実施例及び比較例により本発明を更に詳細に説明するが、本発明は下記実施例等に限定されるものではない。
Next, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.
〔実施例１～１７及び比較例１～４〕
下記調製法により実施例１～１７及び比較例１～４の各水性インク用着色樹脂微粒子の分散液を調製した。
（実施例１）
２リットルのフラスコに、撹拌機、還流冷却器、温度計、窒素ガス導入管、モノマー投入用１０００ｍｌ分液漏斗を取り付け、温水槽にセットし、蒸留水５００ｇ、重合性界面活性剤〔アデカ社製、「アデカリアソープＳＥ－１０Ｎ」〕５０ｇおよび過硫酸アンモニウム３ｇを仕込んで、窒素ガスを導入しながら、内温を５０℃まで昇温した。 [Examples 1 to 17 and Comparative Examples 1 to 4]
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.
下記調製法により実施例１～１７及び比較例１～４の各水性インク用着色樹脂微粒子の分散液を調製した。
（実施例１）
２リットルのフラスコに、撹拌機、還流冷却器、温度計、窒素ガス導入管、モノマー投入用１０００ｍｌ分液漏斗を取り付け、温水槽にセットし、蒸留水５００ｇ、重合性界面活性剤〔アデカ社製、「アデカリアソープＳＥ－１０Ｎ」〕５０ｇおよび過硫酸アンモニウム３ｇを仕込んで、窒素ガスを導入しながら、内温を５０℃まで昇温した。 [Examples 1 to 17 and Comparative Examples 1 to 4]
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.
一方、（Ａ）成分としてフタル酸－２－メタクリロイルオキシエチル〔三菱レイヨン（株）製、アクリルエステルＰＡ、水への溶解度：０．０８質量％〕３００ｇ、（Ｂ）成分としてメタクリル酸ｎ－ブチル２００ｇからなる混合モノマー５００ｇに、水溶性塩基性染料〔保土谷化学工業社製、「ＡＩＺＥＮ ＣＡＴＨＩＬＯＮ ＲＥＤ ＢＬＨ ２００％」〕４０ｇを混合した液を調製した。
この調製液を上記分液漏斗から温度５０℃付近に保った上記フラスコ内に撹拌下で３時間にわたって添加し、乳化重合を行った。さらに５時間熟成して重合を終了し、水性インク用着色樹脂微粒子の分散液を得た。 On the other hand, phthalic acid-2-methacryloyloxyethyl phthalate (manufactured by Mitsubishi Rayon Co., Ltd., acrylic ester PA, solubility in water: 0.08% by mass) as component (A), and 300 g of 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.
この調製液を上記分液漏斗から温度５０℃付近に保った上記フラスコ内に撹拌下で３時間にわたって添加し、乳化重合を行った。さらに５時間熟成して重合を終了し、水性インク用着色樹脂微粒子の分散液を得た。 On the other hand, phthalic acid-2-methacryloyloxyethyl phthalate (manufactured by Mitsubishi Rayon Co., Ltd., acrylic ester PA, solubility in water: 0.08% by mass) as component (A), and 300 g of 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.
（実施例２）
上記実施例１において、（Ｂ）成分としてアクリル酸ｎ－ブチル１５０ｇを用いた以外は、上記実施例１と同様にして、水性インク用着色樹脂微粒子の分散液を得た。 (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.
上記実施例１において、（Ｂ）成分としてアクリル酸ｎ－ブチル１５０ｇを用いた以外は、上記実施例１と同様にして、水性インク用着色樹脂微粒子の分散液を得た。 (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.
（実施例３）
上記実施例１において、（Ｂ）成分としてメタクリル酸ラウリル１５０ｇを用いた以外は、上記実施例１と同様にして、水性インク用着色樹脂微粒子の分散液を得た。 (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).
上記実施例１において、（Ｂ）成分としてメタクリル酸ラウリル１５０ｇを用いた以外は、上記実施例１と同様にして、水性インク用着色樹脂微粒子の分散液を得た。 (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).
（実施例４）
上記実施例１において、（Ｂ）成分としてアクリル酸ミリスチル１５０ｇを用いた以外は、上記実施例１と同様にして、水性インク用着色樹脂微粒子の分散液を得た。 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).
上記実施例１において、（Ｂ）成分としてアクリル酸ミリスチル１５０ｇを用いた以外は、上記実施例１と同様にして、水性インク用着色樹脂微粒子の分散液を得た。 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).
（実施例５）
上記実施例１において、（Ｂ）成分としてメタクリル酸シクロヘキシル１５０ｇを用いた以外は、上記実施例１と同様にして、水性インク用着色樹脂微粒子の分散液を得た。 (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.
上記実施例１において、（Ｂ）成分としてメタクリル酸シクロヘキシル１５０ｇを用いた以外は、上記実施例１と同様にして、水性インク用着色樹脂微粒子の分散液を得た。 (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.
（実施例６）
上記実施例１において、（Ａ）成分としてコハク酸－２－メタクリロイルオキシエチル〔三菱レイヨン（株）製、アクリルエステルＳＡ、水への溶解度：１．８６質量％〕２００ｇを用いた以外は、上記実施例１と同様にして、水性インク用着色樹脂微粒子の分散液を得た。 (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.
上記実施例１において、（Ａ）成分としてコハク酸－２－メタクリロイルオキシエチル〔三菱レイヨン（株）製、アクリルエステルＳＡ、水への溶解度：１．８６質量％〕２００ｇを用いた以外は、上記実施例１と同様にして、水性インク用着色樹脂微粒子の分散液を得た。 (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.
（実施例７）
上記実施例６において、（Ｂ）成分としてアクリル酸ミリスチル１５０ｇを用いた以外は、上記実施例６と同様にして、水性インク用着色樹脂微粒子の分散液を得た。 (Example 7)
In Example 6, 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).
上記実施例６において、（Ｂ）成分としてアクリル酸ミリスチル１５０ｇを用いた以外は、上記実施例６と同様にして、水性インク用着色樹脂微粒子の分散液を得た。 (Example 7)
In Example 6, 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).
（実施例８）
上記実施例６において、（Ｂ）成分としてメタクリル酸シクロヘキシル１５０ｇを用いた以外は、上記実施例６と同様にして、水性インク用着色樹脂微粒子の分散液を得た。 (Example 8)
In 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).
上記実施例６において、（Ｂ）成分としてメタクリル酸シクロヘキシル１５０ｇを用いた以外は、上記実施例６と同様にして、水性インク用着色樹脂微粒子の分散液を得た。 (Example 8)
In 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).
（実施例９）
上記実施例２において、（Ａ）成分としてヘキサヒドロフタル酸－２－メタクリロイルオキシエチル〔三菱レイヨン（株）製、アクリルエステルＨＨ、水への溶解度：３．４０質量％〕２００ｇを用いた以外は、上記実施例２と同様にして、水性インク用着色樹脂微粒子の分散液を得た。 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.
上記実施例２において、（Ａ）成分としてヘキサヒドロフタル酸－２－メタクリロイルオキシエチル〔三菱レイヨン（株）製、アクリルエステルＨＨ、水への溶解度：３．４０質量％〕２００ｇを用いた以外は、上記実施例２と同様にして、水性インク用着色樹脂微粒子の分散液を得た。 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.
（実施例１０）
上記実施例９において、（Ｂ）成分としてメタクリル酸シクロヘキシル１５０ｇを用いた以外は、上記実施例９と同様にして、水性インク用着色樹脂微粒子の分散液を得た。 (Example 10)
In 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 cyclohexyl methacrylate was used as the component (B).
上記実施例９において、（Ｂ）成分としてメタクリル酸シクロヘキシル１５０ｇを用いた以外は、上記実施例９と同様にして、水性インク用着色樹脂微粒子の分散液を得た。 (Example 10)
In 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 cyclohexyl methacrylate was used as the component (B).
（実施例１１）
上記実施例３において、（Ａ）成分としてマレイン酸－２－メタクリロイルオキシエチル〔三菱レイヨン（株）製、アクリルエステルＭＬ、水への溶解度：９．１７質量％〕１５０ｇを用いた以外は、上記実施例３と同様にして、水性インク用着色樹脂微粒子の分散液を得た。 (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.
上記実施例３において、（Ａ）成分としてマレイン酸－２－メタクリロイルオキシエチル〔三菱レイヨン（株）製、アクリルエステルＭＬ、水への溶解度：９．１７質量％〕１５０ｇを用いた以外は、上記実施例３と同様にして、水性インク用着色樹脂微粒子の分散液を得た。 (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.
（実施例１２）
上記実施例１において、水溶性塩基性染料〔保土谷化学工業社製、「ＡＩＺＥＮ ＣＡＴＨＩＬＯＮ ＲＥＤ ＢＬＨ ２００％」〕４０ｇに代え、油溶性染料として、オリエント化学工業社製・ＶＡＬＩＦＡＳＴ ＢＬＡＣＫ ３８３０を用いて、上記実施例１と同様にして水性インク用着色樹脂微粒子の分散液を得た。 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.
上記実施例１において、水溶性塩基性染料〔保土谷化学工業社製、「ＡＩＺＥＮ ＣＡＴＨＩＬＯＮ ＲＥＤ ＢＬＨ ２００％」〕４０ｇに代え、油溶性染料として、オリエント化学工業社製・ＶＡＬＩＦＡＳＴ ＢＬＡＣＫ ３８３０を用いて、上記実施例１と同様にして水性インク用着色樹脂微粒子の分散液を得た。 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.
（実施例１３）
上記実施例１において、水溶性塩基性染料〔保土谷化学工業社製、「ＡＩＺＥＮ ＣＡＴＨＩＬＯＮ ＲＥＤ ＢＬＨ ２００％」〕４０ｇを添加せず、重合後に該水溶性塩基性染料を添加して、水性インク用着色樹脂微粒子の分散液を得た。 (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.
上記実施例１において、水溶性塩基性染料〔保土谷化学工業社製、「ＡＩＺＥＮ ＣＡＴＨＩＬＯＮ ＲＥＤ ＢＬＨ ２００％」〕４０ｇを添加せず、重合後に該水溶性塩基性染料を添加して、水性インク用着色樹脂微粒子の分散液を得た。 (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.
（実施例１４）
２リットルのフラスコに、撹拌機、還流冷却器、温度計、窒素ガス導入管、モノマー投入用１０００ｍｌ分液漏斗を取り付け、温水槽にセットし、蒸留水４２０ｇ、重合性界面活性剤〔アデカ社製、「アデカリアソープＳＥ－１０Ｎ」〕５０ｇおよび過硫酸アンモニウム３ｇを仕込んで、窒素ガスを導入しながら、内温を５０℃まで昇温した。 (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.
２リットルのフラスコに、撹拌機、還流冷却器、温度計、窒素ガス導入管、モノマー投入用１０００ｍｌ分液漏斗を取り付け、温水槽にセットし、蒸留水４２０ｇ、重合性界面活性剤〔アデカ社製、「アデカリアソープＳＥ－１０Ｎ」〕５０ｇおよび過硫酸アンモニウム３ｇを仕込んで、窒素ガスを導入しながら、内温を５０℃まで昇温した。 (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.
一方、（Ａ）成分としてフタル酸－２－メタクリロイルオキシエチル〔三菱レイヨン（株）製、アクリルエステルＰＡ、水への溶解度：０．０８質量％）３００ｇ、（Ｂ）成分として、メタクリル酸ｎ－ブチル２００ｇ、（Ｃ）成分として、ジシクロペンタニルメタクリレート８０ｇからなる混合モノマー５８０ｇに、水溶性塩基性染料〔保土谷化学工業（株）製、「ＡＩＺＥＮ ＣＡＴＨＩＬＯＮ ＲＥＤ ＢＬＨ ２００％」〕４０ｇを混合した液を調製した。
この調製液を上記分液漏斗から温度５０℃付近に保った上記フラスコ内に撹拌下で３時間にわたって添加し、乳化重合を行った。さらに５時間熟成して重合を終了し、水性インク用着色微粒子の分散液を得た。 On the other hand, phthalic acid-2-methacryloyloxyethyl phthalate (manufactured by Mitsubishi Rayon Co., Ltd., acrylic ester PA, solubility in water: 0.08% by mass) as component (A), 300 g of phthalate, n-methacrylic acid as component (B) As a 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.
この調製液を上記分液漏斗から温度５０℃付近に保った上記フラスコ内に撹拌下で３時間にわたって添加し、乳化重合を行った。さらに５時間熟成して重合を終了し、水性インク用着色微粒子の分散液を得た。 On the other hand, phthalic acid-2-methacryloyloxyethyl phthalate (manufactured by Mitsubishi Rayon Co., Ltd., acrylic ester PA, solubility in water: 0.08% by mass) as component (A), 300 g of phthalate, n-methacrylic acid as component (B) As a 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.
（実施例１５）
上記実施例１４において、水溶性塩基性染料〔保土谷化学工業（株）製、「ＡＩＺＥＮ ＣＡＴＨＩＬＯＮ ＲＥＤ ＢＬＨ ２００％」〕４０ｇに代え、油溶性染料として、オリエント化学工業（株）製ＶＡＬＩＦＡＳＴ ＢＬＡＣＫ ３８３０を用いて、上記実施例１４と同様にして水性インク用着色微粒子の分散液を得た。 (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.
上記実施例１４において、水溶性塩基性染料〔保土谷化学工業（株）製、「ＡＩＺＥＮ ＣＡＴＨＩＬＯＮ ＲＥＤ ＢＬＨ ２００％」〕４０ｇに代え、油溶性染料として、オリエント化学工業（株）製ＶＡＬＩＦＡＳＴ ＢＬＡＣＫ ３８３０を用いて、上記実施例１４と同様にして水性インク用着色微粒子の分散液を得た。 (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.
（実施例１６）
上記実施例１４において、ジシクロペンタニルメタクリレートに代え、ジシクロペンタニルアクリレートを用いて、上記実施例１４と同様にして水性インク用着色微粒子の分散液を得た。 (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.
上記実施例１４において、ジシクロペンタニルメタクリレートに代え、ジシクロペンタニルアクリレートを用いて、上記実施例１４と同様にして水性インク用着色微粒子の分散液を得た。 (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.
（実施例１７）
上記実施例１６において、水溶性塩基性染料〔保土谷化学工業（株）製、「ＡＩＺＥＮ ＣＡＴＨＩＬＯＮ ＲＥＤ ＢＬＨ ２００％」〕４０ｇに代え、油溶性染料として、オリエント化学工業（株）製ＶＡＬＩＦＡＳＴ ＢＬＡＣＫ ３８３０を用いて、上記実施例１４と同様にして水性インク用着色微粒子の分散液を得た。 (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.
上記実施例１６において、水溶性塩基性染料〔保土谷化学工業（株）製、「ＡＩＺＥＮ ＣＡＴＨＩＬＯＮ ＲＥＤ ＢＬＨ ２００％」〕４０ｇに代え、油溶性染料として、オリエント化学工業（株）製ＶＡＬＩＦＡＳＴ ＢＬＡＣＫ ３８３０を用いて、上記実施例１４と同様にして水性インク用着色微粒子の分散液を得た。 (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.
（比較例１）
上記実施例１において、（Ｂ）成分としてメタクリル酸メチル１５０ｇを用いた以外は、上記実施例１と同様にして、水性インク用着色樹脂微粒子の分散液を得た。 (Comparative 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.
上記実施例１において、（Ｂ）成分としてメタクリル酸メチル１５０ｇを用いた以外は、上記実施例１と同様にして、水性インク用着色樹脂微粒子の分散液を得た。 (Comparative 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.
（比較例２）
上記実施例６において、（Ｂ）成分としてメタクリル酸メチル１５０ｇを用いた以外は、上記実施例６と同様にして、水性インク用着色樹脂微粒子の分散液を得た。 (Comparative 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).
上記実施例６において、（Ｂ）成分としてメタクリル酸メチル１５０ｇを用いた以外は、上記実施例６と同様にして、水性インク用着色樹脂微粒子の分散液を得た。 (Comparative 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).
（比較例３）
上記実施例９において、（Ｂ）成分としてメタクリル酸メチル１５０ｇを用いた以外は、上記実施例９と同様にして、水性インク用着色樹脂微粒子の分散液を得た。 (Comparative Example 3)
In 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).
上記実施例９において、（Ｂ）成分としてメタクリル酸メチル１５０ｇを用いた以外は、上記実施例９と同様にして、水性インク用着色樹脂微粒子の分散液を得た。 (Comparative Example 3)
In 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).
（比較例４）
上記実施例１１において、（Ｂ）成分としてメタクリル酸メチル１５０ｇを用いた以外は、上記実施例１１と同様にして、水性インク用着色樹脂微粒子の分散液を得た。 (Comparative Example 4)
In Example 11, 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).
上記実施例１１において、（Ｂ）成分としてメタクリル酸メチル１５０ｇを用いた以外は、上記実施例１１と同様にして、水性インク用着色樹脂微粒子の分散液を得た。 (Comparative Example 4)
In Example 11, 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).
（筆記具用水性インク組成物の調製）
上記実施例１～１７及び比較例１～４で得られた各水性インク用着色樹脂微粒子の分散液を用いて下記に示す配合処方にしたがって、常法により各筆記具用水性インク組成物を調製した。
各水性インク用着色樹脂微粒子の分散液は、平均粒子径は０．０５～０．３０μｍの範囲であり、樹脂固形分も１０～５０質量％の範囲内であった。
（配合組成）
各水性インク用着色樹脂微粒子の分散液 ５０質量％
ｐＨ調整剤（トリエタノールアミン） １質量％
水溶性有機溶剤（エチレングリコール） ５質量％
イオン交換水 ４４質量％ (Preparation of water-based ink composition for writing instruments)
Using the dispersions of colored resin fine particles for each water-based ink obtained in Examples 1 to 17 and Comparative Examples 1 to 4 described above, water-based ink compositions for writing instruments were prepared by a conventional method according to the formulation shown below. .
The dispersion of the colored resin fine particles for each water-based ink had an average particle size in the range of 0.05 to 0.30 μm and a resin solid content in the range of 10 to 50% by mass.
(Composition composition)
Dispersion of colored resin fine particles for each water-based ink 50% by mass
pH adjuster (triethanolamine) 1% by mass
Water-soluble organic solvent (ethylene glycol) 5% by mass
Ion-exchanged water 44% by mass
上記実施例１～１７及び比較例１～４で得られた各水性インク用着色樹脂微粒子の分散液を用いて下記に示す配合処方にしたがって、常法により各筆記具用水性インク組成物を調製した。
各水性インク用着色樹脂微粒子の分散液は、平均粒子径は０．０５～０．３０μｍの範囲であり、樹脂固形分も１０～５０質量％の範囲内であった。
（配合組成）
各水性インク用着色樹脂微粒子の分散液 ５０質量％
ｐＨ調整剤（トリエタノールアミン） １質量％
水溶性有機溶剤（エチレングリコール） ５質量％
イオン交換水 ４４質量％ (Preparation of water-based ink composition for writing instruments)
Using the dispersions of colored resin fine particles for each water-based ink obtained in Examples 1 to 17 and Comparative Examples 1 to 4 described above, water-based ink compositions for writing instruments were prepared by a conventional method according to the formulation shown below. .
The dispersion of the colored resin fine particles for each water-based ink had an average particle size in the range of 0.05 to 0.30 μm and a resin solid content in the range of 10 to 50% by mass.
(Composition composition)
Dispersion of colored resin fine particles for each water-based ink 50% by mass
pH adjuster (triethanolamine) 1% by mass
Water-soluble organic solvent (ethylene glycol) 5% by mass
Ion-exchanged water 44% by mass
得られた各筆記具用水性インク組成物（全量１００質量％）について、下記方法により筆記具としてマーキングペンを作製し、下記各評価方法により、安定性、描線乾燥性（筆記用紙、教科書）、水分揮発時における安定性について評価した。
下記表１に実施例１～１７及び比較例１～４の各評価結果を示す。 About each obtained water-based ink composition for writing implements (100 mass% of total quantity), a marking pen is produced as a writing implement by the following method, and stability, drawing dryness (writing paper, textbook), moisture volatilization is carried out by each of the following evaluation methods. Time stability was evaluated.
Table 1 below shows the evaluation results of Examples 1 to 17 and Comparative Examples 1 to 4.
下記表１に実施例１～１７及び比較例１～４の各評価結果を示す。 About each obtained water-based ink composition for writing implements (100 mass% of total quantity), a marking pen is produced as a writing implement by the following method, and stability, drawing dryness (writing paper, textbook), moisture volatilization is carried out by each of the following evaluation methods. Time stability was evaluated.
Table 1 below shows the evaluation results of Examples 1 to 17 and Comparative Examples 1 to 4.
（筆記具：マーキングペンの作製）
マーキングペン〔三菱鉛筆株式会社製、商品名：プロパス・ウインド ＰＵＳ－１０２Ｔ、ペン先、太：ＰＥ樹脂、細：ＰＥＴ繊維〕に上記実施例１～１７及び比較例１～４で製造した各インク組成物を装填してマーキングペンを作製した。 (Writing instrument: Production of marking pen)
Each ink produced in Examples 1 to 17 and Comparative Examples 1 to 4 on a marking pen (Mitsubishi Pencil Co., Ltd., trade name: Propass Wind PUS-102T, nib, thick: PE resin, fine: PET fiber) A marking pen was made by loading the composition.
マーキングペン〔三菱鉛筆株式会社製、商品名：プロパス・ウインド ＰＵＳ－１０２Ｔ、ペン先、太：ＰＥ樹脂、細：ＰＥＴ繊維〕に上記実施例１～１７及び比較例１～４で製造した各インク組成物を装填してマーキングペンを作製した。 (Writing instrument: Production of marking pen)
Each ink produced in Examples 1 to 17 and Comparative Examples 1 to 4 on a marking pen (Mitsubishi Pencil Co., Ltd., trade name: Propass Wind PUS-102T, nib, thick: PE resin, fine: PET fiber) A marking pen was made by loading the composition.
（安定性の評価方法）
上記で得た実施例１～１７及び比較例１～４で調製した各インク組成物をガラス製バイアル瓶に充填し蓋を閉め、５０℃の環境下に保存し、一定期間後に、バイアル瓶内のインクに凝集や沈降が見られない期間を「安定性が維持されている期間」とし、下記評価基準で評価した。
評価基準：
◎：３ヶ月以上
○：１ヶ月以上３ヶ月未満
△：２週間以上１ヶ月未満
×：２週間未満 (Stability evaluation method)
The ink compositions prepared in Examples 1 to 17 and Comparative Examples 1 to 4 obtained above were filled in glass vials, the lids were closed, and stored in an environment of 50 ° C. The period during which no ink was aggregated or settled was defined as the “period during which the stability was maintained” and was evaluated according to the following evaluation criteria.
Evaluation criteria:
◎: 3 months or more ○: 1 month or more and less than 3 months △: 2 weeks or more and less than 1 month ×: Less than 2 weeks
上記で得た実施例１～１７及び比較例１～４で調製した各インク組成物をガラス製バイアル瓶に充填し蓋を閉め、５０℃の環境下に保存し、一定期間後に、バイアル瓶内のインクに凝集や沈降が見られない期間を「安定性が維持されている期間」とし、下記評価基準で評価した。
評価基準：
◎：３ヶ月以上
○：１ヶ月以上３ヶ月未満
△：２週間以上１ヶ月未満
×：２週間未満 (Stability evaluation method)
The ink compositions prepared in Examples 1 to 17 and Comparative Examples 1 to 4 obtained above were filled in glass vials, the lids were closed, and stored in an environment of 50 ° C. The period during which no ink was aggregated or settled was defined as the “period during which the stability was maintained” and was evaluated according to the following evaluation criteria.
Evaluation criteria:
◎: 3 months or more ○: 1 month or more and less than 3 months △: 2 weeks or more and less than 1 month ×: Less than 2 weeks
（描線乾燥性の評価方法）
上記で得た実施例１～１７及び比較例１～４で製造した各インク組成物を装填してマーキングペンを用いて、筆記用紙及び教科書の無地部（諸説日本史・山川出版・２０１３年発行版、以下同様）に手書きで長さ約２５ｃｍの線を描いた。一定時間ごとに筆記線直角方向に指サック（コクヨ株式会社製、事務用指サック・メク－２）を装着した指で軽く擦り、筆記線が擦りとられたり延びたりしなくなった最短の時間を「筆記線の乾燥時間」とし、下記評価基準で評価した。
評価基準：
◎： ３秒以内
○： ５秒以内
△：１０秒以内
×：２０秒未満
××：２０秒以上 (Drawing line dryness evaluation method)
Using the marking pens loaded with the ink compositions prepared in Examples 1 to 17 and Comparative Examples 1 to 4 obtained above, writing paper and plain textbooks (Japanese history, Yamakawa Publishing, published in 2013) A line with a length of about 25 cm was drawn by hand on the plate (the same applies hereinafter). Lightly rub with a finger wearing a finger sack (manufactured by KOKUYO Corporation, office finger sack Mek-2) in the direction perpendicular to the writing line at regular intervals, and the shortest time when the writing line is not rubbed or extended It was set as "writing line drying time" and evaluated according to the following evaluation criteria.
Evaluation criteria:
◎: Within 3 seconds ○: Within 5 seconds △: Within 10 seconds X: Less than 20 seconds XX: 20 seconds or more
上記で得た実施例１～１７及び比較例１～４で製造した各インク組成物を装填してマーキングペンを用いて、筆記用紙及び教科書の無地部（諸説日本史・山川出版・２０１３年発行版、以下同様）に手書きで長さ約２５ｃｍの線を描いた。一定時間ごとに筆記線直角方向に指サック（コクヨ株式会社製、事務用指サック・メク－２）を装着した指で軽く擦り、筆記線が擦りとられたり延びたりしなくなった最短の時間を「筆記線の乾燥時間」とし、下記評価基準で評価した。
評価基準：
◎： ３秒以内
○： ５秒以内
△：１０秒以内
×：２０秒未満
××：２０秒以上 (Drawing line dryness evaluation method)
Using the marking pens loaded with the ink compositions prepared in Examples 1 to 17 and Comparative Examples 1 to 4 obtained above, writing paper and plain textbooks (Japanese history, Yamakawa Publishing, published in 2013) A line with a length of about 25 cm was drawn by hand on the plate (the same applies hereinafter). Lightly rub with a finger wearing a finger sack (manufactured by KOKUYO Corporation, office finger sack Mek-2) in the direction perpendicular to the writing line at regular intervals, and the shortest time when the writing line is not rubbed or extended It was set as "writing line drying time" and evaluated according to the following evaluation criteria.
Evaluation criteria:
◎: Within 3 seconds ○: Within 5 seconds △: Within 10 seconds X: Less than 20 seconds XX: 20 seconds or more
（水分揮発時における安定性の評価方法）
上記で得た実施例１～１７及び比較例１～４で調製した各分散液をガラス製シャーレに充填し、元の重量の３０％となるまで水分を揮発させ、揮発前後の分散液（２５℃）の剪断速度１９１．５ｓｅｃ－１における粘度をViscometer TV-25（東機産業社製）で測定した。 (Evaluation method for stability when moisture evaporates)
Each dispersion prepared in Examples 1 to 17 and Comparative Examples 1 to 4 obtained above was filled in a glass petri dish, and water was volatilized to 30% of the original weight. The viscosity at 19 ° C.- 1 was measured with a Viscometer TV-25 (manufactured by Toki Sangyo Co., Ltd.).
上記で得た実施例１～１７及び比較例１～４で調製した各分散液をガラス製シャーレに充填し、元の重量の３０％となるまで水分を揮発させ、揮発前後の分散液（２５℃）の剪断速度１９１．５ｓｅｃ－１における粘度をViscometer TV-25（東機産業社製）で測定した。 (Evaluation method for stability when moisture evaporates)
Each dispersion prepared in Examples 1 to 17 and Comparative Examples 1 to 4 obtained above was filled in a glass petri dish, and water was volatilized to 30% of the original weight. The viscosity at 19 ° C.- 1 was measured with a Viscometer TV-25 (manufactured by Toki Sangyo Co., Ltd.).
上記表１を考察すると、本発明範囲となる実施例１～１３は、発色性、耐候性、安定性などの色材としての機能に加えて、描線乾燥性を向上させる性質を有する水性インク用着色樹脂微粒子の分散液、並びに、筆記具に好適な筆記具用水性インク組成物となることが判った。更に、実施例１４～１７では、上記実施例１～１３の効果と共に、水分が揮発したとしても安定性が損なわれにくい水性インク用着色樹脂微粒子の分散液、並びに、筆記具に好適な筆記具用水性インク組成物となることが判った。
これに対して、本発明の範囲外となる比較例１～４では、本発明の効果を発揮できないことが判る。 Considering Table 1 above, 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 | water-based ink composition for writing tools suitable for the dispersion liquid of colored resin fine particles, and a writing instrument. Further, in Examples 14 to 17, in addition to the effects of Examples 1 to 13 above, a dispersion of colored resin fine particles for water-based inks that is less likely to lose stability even when water is volatilized, and an aqueous writing instrument suitable for a writing instrument. It was found to be an ink composition.
On the other hand, it can be seen that Comparative Examples 1 to 4 outside the scope of the present invention cannot exhibit the effects of the present invention.
これに対して、本発明の範囲外となる比較例１～４では、本発明の効果を発揮できないことが判る。 Considering Table 1 above, 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 | water-based ink composition for writing tools suitable for the dispersion liquid of colored resin fine particles, and a writing instrument. Further, in Examples 14 to 17, in addition to the effects of Examples 1 to 13 above, a dispersion of colored resin fine particles for water-based inks that is less likely to lose stability even when water is volatilized, and an aqueous writing instrument suitable for a writing instrument. It was found to be an ink composition.
On the other hand, it can be seen that Comparative Examples 1 to 4 outside the scope of the present invention cannot exhibit the effects of the present invention.
サインペンやマーキングペン、ボールペンなどの筆記具などに好適な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が得られる。
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.
Claims (6)
- 少なくとも、酸性官能基として水への溶解度が１０質量％以下のカルボキシル基含有ビニルモノマー（Ａ）と、アクリル酸又はメタクリル酸と炭素数２～１８の直鎖若しくは環状アルコールとのエステルモノマー（Ｂ）と、塩基性染料又は油溶性染料とで構成される着色樹脂微粒子が水に分散されていることを特徴とする水性インク用着色樹脂微粒子の分散液。 At least an ester monomer (B) 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. And a dispersion of colored resin fine particles for water-based inks, wherein the colored resin fine particles composed of a basic dye or an oil-soluble dye are dispersed in water.
- 前記水性インク用着色樹脂微粒子を構成するポリマー成分のうち、前記カルボキシル基含有ビニルモノマー（Ａ）と、前記エステルモノマー（Ｂ）の合計含有量が６０質量％以上であることを特徴とする請求項１記載の水性インク用着色樹脂微粒子の分散液。 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. 1. A dispersion of colored resin fine particles for aqueous ink according to 1.
- 前記カルボキシル基含有ビニルモノマー（Ａ）の含有量が、４０質量％以上であり、前記エステルモノマー（Ｂ）の含有量が、２０質量％以上であることを特徴とする請求項２記載の水性インク用着色樹脂微粒子の分散液。 The aqueous ink according to claim 2, wherein 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. Dispersion of colored resin fine particles.
- 更に、ジシクロペンタ（テ）ニル（メタ）アクリレートモノマー（Ｃ）を有することを特徴とする請求項１～３の何れか１項記載の水性インク用着色樹脂微粒子の分散液。 The dispersion of colored resin fine particles for aqueous ink according to any one of claims 1 to 3, further comprising dicyclopenta (te) nyl (meth) acrylate monomer (C).
- 前記水性インク用着色樹脂微粒子を構成するポリマー成分のうち、前記ジシクロペンタ（テ）ニル（メタ）アクリレートモノマー（Ｃ）の含有量が１～２５質量％であることを特徴とする請求項４記載の水性インク用着色樹脂微粒子の分散液。 The content of the dicyclopenta (te) nyl (meth) acrylate monomer (C) in the polymer component constituting the colored resin fine particles for water-based ink is 1 to 25% by mass. Dispersion of colored resin fine particles for aqueous ink.
- 請求項１～５の何れか１項記載の水性インク用着色樹脂微粒子の分散液と、水溶性有機溶媒と、水とを含有することを特徴とする筆記具用水性インク組成物。 6. A water-based ink composition for a writing instrument comprising a dispersion of colored resin fine particles for water-based ink according to any one of claims 1 to 5, a water-soluble organic solvent, and water.
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| 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 (en) | 2015-04-06 | 2016-03-31 | The water-based ink composition of the writing implement of its preparation of the fine grain dispersion liquid of aqueous ink pigmentary resin and use |
| EP16776458.8A EP3281992B1 (en) | 2015-04-06 | 2016-03-31 | Dispersion liquid of colored resin fine particles for aqueous inks, and aqueous ink composition for writing utensils using same |
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| JP2015077779 | 2015-04-06 | ||
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| JP2015-155221 | 2015-08-05 | ||
| JP2015155221A JP6563731B2 (en) | 2015-04-06 | 2015-08-05 | Water-based ink composition for writing instruments |
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| EP3933001A4 (en) * | 2019-02-28 | 2022-04-20 | FUJIFILM Corporation | COLORED RESIN PARTICLE DISPERSION, INK, INK SET AND INKJET PRINTING PROCESS |
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