JP4758622B2 - Method for producing aqueous pigment dispersion composition, aqueous pigment dispersion composition obtained by the production method and use thereof - Google Patents
Method for producing aqueous pigment dispersion composition, aqueous pigment dispersion composition obtained by the production method and use thereof Download PDFInfo
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- JP4758622B2 JP4758622B2 JP2004216283A JP2004216283A JP4758622B2 JP 4758622 B2 JP4758622 B2 JP 4758622B2 JP 2004216283 A JP2004216283 A JP 2004216283A JP 2004216283 A JP2004216283 A JP 2004216283A JP 4758622 B2 JP4758622 B2 JP 4758622B2
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- Prior art keywords
- pigment
- dispersion
- aqueous
- pigment dispersion
- dispersion composition
- Prior art date
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- 239000006185 dispersion Substances 0.000 title claims description 155
- 239000000049 pigment Substances 0.000 title claims description 153
- 239000000203 mixture Substances 0.000 title claims description 114
- 238000004519 manufacturing process Methods 0.000 title claims description 34
- 239000012860 organic pigment Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 27
- 229920005989 resin Polymers 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 19
- 239000012736 aqueous medium Substances 0.000 claims description 17
- 239000002270 dispersing agent Substances 0.000 claims description 14
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 12
- 239000011164 primary particle Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 7
- 230000002093 peripheral effect Effects 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- -1 fatty acid salts Chemical class 0.000 description 39
- 238000003756 stirring Methods 0.000 description 18
- 239000011324 bead Substances 0.000 description 17
- 150000002736 metal compounds Chemical class 0.000 description 16
- 239000002245 particle Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 239000011362 coarse particle Substances 0.000 description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 238000010008 shearing Methods 0.000 description 13
- 238000004040 coloring Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 10
- 239000000976 ink Substances 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 9
- 239000000194 fatty acid Substances 0.000 description 9
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 235000013372 meat Nutrition 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
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- 238000002156 mixing Methods 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 150000007514 bases Chemical class 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 239000002609 medium Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- DTCCVIYSGXONHU-CJHDCQNGSA-N (z)-2-(2-phenylethenyl)but-2-enedioic acid Chemical compound OC(=O)\C=C(C(O)=O)\C=CC1=CC=CC=C1 DTCCVIYSGXONHU-CJHDCQNGSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- 229910001111 Fine metal Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000010130 dispersion processing Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- IIPCXIGUIPAGQB-OUKQBFOZSA-N (e)-4-dodecoxy-4-oxobut-2-enoic acid Chemical compound CCCCCCCCCCCCOC(=O)\C=C\C(O)=O IIPCXIGUIPAGQB-OUKQBFOZSA-N 0.000 description 1
- IQBLWPLYPNOTJC-FPLPWBNLSA-N (z)-4-(2-ethylhexoxy)-4-oxobut-2-enoic acid Chemical compound CCCCC(CC)COC(=O)\C=C/C(O)=O IQBLWPLYPNOTJC-FPLPWBNLSA-N 0.000 description 1
- RNERBJNDXXEXTK-SREVYHEPSA-N (z)-4-hexoxy-4-oxobut-2-enoic acid Chemical compound CCCCCCOC(=O)\C=C/C(O)=O RNERBJNDXXEXTK-SREVYHEPSA-N 0.000 description 1
- AYAUWVRAUCDBFR-ARJAWSKDSA-N (z)-4-oxo-4-propoxybut-2-enoic acid Chemical compound CCCOC(=O)\C=C/C(O)=O AYAUWVRAUCDBFR-ARJAWSKDSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- IWSZDQRGNFLMJS-UHFFFAOYSA-N 2-(dibutylamino)ethanol Chemical compound CCCCN(CCO)CCCC IWSZDQRGNFLMJS-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- HXDLWJWIAHWIKI-UHFFFAOYSA-N 2-hydroxyethyl acetate Chemical compound CC(=O)OCCO HXDLWJWIAHWIKI-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- PPPFYBPQAPISCT-UHFFFAOYSA-N 2-hydroxypropyl acetate Chemical compound CC(O)COC(C)=O PPPFYBPQAPISCT-UHFFFAOYSA-N 0.000 description 1
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- 229920000178 Acrylic resin Polymers 0.000 description 1
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- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
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- MYONAGGJKCJOBT-UHFFFAOYSA-N benzimidazol-2-one Chemical compound C1=CC=CC2=NC(=O)N=C21 MYONAGGJKCJOBT-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
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- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-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
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
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- OBJNZHVOCNPSCS-UHFFFAOYSA-N naphtho[2,3-f]quinazoline Chemical compound C1=NC=C2C3=CC4=CC=CC=C4C=C3C=CC2=N1 OBJNZHVOCNPSCS-UHFFFAOYSA-N 0.000 description 1
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- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 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
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- 229920000728 polyester Polymers 0.000 description 1
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 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
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 229920005792 styrene-acrylic resin Polymers 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、水性顔料分散組成物の製造方法に関し、特に、水性印刷インキなどの分野に有用である流動性が極めて高い水性顔料分散組成物を製造する方法に関する。 The present invention relates to a method for producing an aqueous pigment dispersion composition, and more particularly to a method for producing an aqueous pigment dispersion composition having extremely high fluidity that is useful in the field of aqueous printing inks and the like.
水性有機顔料分散組成物は、古くから、水性印刷インキなどの着色材料のベース組成物として利用されており、鮮明な発色性と高い着色力を有すること、さらに流動性が良好であることが基本性能とされてきた。そして、この様な水性有機顔料分散組成物の製造方法として、通常、水性媒体中へ有機顔料と分散剤とを添加し、プロペラタイプ、パドルタイプ、タービンタイプなどのロータを有する装置を用いて、プレミックスと称される攪拌混合処理を行った後、パールミル、ダイノミルなどのメディア型分散装置を用いて、有機顔料をより微細に分散させる練肉処理を行う方法が利用されている（例えば、特許文献１）。 Aqueous organic pigment dispersion compositions have long been used as a base composition for coloring materials such as aqueous printing inks. Basically, they have a clear color developability and high coloring power, and also have good fluidity. It has been considered performance. And, as a method for producing such an aqueous organic pigment dispersion composition, usually, an organic pigment and a dispersant are added to an aqueous medium, and a propeller type, paddle type, turbine type, or other apparatus having a rotor is used. After performing a stirring and mixing process called a premix, a method of performing a meat paste process in which an organic pigment is more finely dispersed using a media type dispersing device such as a pearl mill or a dyno mill is used (for example, patents). Reference 1).
また、顔料分散組成物の基本性能としての発色性や流動性を良好にするためには、まず、顔料の粗大粒子を少なくすことが不可欠であることが知られている。さらに、その顔料分散に利用するメディア型分散装置では、球体であるメディア同士が点で接触することから、接触点の近傍では高い応力がかかり、遠くなるにつれて応力が低くなるという機械的な特性があることも知られている。従って、これまでは分散効率を考慮して、接触点から離れた部分でも、顔料を微細に分散するのに十分な応力がかかるように分散条件が設定されてきた。この様な顔料の分散処理は、利用する顔料が難分散性であっても、効率よく水性媒体中に分散することができる代表的な方法である。 Further, it is known that it is indispensable to first reduce the coarse particles of the pigment in order to improve the color development and fluidity as the basic performance of the pigment dispersion composition. Furthermore, in the media type dispersion device used for the pigment dispersion, since the spherical media are in contact with each other at a point, there is a mechanical characteristic that a high stress is applied in the vicinity of the contact point and the stress is reduced as the distance increases. It is also known that there is. Therefore, in the past, in consideration of dispersion efficiency, dispersion conditions have been set so that sufficient stress is applied to finely disperse the pigment even at a portion away from the contact point. Such a pigment dispersion treatment is a typical method that enables efficient dispersion in an aqueous medium even if the pigment used is difficult to disperse.
一方、印刷インキに求められる性能レベルは年々高くなり、最近では顔料の粗大粒子を少なくするばかりでなく、平均粒子径もだんだんと小さくする、微粒子化の方向に移行している。しかし、疎水性の表面を有する有機顔料は、微粒子化すればするほど水性媒体中で安定な分散状態を維持することが困難となり、凝集を起こして流動性や発色性の低下の原因となる。そこで、従来より、印刷インキの分野では、有機顔料と比較して分散剤との濡れ性が良好な体質顔料を併用することにより、流動性の低下を防止する技術などで対応が図られて来た。さらに良好な流動性と発色性が要求されるインクジェット記録液の分野などでは、有機顔料のソルトミリングの際に微粒子の硫酸バリウムなどを混合することにより、有機顔料をより微細に分散させても分散安定性が良好であり、長期にわたって吐出安定性や鮮明性に優れたインクジェット記録液が得られることも知られている（例えば、特許文献２）。しかしながら、これらの技術は、流動性を低下させる根本的な原因を取り除くわけではなく、低下のレベルを軽減するものであるにすぎない。 On the other hand, the level of performance required for printing ink is increasing year by year, and recently, not only the coarse particles of the pigment are reduced, but also the average particle size is gradually becoming smaller, and the trend is toward finer particles. However, an organic pigment having a hydrophobic surface becomes more difficult to maintain a stable dispersion state in an aqueous medium as the particle size is reduced, and causes aggregation and a decrease in fluidity and color developability. Therefore, conventionally, in the field of printing inks, measures have been taken with technologies that prevent deterioration of fluidity by using together with extender pigments that have better wettability with dispersants than organic pigments. It was. In the field of ink jet recording liquids that require better fluidity and color development, it is possible to disperse organic pigments even more finely by mixing fine particles such as barium sulfate during salt milling of organic pigments. It is also known that an inkjet recording liquid having good stability and excellent ejection stability and sharpness over a long period of time can be obtained (for example, Patent Document 2). However, these techniques do not remove the root cause of fluidity reduction, but only reduce the level of degradation.
ところで、メディア型分散装置を利用して顔料を微粒子化するためには、当然、分散処理時に、より大きな力を顔料に与えることが必要となる。それに対して、従来のように分散効率を優先した分散条件（メディアの接触点から離れた部分でも十分な応力がかかる条件）を設定すると、今度は接触点近傍の部分で応力がかかり過ぎて、顔料が過剰に分散した状態となって凝集し、初期および保存期間中に沈降や流動性の低下が起こるという問題が発生する。将来にわたって、インキに要求される性能レベルがますます高くなることを考えると、顔料のさらなる微粒子化は不可欠であるが、それに伴って、より過剰に分散した顔料が増加することになる。そして、この様な顔料の過剰分散が生じる条件では、先に記載したような体質顔料や微粒子を含有するソルトミリング顔料の利用だけで、流動性の低下などを解決することは到底不可能であり、流動性低下の根本的な原因を取り除くことが必要である。 By the way, in order to make a pigment into fine particles by using a media type dispersing device, naturally, it is necessary to apply a greater force to the pigment during the dispersion treatment. On the other hand, if you set the dispersion condition that gives priority to the dispersion efficiency (conditions where sufficient stress is applied to the part away from the contact point of the media) as before, too much stress is applied in the part near the contact point, There is a problem that the pigment is aggregated in an excessively dispersed state, and sedimentation and fluidity decrease occur at the initial stage and during the storage period. Given the ever-increasing performance levels required for inks, further micronization of pigments is essential, but with this, more overdispersed pigments will increase. Under such conditions that excessive dispersion of the pigment occurs, it is impossible to solve the decrease in fluidity only by using the extender pigment or the salt milling pigment containing fine particles as described above. It is necessary to remove the root cause of fluidity drop.
そこで、顔料が過剰分散状態とならないように、メディアの接触点近傍の部分で適正な応力がかかる条件を設定すると、分散効率が極めて低くなり、水性有機顔料分散組成物の製造に必要な時間やエネルギーが大幅に増加することになる。 Therefore, setting the conditions under which an appropriate stress is applied in the vicinity of the contact point of the media so that the pigment is not excessively dispersed, the dispersion efficiency becomes extremely low, and the time required for the production of the aqueous organic pigment dispersion composition Energy will increase significantly.
この様に、従来から効率よく大量に水性有機顔料分散組成物を製造する方法として知られているメディア型分散装置では、機械的な特性から、より高い分散条件が必要となった時に、顔料の分散効率を低下させずに、過剰に分散した状態を回避することは極めて困難であり、根本的な有機顔料の分散方法の見直しが迫られている。 As described above, in the media type dispersion apparatus conventionally known as a method for producing an aqueous organic pigment dispersion composition efficiently and in large quantities, due to mechanical properties, when higher dispersion conditions are required, It is extremely difficult to avoid an excessively dispersed state without lowering the dispersion efficiency, and a fundamental review of the organic pigment dispersion method is being urged.
本発明の解決しようとする課題は、上述した問題を解決し、効率よく、着色力、流動性などが優れた水性顔料分散組成物を製造する方法を提供することにある。 The problem to be solved by the present invention is to provide a method for producing an aqueous pigment dispersion composition that solves the above-mentioned problems and that is excellent in coloring power and fluidity.
本発明者らは、上記課題を解決するために鋭意研究を重ねた結果、有機顔料、分散剤、水性媒体を含有する混合液に、さらに微細金属化合物を加えた混合液を、高速回転するロータと静止状態のステータなどとの間隙を通過させ混合物に高いせん断応力が付加できる高速せん断攪拌装置で分散処理した後、さらにメディア型分散装置で分散処理する工程からなる分散処理を行うことにより、問題を解決できることを見出し、本発明を完成するに到ったものである。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a mixed liquid obtained by adding a fine metal compound to a mixed liquid containing an organic pigment, a dispersant, and an aqueous medium is rotated at high speed. The problem is that the dispersion process consists of a dispersion process using a high-speed shearing stirrer that can pass a gap between the stator and a stationary stator, etc., and can apply high shear stress to the mixture, and then a dispersion process using a media-type dispersion unit. It has been found that the above can be solved, and the present invention has been completed.
すなわち、本発明はつぎの水性顔料分散組成物の製造方法、水性顔料分散組成物およびその用途を提供する。
（１）水性媒体と有機顔料と分散剤とを含む混合物を分散処理することにより、水性媒体中に有機顔料を分散させる水性顔料分散組成物の製造方法において、前記混合物は、さらに有機顔料１００質量部に対して、平均一次粒子径０．０５〜１μｍの硫酸バリウムを２〜２０質量部の割合で含み、粘度が０．２〜１０Ｐａ・ｓの混合液であり、前記分散処理は、少なくとも一組のロータとステータとの間隙を高速で通過させ、混合物に高いせん断応力が付加できる高速せん断攪拌装置として用いて分散処理した後、さらにメディア型分散装置で分散処理する工程からなり、
硫酸バリウムが、高速せん断攪拌装置として用いて分散処理する際には予め配合されており、
前記分散処理において、(前記高速せん断攪拌装置のロータの外径)／（前記混合物を収納する容器内径の径）の比が０．１以上、０．４以下であり、前記高速せん断攪拌装置のロータを、周速１５〜２５ｍ／ｓｅｃで回転させる
ことを特徴とする水性顔料分散組成物の製造方法。
（２）前記分散剤が、界面活性剤、水性樹脂および顔料誘導体よりなる群から選ばれる少なくとも１種である前記（１）項記載の水性顔料分散組成物の製造方法。
That is, this invention provides the manufacturing method of the following aqueous pigment dispersion composition, an aqueous pigment dispersion composition, and its use.
(1) In the method for producing an aqueous pigment dispersion composition in which the organic pigment is dispersed in the aqueous medium by dispersing the mixture containing the aqueous medium, the organic pigment, and the dispersant, the mixture further includes 100 masses of the organic pigment. Part of barium sulfate having an average primary particle size of 0.05 to 1 μm at a ratio of 2 to 20 parts by mass, and a viscosity of 0.2 to 10 Pa · s. the gap between the pair of rotor and the stay data passed at high speed, after the high shear to the mixture was dispersed with a high shear stirring device can be added, consists further step of distributed processing media type dispersing device,
When barium sulfate is dispersed as a high-speed shear stirrer, it is blended in advance.
In the dispersion treatment, the ratio of (the outer diameter of the rotor of the high-speed shear stirrer) / (the diameter of the inner diameter of the container storing the mixture) is 0.1 or more and 0.4 or less. A method for producing an aqueous pigment dispersion composition, wherein the rotor is rotated at a peripheral speed of 15 to 25 m / sec .
(2) The method for producing an aqueous pigment dispersion composition according to (1), wherein the dispersant is at least one selected from the group consisting of a surfactant, an aqueous resin, and a pigment derivative .
つぎに本発明の課題が如何にして達成されるかについて説明する。 Next, how the object of the present invention is achieved will be described.
本発明は、水性媒体と有機顔料と分散剤とを含む混合物を分散処理することにより、水性媒体中に有機顔料を分散させて水性顔料分散組成物を製造するものである。 In the present invention, an aqueous pigment dispersion composition is produced by dispersing a mixture containing an aqueous medium, an organic pigment, and a dispersant to disperse the organic pigment in the aqueous medium.
まず、従来の顔料分散技術の考え方について説明する。 First, the concept of conventional pigment dispersion technology will be described.
微細な一次粒子が凝集した状態で存在する顔料は、分散が進むにしたがって新たな表面が露出する。そして、その露出した表面に分散剤が速やかに吸着・湿潤しなければ、顔料混合液の流動性が損なわれてしまうが、顔料の分散処理中にそのような状態になると、例えばメディア型分散装置ではロック現象（メディアと顔料混合液とが一体化して流動しない現象）などが発生する。そこで、ある程度の微細な粒子径となるまでゆるやかな力で顔料を分散させ、顔料表面に分散剤を吸着・湿潤させるプレミックス処理を行うことにより、分散装置内で顔料混合液の流動性が維持できて、顔料に十分なせん断応力がかかる方法が利用されている。 The pigment existing in a state where fine primary particles are aggregated exposes a new surface as the dispersion proceeds. If the dispersant does not quickly adsorb / wet on the exposed surface, the fluidity of the pigment mixture is impaired. If such a state occurs during the pigment dispersion process, for example, a media-type dispersion device Then, a lock phenomenon (a phenomenon in which the media and the pigment mixed solution are not integrated and flow) occurs. Therefore, the fluidity of the pigment mixture is maintained in the dispersion device by pre-mixing the pigment with a gentle force until it reaches a fine particle size and then adsorbing and wetting the dispersant onto the pigment surface. In other words, a method in which a sufficient shear stress is applied to the pigment is used.
さらに、後の練肉処理では顔料をより微細に分散させるが、顔料を一次粒子の近くまで分散させるためには、粒子同士の凝集力より大きな応力を付加することが必要である。この様な顔料に応力を付加する装置として、ビーズミルなどに代表されるメディア型分散装置がある。ビーズミルは、球体のメディアをベッセルと呼ばれる筒状の槽内で攪拌させて応力を発生させる機構を有し、プレミックス処理された顔料混合物がベッセル内を通過する間に、メディア同士の衝突やずりによって発生する衝撃力やせん断力を顔料凝集体に付加して分散させるようになっている。しかし、球体のメディアの接触は一点で起こるため、衝突やずりによって発生する応力も接触点の部分が最も強く、その点から離れるにしたがってメディア間の隙間が大きくなり、かかる応力が低下するという機械的特性がある。メディア型分散装置では、メディアの攪拌速度を可変にして応力の調節ができるようになっているが、メディアの接触点でのみ顔料凝集体の凝集力より大きな応力が得られるような設定では、分散効率が極めて悪くなる。そこで、通常、接触点から少し離れた部分でも、顔料を分散させるのに必要な応力がかかるように分散条件が設定されている。 Furthermore, although the pigment is more finely dispersed in the subsequent kneading process, in order to disperse the pigment to the vicinity of the primary particles, it is necessary to apply a stress larger than the cohesive force between the particles. As a device for applying stress to such a pigment, there is a media type dispersion device represented by a bead mill. The bead mill has a mechanism that generates stress by stirring spherical media in a cylindrical tank called a vessel. Collisions and shearing of media occur while the premixed pigment mixture passes through the vessel. Is applied to the pigment aggregate to disperse it. However, since the contact of the sphere media occurs at one point, the stress generated by the collision or shear is the strongest at the contact point portion, and as the distance from the point increases, the gap between the media increases and the stress decreases. Characteristic. In the media type dispersion device, the stress can be adjusted by changing the stirring speed of the media. However, if the stress is greater than the cohesive force of the pigment aggregate only at the contact point of the media, Efficiency is extremely poor. Therefore, the dispersion conditions are usually set so that a stress necessary to disperse the pigment is applied even at a part slightly away from the contact point.
最近の水性顔料分散組成物に対する要求性能を満足するためには、より多くの顔料を一次粒子の近くまで分散させることが必要で、それに伴って、ベッセル内を通過する間に、より多くの顔料凝集体が、凝集力より大きな応力を受けることが必要となる。顔料凝集体がメディア間のどの位置で捕捉されるかは確率の問題であるため、顔料凝集体が凝集力より大きな応力のかかる位置で捕捉される確率を高くすること、とりわけ、分散効率を考慮すると、メディアの攪拌速度をより速くして、全体的にメディア間にかかる応力を高くすることが肝要である。しかし、この様な方法で顔料を分散させた場合、今度はメディアの接触点付近での応力が高くなり過ぎて、その位置で捕捉された顔料は過剰分散状態となるため、経時で凝集体を形成して性能を低下させる結果となる。 In order to satisfy the performance requirements for recent aqueous pigment dispersion compositions, it is necessary to disperse more pigment to the vicinity of the primary particles, and as a result, more pigment while passing through the vessel. It is necessary that the aggregate is subjected to a stress greater than the cohesive force. Where the pigment agglomerates are captured between the media is a matter of probability, so increasing the probability that the pigment agglomerates are captured at locations where stress is greater than the agglomeration force, especially considering dispersion efficiency Then, it is important to increase the agitation speed of the media and increase the stress applied between the media as a whole. However, when the pigment is dispersed by such a method, the stress near the contact point of the media becomes too high, and the pigment trapped at that position becomes excessively dispersed. This results in reduced performance.
一方、顔料が過剰分散にならない機械的条件で、より多くの顔料を一次粒子の近くまで分散させるには、顔料凝集体のベッセル内での移動速度を遅くするか、あるいは何度も通過させるなどといった、トータル的に高い応力のかかる回数を増加させる方法があるが、この方法では分散効率が低下して、分散装置の動力コストや作業時間などの増大を招く結果となる。 On the other hand, in order to disperse more pigment close to the primary particles under mechanical conditions where the pigment is not excessively dispersed, the moving speed of the pigment aggregate in the vessel is slowed or passed many times. There is a method of increasing the total number of times that high stress is applied. However, in this method, the dispersion efficiency is lowered, resulting in an increase in the power cost and working time of the dispersion device.
次に、本発明による、高い分散効率で、顔料が過分散状態になることなく、一次粒子径に近くまで分散できる方法の考え方について説明する。 Next, the concept of a method according to the present invention that can disperse pigments close to the primary particle size without causing the pigment to be overdispersed with high dispersion efficiency will be described.
上記の様に、メディア型分散装置は、顔料に高い応力を付加することが可能で、短時間のうちに微細に分散できるという特徴がある。しかしながら、応力のかかり方が不均一であるため、従来の分散効率を重視した分散方法では、得られる顔料分散物の粒度分布が広く、分散の進んでいない粗大粒子と、過剰に分散した状態の粒子の両方が多く存在し、それが最終組成物における性能の低下につながっていた。 As described above, the media-type dispersion apparatus has a feature that it can apply high stress to the pigment and can finely disperse in a short time. However, since the method of applying stress is non-uniform, in the conventional dispersion method in which the emphasis is placed on the dispersion efficiency, the resulting pigment dispersion has a wide particle size distribution, coarse particles that have not been dispersed, and excessively dispersed state. Many of both particles were present, which led to a decrease in performance in the final composition.
一方、他の顔料分散装置として、細いオリフィスやノズルを高圧・高速で通過させ、衝突やせん断力を利用する高圧分散処理装置、ロータの回転により処理物を移送するタイプであって、ロータとステータなどとの間隙を通過させて、処理物に高いせん断応力を付加する高速せん断攪拌装置などが知られている。そして、これらの分散装置では、メディア型分散装置と比較して、顔料に付加できる応力が均一である反面、一般的に高い応力を付加するのが困難である。また、高圧分散処理装置では、低粘度の処理物でなければ利用できず、一方、高速せん断攪拌装置では、ロータの回転によって処理物を吸引し、狭い間隙に導くという装置の構造から、処理液の流動性がより一層良好でなければならないという問題がある。 On the other hand, as other pigment dispersion devices, a high-pressure dispersion processing device that passes through a narrow orifice or nozzle at high pressure and high speed, and uses collision or shear force, and a type in which the processed material is transferred by rotation of the rotor, the rotor and stator A high-speed shearing agitation apparatus that applies a high shearing stress to a processed material by passing through a gap with the like is known. In these dispersing apparatuses, the stress that can be applied to the pigment is uniform as compared with the media type dispersing apparatus, but it is generally difficult to apply a high stress. In addition, the high-pressure dispersion treatment apparatus can be used only for a low-viscosity treatment product, while the high-speed shearing agitation device draws the treatment product by rotation of the rotor and guides it to a narrow gap. There is a problem that the fluidity of the water must be even better.
この様に、それぞれ分散装置はそれらの構造に由来する何らかの欠点がある。本発明の課題は、顔料に応力を均一に付加して、粗大粒子や過剰に分散した粒子がない状態で、微粒子化を効率的に行うことを目的とするものであるが、いずれの分散装置を用いても、高いレベルで実現できるものではない。 In this way, the respective dispersion devices have some drawbacks due to their structure. An object of the present invention is to apply a stress uniformly to a pigment so as to efficiently make fine particles in a state where there are no coarse particles or excessively dispersed particles. Even if is used, it cannot be realized at a high level.
そこで、本発明者らは、上記の目的のかなう顔料分散方法について検討を重ねた結果、まず、高速せん断攪拌装置を用いて、顔料の軟らかい凝集体を微細に分散させた後、残った顔料の硬い凝集体（粗大粒子）を、メディア型分散装置を用いて、微細に分散できる最低限に近い応力がかかる設定で分散させることにより、粗大粒子や過剰に分散した粒子を発生させることなく、最も効率的に顔料を微細に分散できる方法を見出した。しかしながら、有機顔料は水性媒体中では難分散性の顔料であるため、上記の分散方法だけでは、十分な効率化は困難という問題があった。 Therefore, as a result of repeated investigations on a pigment dispersion method that meets the above-mentioned purpose, the present inventors first dispersed a soft aggregate of pigment finely using a high-speed shear stirrer, and then the remaining pigment. By dispersing hard agglomerates (coarse particles) using a media-type dispersion device under a setting that applies a stress that is close to the minimum that can be finely dispersed, it is possible to generate the largest particles without generating coarse particles or excessively dispersed particles. The present inventors have found a method that can efficiently disperse the pigment finely. However, since the organic pigment is a hardly dispersible pigment in an aqueous medium, there is a problem that it is difficult to achieve sufficient efficiency only by the above dispersion method.
そこで、本発明者らは、さらに分散処方などについても検討した結果、高速せん断攪拌装置による分散処理時に、有機顔料と高比重成分で微粒子である水不溶性または水難溶性の金属化合物を併用することにより、粗大粒子を格段に減少させることに成功し、本発明を完成させたものである。この高比重成分である金属化合物の併用は、高速せん断攪拌装置の処理時に、非常に微細なメディアとして作用し、その摩砕効果により、多くの粗大粒子を分散させる効果につながったものと推察される。 Therefore, the present inventors further examined the dispersion formulation and the like, and as a result of using a combination of an organic pigment and a water-insoluble or poorly water-soluble metal compound that is a fine particle with a high specific gravity component at the time of dispersion treatment with a high-speed shear stirrer. The present invention has been completed by successfully reducing coarse particles. It is inferred that the combined use of the metal compound, which is a high specific gravity component, acts as a very fine medium during the processing of the high-speed shearing stirrer, leading to the effect of dispersing many coarse particles due to its grinding effect. The
このような高速せん断攪拌装置とメディア型分散装置で分散処理を行うと、より少ないエネルギーで、効率よく顔料を一次粒子の近くまで分散でき、さらに過分散状態の顔料が発生しないという、極めて有用な水性顔料分散組成物の製造方法が実現できるものである。 Dispersing with such a high-speed shear stirrer and a media type dispersing device is extremely useful in that the pigment can be efficiently dispersed to the vicinity of the primary particles with less energy, and further no overdispersed pigment is generated. A method for producing an aqueous pigment dispersion composition can be realized.
現在行われている一般的な顔料の分散処理では、目的とする水性顔料分散組成物を得ようとすると、ディスパーなどの攪拌装置で長時間プレミックス処理後、ビーズミルなどで十分に有機顔料に応力がかかるように、例えば、ビーズの攪拌速度を速く、顔料混合物のベッセル内の通過速度を遅く設定して練肉を行い、目的とする水性顔料分散組成物を得ていた。また、機械的な特性から、得られる水性顔料分散組成物は、顔料の粗大粒子を多く含むものとなっていた。 In a general pigment dispersion treatment currently being performed, if an intended aqueous pigment dispersion composition is to be obtained, a premix treatment is performed for a long time with a stirring device such as a disper, and then the organic pigment is sufficiently stressed with a bead mill or the like. As described above, for example, kneading is performed by setting the stirring speed of the beads fast and the passing speed of the pigment mixture in the vessel slow to obtain the desired aqueous pigment dispersion composition. Moreover, from the mechanical characteristics, the obtained aqueous pigment dispersion composition contains a large amount of coarse pigment particles.
しかし、本発明の水性顔料分散組成物の製造方法では、プレミックス処理を行うとしても、ディスパーなどで数分攪拌混合した後、先にハイシアーミキサーなどの高速せん断分散装置で十分な分散処理を行えば、次のビーズミルなどの分散の段階では、分散処理物の吐出量を従来よりもずっと多くして（顔料混合物のベッセル内の通過速度を速くすることで、高速せん断分散装置で分散処理した効果により、プレミックス処理だけより３〜５倍程度まで吐出量を多くすることができる）、目的とする水性顔料分散組成物が得られる。その結果として、従来の製造方法よりも分散処理にかかる時間が短かくなり、トータルでの製造時間の短縮が可能となる。 However, in the method for producing an aqueous pigment dispersion composition of the present invention, even if a premix treatment is performed, after stirring and mixing for several minutes with a disper or the like, a sufficient dispersion treatment is first performed with a high-speed shearing dispersion device such as a high shear mixer. In the next dispersion stage such as the bead mill, the amount of the dispersion processed material is increased more than before (by increasing the passage speed of the pigment mixture in the vessel, the dispersion processing is performed with a high-speed shearing dispersion device. According to the effect, the discharge amount can be increased up to about 3 to 5 times from the premix treatment alone), and the desired aqueous pigment dispersion composition can be obtained. As a result, the time required for the dispersion process is shorter than in the conventional manufacturing method, and the total manufacturing time can be shortened.
また、ビーズミルは、重量のあるビーズを高速で攪拌する機構であるため、通常、ロータを回転させるタイプの分散装置と比較して多くのエネルギーを必要とする。したがって、ビーズミルによる練肉処理時間の短縮は、トータルでの消費エネルギーの削減にもつながるものである。 Further, since the bead mill is a mechanism for stirring heavy beads at high speed, it usually requires more energy than a dispersion device that rotates a rotor. Therefore, shortening of the meat processing time by the bead mill leads to a reduction in total energy consumption.
さらに、本発明の特徴である金属化合物の使用により、高速せん断分散装置での処理において、粗大粒子の数を減少させることができるため、得られる水性顔料分散組成物では、顔料が過分散状態まで顔料を分散させることなく、粗大粒子の数を大幅に減少させることができる。 Furthermore, since the number of coarse particles can be reduced in the treatment with a high-speed shear disperser by using the metal compound which is a feature of the present invention, the resulting aqueous pigment dispersion composition has a pigment in an overdispersed state. The number of coarse particles can be greatly reduced without dispersing the pigment.
その結果、本発明の製造方法で得られる水性顔料分散組成物は、流動性、着色力に優れたものとなる。 As a result, the aqueous pigment dispersion composition obtained by the production method of the present invention has excellent fluidity and coloring power.
本発明の水性顔料分散組成物の製造方法について説明する。 The manufacturing method of the aqueous pigment dispersion composition of this invention is demonstrated.
本発明は、有機顔料、分散剤、金属化合物および水性媒体を含む粘度０．２〜１０Ｐａ・ｓの混合液を、少なくとも一組の高速回転するロータと静止状態のステータとの間隙、または少なくとも一組の高速回転するロータと反対回転するロータとの間隙を通過させ混合物に高いせん断応力が付加できる高速せん断攪拌装置で分散処理した後、さらにメディア型分散装置で分散処理することにより、水性媒体中に有機顔料を分散させる水性顔料分散組成物の製造方法である。 According to the present invention, a liquid mixture having a viscosity of 0.2 to 10 Pa · s containing an organic pigment, a dispersant, a metal compound, and an aqueous medium is mixed with at least one gap between a high-speed rotating rotor and a stationary stator, or at least one. After dispersion treatment with a high-speed shearing stirrer that can pass a gap between the pair of high-speed rotating rotors and the counter-rotating rotor and add high shear stress to the mixture, further dispersion treatment with a media-type dispersion device It is a manufacturing method of the aqueous pigment dispersion composition which disperse | distributes an organic pigment in.
ここで本発明の水性顔料分散組成物の製造方法で使用可能な有機顔料としては、キナクリドン系顔料、ジオキサジン系顔料、フタロシアニン系顔料、アントラピリミジン系顔料、アンサンスロン系顔料、インダンスロン系顔料、フラバンスロン系顔料、ペリレン系顔料、ジケトピロロピロール系顔料、ペリノン系顔料、キノフタロン系顔料、アントラキノン系顔料、チオインジゴ系顔料、ベンツイミダゾロン系顔料、イソインドリノン系顔料、アゾメチン系顔料、アゾ系顔料などの有機顔料を挙げることができる。 Examples of organic pigments that can be used in the method for producing the aqueous pigment dispersion composition of the present invention include quinacridone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, ansanthrone pigments, indanthrone pigments, Flavanthrone pigment, perylene pigment, diketopyrrolopyrrole pigment, perinone pigment, quinophthalone pigment, anthraquinone pigment, thioindigo pigment, benzimidazolone pigment, isoindolinone pigment, azomethine pigment, azo Mention may be made of organic pigments such as pigments.
また、本発明の水性顔料分散組成物の製造方法で使用可能な分散剤としては、界面活性剤、水性樹脂、顔料誘導体などが例示できる。 Examples of the dispersant that can be used in the method for producing the aqueous pigment dispersion composition of the present invention include surfactants, aqueous resins, and pigment derivatives.
界面活性剤としてはアニオン性界面活性剤、非イオン性界面活性剤またはカチオン性活性剤のいずれも使用できる。アニオン性界面活性剤としては、脂肪酸塩、アルキル硫酸エステル塩、アルキルアリールスルホン酸塩、アルキルナフタレンスルホン酸塩、ジアルキルスルホン酸塩、ジアルキルスルホコハク酸塩、アルキルジアリールエーテルジスルホン酸塩、アルキルリン酸塩、ポリオキシエチレンアルキルエーテル硫酸塩、ポリオキシエチレンアルキルアリールエーテル硫酸塩、ナフタレンスルホン酸フォルマリン縮合物、ポリオキシエチレンアルキルリン酸エステル塩、グリセロールボレイト脂肪酸エステル、ポリオキシエチレングリセロール脂肪酸エステルなどが例示でき、非イオン性界面活性剤としては、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルアリールエーテル、ポリオキシエチレンオキシプロピレンブロックコポリマー、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンソルビトール脂肪酸エステル、グリセリン脂肪酸エステル、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレンアルキルアミン、フッ素系、シリコーン系などの非イオン性活性剤が例示でき、カチオン性界面活性剤としては、アルキルアミン塩、第四級アンモニウム塩、ポリオキシエチレンアルキルアミンなどが例示できる。 As the surfactant, any of an anionic surfactant, a nonionic surfactant, or a cationic surfactant can be used. Anionic surfactants include fatty acid salts, alkyl sulfate salts, alkylaryl sulfonates, alkylnaphthalene sulfonates, dialkyl sulfonates, dialkyl sulfosuccinates, alkyl diaryl ether disulfonates, alkyl phosphates, Examples include polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, naphthalenesulfonic acid formalin condensate, polyoxyethylene alkyl phosphate ester salt, glycerol borate fatty acid ester, polyoxyethylene glycerol fatty acid ester, etc. Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene oxypropylene block copolymer. Nonionic active agents such as mer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, fluorine-based, silicone-based Examples of the cationic surfactant include alkylamine salts, quaternary ammonium salts, and polyoxyethylene alkylamines.
また、水性樹脂としては、既知の顔料を分散するために利用される、カチオン性基含有またはアニオン性基含有のビニル系、ポリエステル系、ポリアミド系、ポリウレタン系などの水に溶解する樹脂が用いられ、その中でも好ましいのは、アクリル系、スチレン−アクリル系、スチレン−マレイン酸系、スチレン−アクリル−マレイン酸系樹脂のアニオン性基を含有するビニル系樹脂で、さらに好ましくは、芳香環を有する単量体の少なくとも１種を２０〜７０質量％含有するビニル系樹脂である（なお、アクリル系樹脂とは少なくとも２種のアクリル系単量体を、スチレン−アクリル系樹脂とは少なくとも１種のスチレン系単量体と少なくとも１種のアクリル系単量体を、スチレン−マレイン酸系樹脂とは少なくとも１種のスチレン系単量体と少なくとも１種のマレイン酸系単量体を、そしてスチレン−アクリル−マレイン酸系樹脂とは少なくとも１種のスチレン系単量体、少なくとも１種のマレイン酸系単量体および少なくとも１種のアクリル系単量体を共重合成分とする共重合体樹脂である）。 In addition, as the aqueous resin, a resin that dissolves in water such as a vinyl group, a polyester group, a polyamide group, or a polyurethane group that contains a cationic group or an anionic group and is used for dispersing a known pigment is used. Among them, preferred are vinyl resins containing anionic groups of acrylic, styrene-acrylic, styrene-maleic acid, and styrene-acrylic-maleic acid resins, and more preferred are single resins having an aromatic ring. It is a vinyl-based resin containing 20 to 70% by mass of at least one monomer (Note that an acrylic resin is at least two acrylic monomers, and a styrene-acrylic resin is at least one styrene. A styrene monomer and at least one acrylic monomer, and a styrene-maleic acid resin is at least one styrene monomer. And at least one maleic monomer, and styrene-acrylic-maleic resin is at least one styrene monomer, at least one maleic monomer and at least one acrylic. It is a copolymer resin having a monomer as a copolymer component).
例えば、この様なアニオン性基を含有するビニル系樹脂で使用できるアクリル系単量体としては、アクリル酸、メタクリル酸、および、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレートなどの（メタ）アクリル酸アルキルエステル化合物、ベンジル（メタ）アクリレート、ナフチル（メタ）アクリレートなどの芳香族環を含む（メタ）アクリル酸エステル化合物、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、３−ヒドロキシプロピル（メタ）アクリレートなどの（メタ）アクリル酸ヒドロキシアルキルエステル化合物、ポリプロピレングリコールモノ（メタ）アクリル酸エステル系化合物が利用できる。使用できるスチレン系単量体としては、スチレン、α−メチルスチレン、ビニルトルエンとそれらの誘導体が利用できる。使用できるマレイン酸系単量体としては、（無水）マレイン酸、および、マレイン酸モノメチル、マレイン酸モノエチル、マレイン酸モノプロピル、マレイン酸モノブチル、マレイン酸モノヘキシル、マレイン酸モノオクチル、マレイン酸モノ２−エチルヘキシル、マレイン酸モノラウリル、マレイン酸モノステアリルなどのマレイン酸モノアルキルエステルが利用でき、さらに、マレイン酸ジメチル、マレイン酸ジエチル、マレイン酸ジブチルなどのマレイン酸ジアルキルエステル化合物も利用できる。また、これらの共重合体樹脂は、必要に応じて、（メタ）アクリルアミド、クロトン酸とそのエステル化合物、イタコン酸とそのエステル化合物、シトラコン酸とそのエステル化合物、アクリロニトリル、オレフィン化合物などの他の共重合可能な単量体を共重合成分としてもよい。 For example, acrylic monomers that can be used in vinyl resins containing such anionic groups include acrylic acid, methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate. , (Meth) acrylic acid alkyl ester compounds such as butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, naphthyl (Meth) acrylic acid ester compounds containing an aromatic ring such as (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate (meth) Hydroxyalkyl ester compounds of acrylic acid, polypropylene glycol mono (meth) acrylate compound can be utilized. Styrene monomers that can be used include styrene, α-methylstyrene, vinyltoluene and their derivatives. Examples of maleic monomers that can be used include (anhydrous) maleic acid and monomethyl maleate, monoethyl maleate, monopropyl maleate, monobutyl maleate, monohexyl maleate, monooctyl maleate, mono-2- maleate Maleic acid monoalkyl esters such as ethylhexyl, monolauryl maleate and monostearyl maleate can be used, and dialkyl maleate compounds such as dimethyl maleate, diethyl maleate and dibutyl maleate can also be used. In addition, these copolymer resins may contain other copolymers such as (meth) acrylamide, crotonic acid and its ester compound, itaconic acid and its ester compound, citraconic acid and its ester compound, acrylonitrile, and olefin compound as necessary. A polymerizable monomer may be used as a copolymerization component.
そして、アニオン性基含有樹脂を水に溶解させる塩基性化合物としては、水酸化ナトリウム、水酸化カリウムのような無機塩基性化合物や、アンモニア、メチルアミン、エチルアミン、モノエタノールアミン、Ｎ、Ｎ−ジメチルエタノールアミン、Ｎ、Ｎ−ジエチルエタノールアミン、Ｎ、Ｎ−ジブチルエタノールアミン、ジエタノールアミン、Ｎ−メチルジエタノールアミン、トリエタノールアミン、モルホリン、Ｎ−メチルモルホリン、Ｎ−エチルモルホリンのような有機塩基性化合物などが挙げられる。これらは単独で、または２種以上を混合して用いることができる。カチオン性基含有樹脂を水に溶解させる酸性化合物としては、塩酸、硫酸、燐酸、硝酸などの無機酸類、蟻酸、酢酸、乳酸、プロピオン酸などの有機酸類などが挙げられる。これらは単独で、または２種以上を混合して用いることができる。 Examples of the basic compound for dissolving the anionic group-containing resin in water include inorganic basic compounds such as sodium hydroxide and potassium hydroxide, ammonia, methylamine, ethylamine, monoethanolamine, N, N-dimethyl. Organic basic compounds such as ethanolamine, N, N-diethylethanolamine, N, N-dibutylethanolamine, diethanolamine, N-methyldiethanolamine, triethanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine, etc. Can be mentioned. These can be used alone or in admixture of two or more. Examples of the acidic compound that dissolves the cationic group-containing resin in water include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid, and organic acids such as formic acid, acetic acid, lactic acid, and propionic acid. These can be used alone or in admixture of two or more.
さらに、顔料誘導体としては、例えば、有機顔料に発煙硫酸、濃硫酸などのスルホン化剤を作用させてスルホン酸基を導入したもの、有機顔料に三酸化硫黄ガスを用いて気相−固相状態でスルホン酸基を導入したものなどが挙げられ、具体的には、アントラキノン、キナクリドン、ジケトピロロピロール、銅フタロシアニン、イソインドリノンなどの顔料骨格にスルホン酸基を導入した化合物などが挙げられる。 Further, as the pigment derivative, for example, a sulfonic acid group introduced by causing a sulfonating agent such as fuming sulfuric acid or concentrated sulfuric acid to act on the organic pigment, or a gas phase-solid phase state using sulfur trioxide gas for the organic pigment And those having a sulfonic acid group introduced into the pigment skeleton, such as anthraquinone, quinacridone, diketopyrrolopyrrole, copper phthalocyanine, and isoindolinone.
本発明の水性顔料分散組成物の製造方法で使用される金属化合物としては、水に不溶性または難溶性で、水性媒体中でほとんどが不溶成分として存在するものが好適である。このような金属化合物としては、硫酸バリウムなどの金属塩、酸化亜鉛などの金属酸化物などが例示できる。これら金属化合物は単独でまたは２種以上を組み合わせて使用できる。そして、金属化合物の比重は３〜６で、平均一次粒子径は０．０５μｍ〜１μであり、好ましくは０．０６〜０．１μｍである。使用する金属化合物の比重が３より小さいと本発明の効果がえられず、６より大きいと水性媒体中で分散できずに沈降するといった問題が発生する。また、同様に金属化合物の平均一次粒子径が前記範囲より小さいと本発明の効果がえられず、前記範囲より大きいと沈降の問題が発生する。 As the metal compound used in the method for producing an aqueous pigment dispersion composition of the present invention, a metal compound that is insoluble or hardly soluble in water and is mostly present as an insoluble component in an aqueous medium is suitable. Examples of such metal compounds include metal salts such as barium sulfate and metal oxides such as zinc oxide. These metal compounds can be used alone or in combination of two or more. And the specific gravity of a metal compound is 3-6, and an average primary particle diameter is 0.05 micrometer-1 micrometer, Preferably it is 0.06-0.1 micrometer. If the specific gravity of the metal compound to be used is less than 3, the effect of the present invention cannot be obtained, and if it is more than 6, the problem arises that it cannot settle in an aqueous medium and settles. Similarly, if the average primary particle diameter of the metal compound is smaller than the above range, the effect of the present invention cannot be obtained, and if it is larger than the above range, the problem of sedimentation occurs.
本発明の水性顔料分散組成物の製造方法で使用される水性媒体としては、水、または水と水混和性有機溶剤との混合物が使用できる。 As an aqueous medium used in the method for producing an aqueous pigment dispersion composition of the present invention, water or a mixture of water and a water-miscible organic solvent can be used.
水混和性有機溶剤としては、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−プロピルアルコールなどの低級アルコール類、エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール、グリセリンなどの多価アルコール類、エチレングリコーモノメチルエーテル、エチレングリコーモノエチルエーテル、プロピレングリコールモノメチルエーテル、プロピ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などの（ポリ）アルキレングリコールのものアルキルエーテル類、エチレングリコールモノアセテート、プロピレングリコールモノアセテートなどの（ポリ）アルキレングリコ−ルのモノ脂肪酸エステル類などが挙げられる。これら水混和性有機溶剤は単独でまたは２種以上組み合わせて使用できる。 Examples of the water-miscible organic solvent include lower alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol and n-propyl alcohol, polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol and glycerin, ethylene glycol Alkyl ethers of (poly) alkylene glycols such as monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monoacetate, propylene glycol monoacetate (Poly) alkylene glycol mono-fatty acid such as Such as ethers, and the like. These water-miscible organic solvents can be used alone or in combination of two or more.
以上の材料を混合して得られる混合物における各材料の組成として、有機顔料は概ね混合物１００質量部中に１〜４５質量部程度であるのが好ましく、より好ましくは１０〜４０質量部程度である。また、分散剤の使用量は、顔料１００質量部に対して２〜２５質量部程度であることが好ましい。さらに、金属化合物の含有量は、有機顔料１００質量部に対して、２〜２０質量部、好ましくは３〜１０質量部、より好ましくは５〜１０質量部となるように加えられる。金属化合物の含有量が前記範囲より少ないと、高速せん断攪拌装置による分散処理が終了しても粗大粒子が残る傾向があり、その後に行われるメディア装置による分散処理の前記の問題点の解消が困難となる。一方、金属化合物の含有量を前記範囲より多くしても、分散効果はそれ以上良好にならない。 As a composition of each material in the mixture obtained by mixing the above materials, the organic pigment is preferably about 1 to 45 parts by mass, more preferably about 10 to 40 parts by mass in 100 parts by mass of the mixture. . Moreover, it is preferable that the usage-amount of a dispersing agent is about 2-25 mass parts with respect to 100 mass parts of pigments. Furthermore, content of a metal compound is added so that it may become 2-20 mass parts with respect to 100 mass parts of organic pigments, Preferably it is 3-10 mass parts, More preferably, it becomes 5-10 mass parts. If the content of the metal compound is less than the above range, coarse particles tend to remain even after the dispersion treatment by the high-speed shear stirrer is completed, and it is difficult to solve the above-described problems of the dispersion treatment by the media device performed thereafter. It becomes. On the other hand, even if the content of the metal compound is increased from the above range, the dispersion effect is not further improved.
上記のような組成で水性媒体中に各材料が添加混合され、ほぼ均一に混合された状態において、混合液の調整時の温度下で０．２〜１０Ｐａ・ｓとなるように混合液の粘度が調整される。混合液の粘度が上記の範囲より低い場合は、分散処理において十分な分散応力がかからず、顔料を十分に分散させることができない傾向がある。一方、上記の範囲より高い場合は、混合物の流動性が低下して、分散処理が困難になる傾向があり、好ましくない。なお、前記混合物の調製は、プロペラタイプ、パドルタイプ、タービンタイプなどのロータを有する装置を利用して、３〜３０分間程度攪拌・混合して行うことが好ましい。 In the state where each material is added and mixed in the aqueous medium with the above composition, and the mixture is almost uniformly mixed, the viscosity of the mixed solution is 0.2 to 10 Pa · s at the temperature when adjusting the mixed solution. Is adjusted. When the viscosity of the mixed liquid is lower than the above range, sufficient dispersion stress is not applied in the dispersion treatment, and the pigment tends to be not sufficiently dispersed. On the other hand, when it is higher than the above range, the fluidity of the mixture is lowered, and the dispersion treatment tends to be difficult, which is not preferable. The mixture is preferably prepared by stirring and mixing for about 3 to 30 minutes using an apparatus having a rotor such as a propeller type, paddle type, or turbine type.
本発明の水性顔料分散組成物の製造方法で使用される高速せん断攪拌装置としては、少なくとも一組の高速回転するロータと静止状態のステータとの間隙、または、少なくとも一組の高速回転するロータと通常反対方向に回転するロータとの間隙を通過させ、混合液に高いせん断応力が付加できる装置が利用できる。 The high-speed shear stirring device used in the method for producing the aqueous pigment dispersion composition of the present invention includes at least one pair of high-speed rotating rotors and a stationary stator, or at least one set of high-speed rotating rotors. An apparatus that can pass a gap with a rotor that normally rotates in the opposite direction and can apply a high shear stress to the mixed solution can be used.
この様な装置の代表的なものとしては、例えば、ハイシアーミキサーＢＸ、ＣＸ、ＤＸ、ＥＸ、ＦＸ、ＧＸ１０、ＧＸ２０、７００Ｘ、ＨＸ１０、ＨＸ３０、ＪＸ、ＫＸ（以上シルバーソン社製）、ハイシアーミキサーＩＫＡ２０００シリーズ（ＩＫＡ社製）、Ｔ．Ｋ．ホモミキサー（特殊機化工業（株）製）、ウルトラホモミキサー（みずほ工業（株）製）、クレアミックス（エム・テクニック社製）、キャビトロン（太平洋機工（株）製）などが挙げられる。なかでも、特にロータとステータを有するハイシアーミキサーやそれに類似する構造のものが好ましい。 Representative examples of such devices include, for example, high shear mixers BX, CX, DX, EX, FX, GX10, GX20, 700X, HX10, HX30, JX, KX (above Silverson), High Shear Mixer IKA2000 series (manufactured by IKA), T.K. K. Homomixer (made by Special Machine Industry Co., Ltd.), ultrahomomixer (made by Mizuho Industry Co., Ltd.), Claremix (made by M Technique Co., Ltd.), Cavitron (made by Taiheiyo Kiko Co., Ltd.) and the like. Of these, a high shear mixer having a rotor and a stator and a similar structure are particularly preferred.
図面に基づいて本発明で使用する高速せん断攪拌装置を説明する。図１は高速せん断攪拌装置の一実施例を示す概略説明図であり、図２はその要部拡大図である。図１〜２に示される高速せん断攪拌装置はロータとステータを有するハイシアーミキサーの一例である。このハイシアーミキサーでは、ロータとステータとから構成される分散部１が容器１０に収容された分散処理に付される混合物１１中に浸漬されるように構成されている。ロータ２は原動機３の回転軸４に取り付けられ、高速回転するように構成されている。５は固定されたステータであり、ステータ５には多数の孔６が設けられている。１２は分散部１を支持するための支持具である。ステータ５内におけるロータ２の高速回転により、容器１０の底部の混合物１１は分散部１内に引き込まれる。分散部１に引き込まれた混合物１１はロータの生み出す遠心力によって、ステータ５の方向に振り出され、そのときロータ２のブレード部とステータの内壁との間隙で高いせん断応力を受ける。高速で高いせん断応力を加えられた混合物はステータ５に設けられた孔６から外側に押し出される。分散部１の外側に押し出された混合物は、容器１０の内壁に沿って循環し、同時に新しい材料が分散部１の下側から連続的に供給されてこの作業が繰り返される。
A high-speed shear stirring apparatus used in the present invention will be described with reference to the drawings. FIG. 1 is a schematic explanatory view showing an embodiment of a high-speed shear stirring apparatus, and FIG. The high-speed shear stirrer shown in FIGS. 1 and 2 is an example of a high shear mixer having a rotor and a stator. In this high shear mixer, the
そして、ロータの回転速度は、動力装置やロータとステータとの間隙（通常０．１〜１ｍｍ程度）、ロータ径などの機械的条件の他、分散させる材料の粘度、投入電力量などに依存するが、本発明においては、ロータの周速を１５ｍ／ｓｅｃ以上で回転させることが可能なタイプのものから選択することが好ましく、さらにロータの周速が速くなればなるほど高いせん断応力を付加できるという点から有利である。なお、顔料の分散処理の効率の面から、概ね、周速としては１５〜２５ｍ／ｓｅｃ程度で処理を行うことが好ましい。さらに、容器内の混合物が全体として均一に分散処理を受けやすくするため、ロータと混合物を収納する容器との関係において、ロータの外径／容器内径の比が０．１以上であるのが好ましい。ロータの外径／容器内径の比が前記範囲より小さいと、混合物の循環が悪くなる場所が発生し、顔料分散が低下する傾向がある。ロータの外径／容器内径の比の上限値は特に限定されないが、装置の操作性の点からは、ロータの外径／容器内径の比の上限値は０．４程度である。 The rotational speed of the rotor depends on the power device, the gap between the rotor and the stator (usually about 0.1 to 1 mm), the mechanical conditions such as the rotor diameter, the viscosity of the material to be dispersed, the input power amount, and the like. However, in the present invention, it is preferable to select from the types that can rotate the rotor peripheral speed at 15 m / sec or more, and the higher the rotor peripheral speed, the higher the shear stress that can be applied. This is advantageous from the point of view. In general, from the viewpoint of the efficiency of the pigment dispersion treatment, the treatment is preferably performed at a peripheral speed of about 15 to 25 m / sec. Furthermore, in order to make the mixture in the container easy to be uniformly dispersed as a whole, the ratio of the outer diameter / inner diameter of the rotor is preferably 0.1 or more in the relationship between the rotor and the container for storing the mixture. . When the ratio of the outer diameter of the rotor / the inner diameter of the container is smaller than the above range, a place where the circulation of the mixture is deteriorated occurs, and the pigment dispersion tends to decrease. The upper limit value of the ratio of the outer diameter of the rotor / the inner diameter of the container is not particularly limited, but the upper limit value of the ratio of the outer diameter of the rotor / the inner diameter of the container is about 0.4 from the viewpoint of operability of the apparatus.
本発明の高速せん断攪拌装置を用いて行う分散処理は、終点（それ以上分散処理を行っても分散がほとんど進行しないところまで達した状態）まで分散処理を行うことが好ましい（高速せん断攪拌装置の処理能力、分散処理量などにより終点までの時間は異なる）。 The dispersion treatment performed using the high-speed shear stirrer of the present invention is preferably performed to the end point (a state where the dispersion has hardly progressed even if further dispersion treatment is performed). The time to the end point varies depending on the processing capacity and distributed processing amount).
本発明の水性顔料分散組成物の製造方法で使用されるメディア型分散装置としては、通常、利用されるパールミル、ダイノミルなどのビーズミル型分散装置、アトライター、ボールミルなどのメディア型分散装置が挙げられる。使用するメディアも特に制限されず、通常のものがいずれも使用可能であり、たとえば、ジルコニアビーズ、磁性ビーズ、ガラスビーズ、ステンレス製ビーズなどの材質のもので、大きさが０．１〜３ｍｍ程度のものが挙げられる。 Examples of the media type dispersing device used in the method for producing the aqueous pigment dispersion composition of the present invention include commonly used bead mill type dispersing devices such as pearl mill and dyno mill, and media type dispersing devices such as attritor and ball mill. . The medium to be used is not particularly limited, and any ordinary one can be used. For example, the medium is made of zirconia beads, magnetic beads, glass beads, stainless steel beads, and the size is about 0.1 to 3 mm. Can be mentioned.
このようなメディア型分散装置では、従来のプレミックス処理を行った場合、残存する顔料の粗大粒子を分散させるために、より高い応力がかかる条件で練肉処理を行なう必要があった。例えば、ビーズミル型分散装置では、メディアの攪拌速度を高くしたり、プレミックス処理物のベッセル内の通過速度を遅く設定したりする必要があった。しかしながら、本発明に係る上記の高速せん断攪拌装置で分散処理を行った場合は、メディア型分散装置において、従来よりも低い応力の発生する条件、あるいは混合物が速い速度でベッセル内を通過する条件での練肉処理においても、良好な顔料分散組成物が得られるものである。そこで、メディアの攪拌速度や混合物のベッセル内通過時間などについては、有機顔料の過剰に分散された状態を発生させないという条件を第一義として、それぞれ利用する材料、高速せん断攪拌装置での処理条件などを加味して、適宜、最良の条件となるように設定することが好ましい。 In such a media-type dispersion apparatus, when the conventional premix process is performed, it is necessary to perform the kneading process under higher stress conditions in order to disperse the coarse particles of the remaining pigment. For example, in a bead mill type dispersion apparatus, it is necessary to increase the stirring speed of the media or to set the passing speed of the premix processed product in the vessel slower. However, when the dispersion treatment is performed with the above-described high-speed shear stirrer according to the present invention, in the media-type dispersion device, a condition in which stress is lower than that in the past, or a condition in which the mixture passes through the vessel at a high speed. A good pigment dispersion composition can be obtained also in the kneaded meat treatment. Therefore, with regard to the stirring speed of the media and the passage time of the mixture in the vessel, the condition that the organic pigment is not excessively dispersed is the primary condition, and the materials used and the processing conditions in the high-speed shearing stirrer are used. In consideration of the above, it is preferable to set the best conditions as appropriate.
本発明の水性顔料分散組成物の製造方法によれば、得られる有機顔料分散体の粒子径は特に制限されないが、平均一次粒子径が１μｍ以下である有機顔料分散体を得る際に好適に適用される。 According to the method for producing an aqueous pigment dispersion composition of the present invention, the particle diameter of the obtained organic pigment dispersion is not particularly limited, but is suitably applied when obtaining an organic pigment dispersion having an average primary particle diameter of 1 μm or less. Is done.
最後に本発明の水性顔料分散組成物の用途について説明する。本発明の水性顔料分散組成物は、用途に応じて、さらに各種樹脂、水性媒体や、ブロッキング防止剤、湿潤剤、粘度調整剤、ｐＨ調整剤、消泡剤、一般の界面活性剤などの種々の添加剤を適宜加えて、例えば、フレキソ印刷インキ、水性グラビアインキ、水性塗料、水性インクッジェト用インクなどに使用できるものである。 Finally, the use of the aqueous pigment dispersion composition of the present invention will be described. The water-based pigment dispersion composition of the present invention may further include various resins, aqueous media, anti-blocking agents, wetting agents, viscosity adjusting agents, pH adjusting agents, antifoaming agents, general surfactants, and the like depending on applications. These additives can be added as appropriate, and can be used, for example, in flexographic printing inks, aqueous gravure inks, aqueous paints, aqueous ink jet inks, and the like.
以下、実施例により本発明をさらに詳細に説明するが、本発明はこれら実施例に限定されるものではない。なお、表１における各材料の使用比率は、「質量％」を表す。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. In addition, the use ratio of each material in Table 1 represents “mass%”.
［水性樹脂ワニス１の調製］
分散剤として酸価２１０、質量平均分子量１６，０００のスチレン−アクリル酸共重合体２５質量部を、当該共重合体全量を中和するのに必要な量の塩基性化合物（アンモニア／ジメチルエタノールアミン＝９／１（当量比））を含む水７５質量部中に加熱溶解させて水性樹脂ワニス１（前記共重合体濃度：２５質量％）を得た。
[Preparation of aqueous resin varnish 1]
As a dispersant, 25 parts by mass of a styrene-acrylic acid copolymer having an acid value of 210 and a mass average molecular weight of 16,000 is added to a basic compound (ammonia / dimethylethanolamine) in an amount necessary to neutralize the total amount of the copolymer. = 9/1 (equivalent ratio)) was dissolved by heating in 75 parts by mass of water to obtain an aqueous resin varnish 1 (the copolymer concentration: 25% by mass).
実施例１〜４
表１に示した配合組成の混合物をディスパーで５分攪拌した後、下記の条件の高速せん断攪拌装置で分散処理し、次いで練肉用のメディア型分散装置を用いて分散処理を行い、さらに残余の成分を添加して実施例１〜４の水性顔料分散組成物を得た。ディスパーで攪拌後の混合物についておよび最終の水性顔料分散組成物について粘度を（株）トキメック製Ｂ型粘度計（２５℃、６０ｒｐｍ）で測定した。
Examples 1-4
The mixture having the composition shown in Table 1 was stirred with a disper for 5 minutes, then dispersed with a high-speed shearing stirrer under the following conditions, then dispersed with a media-type dispersing device for kneaded meat, and the rest The aqueous pigment dispersion composition of Examples 1-4 was obtained by adding these components. The viscosity of the mixture after stirring with the disper and the final aqueous pigment dispersion composition was measured with a B-type viscometer (25 ° C., 60 rpm) manufactured by Tokimec Co., Ltd.
＜高速せん断攪拌装置＞
機種 ： ハイシアーミキサーＥＸタイプ（シルバーソン社製）
モーター容量 ： ４ｋｗ
回転数 ： ３６００ｒｐｍ
ロータ周速 ： １９．１４ｍ／ｓｅｃ
容器内径 ： ６００ｍｍ
ロータ外径 ： １０１．１６ｍｍ
評価スケール ： ２００ｋｇ
処理時間 ： ６０分
<High-speed shear stirrer>
Model: High Shear Mixer EX type (Silverson)
Motor capacity: 4kw
Rotation speed: 3600rpm
Rotor peripheral speed: 19.14 m / sec
Container inner diameter: 600 mm
Rotor outer diameter: 101.16mm
Evaluation scale: 200kg
Processing time: 60 minutes
＜練肉用メディア分散装置＞
機種 ： ビーズミル
メディア材質 ： ジルコニアビーズ
メディア径 ： １．０ｍｍ
ベッセル容量 ： １５リットル
吐出量 ： ２００ｋｇ／ｈｒ
<Mixed meat distribution device>
Model: Bead Mill Media Material: Zirconia Bead Media Diameter: 1.0mm
Vessel capacity: 15 liters Discharge rate: 200 kg / hr
比較例１〜２
表１に示した配合組成の混合物をディスパーで６０分攪拌した後、下記の条件の練肉用メディア分散装置を用いて分散処理を行い、さらに残余の成分を添加して比較例１および２の水性顔料分散組成物を得た（従来行われている分散処理）。得られた水性顔料分散組成物について粘度をＢ型粘度計で測定した。
Comparative Examples 1-2
After the mixture having the composition shown in Table 1 was stirred with a disper for 60 minutes, the mixture was subjected to a dispersion treatment using a medium dispersing apparatus for kneaded meat under the following conditions, and the remaining components were further added. An aqueous pigment dispersion composition was obtained (dispersion treatment conventionally performed). The viscosity of the obtained aqueous pigment dispersion composition was measured with a B-type viscometer.
＜練肉用メディア分散装置＞
機種 ： ビーズミル
メディア材質 ： ジルコニアビーズ
メディア径 ： １．０ｍｍ
ベッセル容量 ： １５リットル
吐出量 ： １００ｋｇ／ｈｒ
<Mixed meat distribution device>
Model: Bead Mill Media Material: Zirconia Bead Media Diameter: 1.0mm
Vessel capacity: 15 liters Discharge rate: 100 kg / hr
比較例３〜６
表１に示した配合組成の混合物をディスパーで５分攪拌した後、下記の条件の高速せん断攪拌装置のみで分散処理を行い、さらに残余の成分を添加して比較例３〜６の水性顔料分散組成物を得た。ディスパーで攪拌後の混合物についておよび最終の水性顔料分散組成物について粘度をＢ型粘度計で測定した。
Comparative Examples 3-6
After the mixture having the composition shown in Table 1 was stirred with a disper for 5 minutes, the dispersion treatment was performed only with a high-speed shearing stirrer under the following conditions, and the remaining components were added to disperse the aqueous pigment in Comparative Examples 3-6. A composition was obtained. The viscosity of the mixture after stirring with the disper and the final aqueous pigment dispersion composition was measured with a B-type viscometer.
＜高速せん断攪拌装置＞
機種 ： ハイシアーミキサーＥＸタイプ（シルバーソン社製）
モーター容量 ： ４ｋｗ
回転数 ： ３６００ｒｐｍ
周速 ： １９．１４ｍ／ｓｅｃ
容器内径 ： ６００ｍｍ
ロータ外径 ： １０１．１６ｍｍ
評価スケール ： １００ｋｇ
処理時間 ： ９０分
<High-speed shear stirrer>
Model: High Shear Mixer EX type (Silverson)
Motor capacity: 4kw
Rotation speed: 3600rpm
Peripheral speed: 19.14m / sec
Container inner diameter: 600 mm
Rotor outer diameter: 101.16mm
Evaluation scale: 100kg
Processing time: 90 minutes
高速せん断攪拌装置のみで分散処理を行う比較例３〜６においては、６０分で分散が終了に近い状態になり、それ以上分散処理を行ってもほとんど分散は進まなかったが、念のため９０分間分散処理したものについて性能評価した。 In Comparative Examples 3 to 6 in which the dispersion treatment was performed only with the high-speed shearing stirrer, the dispersion was nearly finished in 60 minutes, and even if the dispersion treatment was further performed, the dispersion hardly proceeded. Performance evaluation was performed on the sample that was dispersed for a minute.
前記実施例１〜４および比較例１〜６の水性顔料分散組成物の製造について、下記の項目を評価した。結果を表１および図３〜４に示す。 The following items were evaluated for the production of the aqueous pigment dispersion compositions of Examples 1-4 and Comparative Examples 1-6. The results are shown in Table 1 and FIGS.
［製造時間］
表１に示すように、本発明の製造方法では、比較例１、２で挙げた従来技術に比べて短い製造時間で、高い性能を有する水性顔料分散組成物を得ることが可能となった。
[Manufacturing time]
As shown in Table 1, according to the production method of the present invention, it is possible to obtain an aqueous pigment dispersion composition having high performance in a production time shorter than that of the prior arts described in Comparative Examples 1 and 2.
［粒径分布］
実施例２および比較例２で得られた水性顔料分散組成物について、光散乱による粒度分布計（ＭＩＣＲＯＴＲＡＣ ＵＰＡ：ＭＯＤＥＬ９３４０、ＵＰＡ日機装（株）製）を用いて、粒径分布を測定した。結果を図３（実施例２）および図４（比較例２）に示す。
[Particle size distribution]
About the water-based pigment dispersion composition obtained in Example 2 and Comparative Example 2, the particle size distribution was measured using a particle size distribution meter (MICROTRAC UPA: MODEL9340, manufactured by UPA Nikkiso Co., Ltd.) by light scattering. The results are shown in FIG. 3 (Example 2) and FIG. 4 (Comparative Example 2).
図３と図４の対比から明らかなように、微細な金属化合物を使用する高速せん断攪拌装置とメディア型分散装置を併用する実施例２では、粗大粒子の含有量が低減されているのに対して、高速せん断攪拌装置のみを使用しメディア型分散装置を併用しない比較例２では粗大粒子の含有量が多い。 As is clear from the comparison between FIG. 3 and FIG. 4, in Example 2 in which the high-speed shear stirrer using the fine metal compound and the media type dispersing device are used in combination, the content of coarse particles is reduced. In Comparative Example 2 in which only a high-speed shear stirrer is used and no media type dispersing device is used, the content of coarse particles is large.
［着色力］
着色力評価用白色水性顔料分散組成物として、酸化チタンの３０質量部と水性バインダー樹脂１の６質量部とを攪拌混合してビーズミル分散装置で練肉した後、さらに水性バインダー樹脂１および水の合計６４質量部で、系の粘度が０．５Ｐａ・ｓとなるように希釈して白色水性顔料分散組成物を得た。
[Coloring power]
As a white aqueous pigment dispersion composition for evaluating coloring power, 30 parts by mass of titanium oxide and 6 parts by mass of the
比較例１の水性顔料分散組成物１０質量部を前記着色力評価用白色水性顔料分散組成物１００質量部で希釈した時の色濃度と同一になるまで、実施例１、比較例３、５の各水性顔料分散組成物１０部を希釈するのに要した白色水性顔料分散組成物の量（質量部）により、着色力を評価した。 Until 10 parts by weight of the aqueous pigment dispersion composition of Comparative Example 1 was diluted with 100 parts by weight of the white aqueous pigment dispersion composition for evaluation of coloring power, the color density was the same as in Example 1, Comparative Examples 3 and 5. The coloring power was evaluated by the amount (part by mass) of the white aqueous pigment dispersion composition required to dilute 10 parts of each aqueous pigment dispersion composition.
また、比較例２の水性顔料分散組成物１０質量部に着色力評価用白色水性顔料分散組成物１００質量部で希釈した時の色濃度と同一になるまで実施例２〜４、比較例４、６の各水性顔料分散組成物１０部を希釈するのに要した白色水性顔料分散組成物の量（質量部）により、着色力を評価した。 Further, Examples 2 to 4 and Comparative Example 4 until the color density when diluted with 100 parts by mass of the white aqueous pigment dispersion composition for evaluating coloring power in 10 parts by mass of the aqueous pigment dispersion composition of Comparative Example 2 were the same. The coloring power was evaluated by the amount (part by mass) of the white aqueous pigment dispersion composition required to dilute 10 parts of each aqueous pigment dispersion composition of No. 6.
なお、同一の色濃度となるまでに、より多くの白色水性顔料分散組成物での希釈を必要とするものを、着色力が高いと判定する。 In addition, it determines with the coloring power being high that what needs dilution with more white aqueous pigment dispersion compositions until it becomes the same color density.
［流動性］
実施例１〜４、比較例１〜６の水性顔料分散組成物について、水性顔料分散組成物の初期粘度と、４０℃で７日間保存後の粘度の比率から粘度安定性を評価した。
Ａ：粘度比が２．０以下のもの
Ｂ：粘度比が２．０を超えるもの
[Liquidity]
For the aqueous pigment dispersion compositions of Examples 1 to 4 and Comparative Examples 1 to 6, the viscosity stability was evaluated from the ratio of the initial viscosity of the aqueous pigment dispersion composition and the viscosity after storage at 40 ° C. for 7 days.
A: Viscosity ratio is 2.0 or less B: Viscosity ratio exceeds 2.0
１ 分散部
２ ロータ
３ 原動機
４ 回転軸
５ ステータ
６ 孔
１０ 容器
１１ 混合物
DESCRIPTION OF
Claims (2)
硫酸バリウムが、高速せん断攪拌装置を用いて分散処理する際には予め配合されており、
前記分散処理において、(前記高速せん断攪拌装置のロータの外径)／（前記混合物を収納する容器内径の径）の比が０．１以上、０．４以下であり、前記高速せん断攪拌装置のロータを、周速１５〜２５ｍ／ｓｅｃで回転させることを特徴とする水性顔料分散組成物の製造方法（ただし、前記顔料が、顔料粉体に下記一般式
Barium sulfate is pre-mixed when dispersed using a high-speed shear stirrer,
In the dispersion treatment, the ratio of (the outer diameter of the rotor of the high-speed shear stirrer) / (the diameter of the inner diameter of the container storing the mixture) is 0.1 or more and 0.4 or less. method for producing an aqueous pigment dispersion composition characterized by rotating the rotor, at a peripheral speed 15~25m / sec (provided that the pigment is represented by the following general formula to the pigment powder
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| JP2006036857A JP2006036857A (en) | 2006-02-09 |
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| WO2012023609A1 (en) * | 2010-08-19 | 2012-02-23 | 株式会社明治 | Atomization device |
| US9358513B2 (en) * | 2013-04-10 | 2016-06-07 | Xerox Corporation | Method and system for magnetic actuated mixing |
| JP2015040790A (en) * | 2013-08-22 | 2015-03-02 | 荏原工業洗浄株式会社 | Treating method and device of oil in radiation controlled area |
| CN106964298A (en) * | 2015-11-18 | 2017-07-21 | 刘操 | A kind of circulating dual device for dispersing paint |
| CN111249941B (en) * | 2020-02-10 | 2021-09-14 | 深圳市尚水智能设备有限公司 | Impeller assembly for dispersing solid in liquid and solid-liquid mixing equipment using same |
| CN114149724B (en) * | 2021-12-27 | 2022-08-02 | 黄山联固新材料科技有限公司 | Non-ionic water-based epoxy resin emulsion and preparation method thereof |
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