JP5776549B2 - Dispersant for pigment and use thereof - Google Patents
Dispersant for pigment and use thereof Download PDFInfo
- Publication number
- JP5776549B2 JP5776549B2 JP2011518446A JP2011518446A JP5776549B2 JP 5776549 B2 JP5776549 B2 JP 5776549B2 JP 2011518446 A JP2011518446 A JP 2011518446A JP 2011518446 A JP2011518446 A JP 2011518446A JP 5776549 B2 JP5776549 B2 JP 5776549B2
- Authority
- JP
- Japan
- Prior art keywords
- calcium carbonate
- monomer
- meth
- dispersant
- copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000002270 dispersing agent Substances 0.000 title claims description 69
- 239000000049 pigment Substances 0.000 title description 24
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 199
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 98
- 239000006185 dispersion Substances 0.000 claims description 73
- 239000000178 monomer Substances 0.000 claims description 52
- 229920001577 copolymer Polymers 0.000 claims description 48
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 47
- 229920000642 polymer Polymers 0.000 claims description 37
- 238000006386 neutralization reaction Methods 0.000 claims description 34
- 238000010298 pulverizing process Methods 0.000 claims description 30
- 239000007864 aqueous solution Substances 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 17
- -1 amine salt Chemical class 0.000 claims description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 15
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical group NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 13
- 150000001412 amines Chemical class 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 7
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 claims description 7
- 229920002125 Sokalan® Polymers 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical group CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- 238000005227 gel permeation chromatography Methods 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 235000010216 calcium carbonate Nutrition 0.000 claims 12
- 239000013558 reference substance Substances 0.000 claims 1
- 239000002002 slurry Substances 0.000 description 58
- 239000002245 particle Substances 0.000 description 43
- 238000000034 method Methods 0.000 description 33
- 239000007787 solid Substances 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 238000004519 manufacturing process Methods 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 15
- 150000003839 salts Chemical class 0.000 description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- 239000001023 inorganic pigment Substances 0.000 description 12
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 150000007514 bases Chemical class 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000005498 polishing Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 7
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 239000007870 radical polymerization initiator Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000001771 impaired effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 150000003512 tertiary amines Chemical class 0.000 description 4
- 238000001238 wet grinding Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-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 Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 230000008719 thickening Effects 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- KJRCEJOSASVSRA-UHFFFAOYSA-N propane-2-thiol Chemical compound CC(C)S KJRCEJOSASVSRA-UHFFFAOYSA-N 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 1
- ONQBOTKLCMXPOF-UHFFFAOYSA-N 1-ethylpyrrolidine Chemical compound CCN1CCCC1 ONQBOTKLCMXPOF-UHFFFAOYSA-N 0.000 description 1
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 1
- CBQFBEBEBCHTBK-UHFFFAOYSA-N 1-phenylprop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)C(C=C)C1=CC=CC=C1 CBQFBEBEBCHTBK-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- HQOVXPHOJANJBR-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)butane Chemical compound CC(C)(C)OOC(C)(CC)OOC(C)(C)C HQOVXPHOJANJBR-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-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
- XKBHBVFIWWDGQX-UHFFFAOYSA-N 2-bromo-3,3,4,4,5,5,5-heptafluoropent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(Br)=C XKBHBVFIWWDGQX-UHFFFAOYSA-N 0.000 description 1
- MIRQGKQPLPBZQM-UHFFFAOYSA-N 2-hydroperoxy-2,4,4-trimethylpentane Chemical compound CC(C)(C)CC(C)(C)OO MIRQGKQPLPBZQM-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical compound OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 description 1
- OBNZQBVPDZWAEB-UHFFFAOYSA-N 2-phenylprop-1-ene-1-sulfonic acid Chemical compound OS(=O)(=O)C=C(C)C1=CC=CC=C1 OBNZQBVPDZWAEB-UHFFFAOYSA-N 0.000 description 1
- VFTWMPNBHNNMAV-UHFFFAOYSA-N 2-tert-butylperoxy-1,4-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=C(C(C)C)C(OOC(C)(C)C)=C1 VFTWMPNBHNNMAV-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- BYLRZCIZXYKLQL-UHFFFAOYSA-N 3-[3-(3-sulfopropoxycarbonyl)but-3-enoyloxy]propane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCOC(=O)CC(=C)C(=O)OCCCS(O)(=O)=O BYLRZCIZXYKLQL-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- HTLZVHNRZJPSMI-UHFFFAOYSA-N N-ethylpiperidine Chemical compound CCN1CCCCC1 HTLZVHNRZJPSMI-UHFFFAOYSA-N 0.000 description 1
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- LAWOZCWGWDVVSG-UHFFFAOYSA-N dioctylamine Chemical compound CCCCCCCCNCCCCCCCC LAWOZCWGWDVVSG-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [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])* 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002356 laser light scattering Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 1
- UQKAOOAFEFCDGT-UHFFFAOYSA-N n,n-dimethyloctan-1-amine Chemical compound CCCCCCCCN(C)C UQKAOOAFEFCDGT-UHFFFAOYSA-N 0.000 description 1
- MJCJUDJQDGGKOX-UHFFFAOYSA-N n-dodecyldodecan-1-amine Chemical compound CCCCCCCCCCCCNCCCCCCCCCCCC MJCJUDJQDGGKOX-UHFFFAOYSA-N 0.000 description 1
- RIVIDPPYRINTTH-UHFFFAOYSA-N n-ethylpropan-2-amine Chemical compound CCNC(C)C RIVIDPPYRINTTH-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 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
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229940070710 valerate Drugs 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene 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
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/45—Anti-settling agents
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、顔料及び各種無機粒子用分散剤に関する。より好ましくは炭酸カルシウム用分散剤であって、固形分７０％を超える高濃度顔料スラリーや、特に粒径の小さな顔料スラリーを製造するために使用した場合に、分散安定化効果が高く、微粒子状で、良好な流動性を維持しながら分散させることができ、スラリーの経時的な増粘やｐＨの低下を抑制しながら長期間にわたって安定に分散させることができる（メタ）アクリル酸系（共）重合体の顔料用分散剤を提供するものである。 The present invention relates to a pigment and a dispersant for various inorganic particles. More preferably, it is a dispersing agent for calcium carbonate, and when used to produce a high-concentration pigment slurry having a solid content exceeding 70%, or particularly a pigment slurry having a small particle size, the dispersion stabilizing effect is high, and the particulate form (Meth) acrylic acid (co) can be dispersed while maintaining good fluidity, and can be stably dispersed over a long period of time while suppressing increase in slurry viscosity and pH decrease over time. A dispersant for a pigment of a polymer is provided.
従来、炭酸カルシウム、カオリン、サチンホワイト、酸化チタン、タルクなどの無機顔料を水中に安定に分散させるための分散剤として、アクリル酸（塩）の単独重合体及びアクリル酸（塩）と他の共重合性単量体との共重合体が知られている。
特許文献１（特開昭５４−８２４１６）においては、ポリカルボン酸（塩）からなる分散剤で顔料の分散を行っている。特許文献２（特開昭４９−１３０９１５）においては、カルボン酸（塩）を含む単量体、炭素数が１〜４である（メタ）アクリル酸エステル単量体の共重合体から成る分散剤で顔料の分散を行っている。特許文献３（特開２００５−３０７０２３）においては、カルボン酸（塩）を含む単量体、その他の単量体の共重合体中の末端基の一部が、炭素数１〜３のアルコール由来の官能基である分散剤で顔料の分散を行っている。Conventionally, as a dispersant for stably dispersing inorganic pigments such as calcium carbonate, kaolin, satin white, titanium oxide, and talc in water, homopolymers of acrylic acid (salt) and acrylic acid (salt) and other co-polymers are used. Copolymers with polymerizable monomers are known.
In Patent Document 1 (Japanese Patent Laid-Open No. 54-82416), the pigment is dispersed with a dispersant composed of a polycarboxylic acid (salt). In Patent Document 2 (Japanese Patent Laid-Open No. 49-130915), a dispersant comprising a monomer containing a carboxylic acid (salt) and a copolymer of (meth) acrylic acid ester monomers having 1 to 4 carbon atoms. The pigment is dispersed. In Patent Document 3 (Japanese Patent Application Laid-Open No. 2005-307023), a monomer containing a carboxylic acid (salt) and a part of terminal groups in a copolymer of other monomers are derived from an alcohol having 1 to 3 carbon atoms. The pigment is dispersed with a dispersant that is a functional group.
しかしながら、近年では従来と比較してより高濃度の分散や、微粒子状の分散が求められており、従来以上に無機顔料スラリーに対する経時増粘の抑制が要求されるようになっている。
とくに、粒径の小さな無機顔料などは、表面積が増大するために粒子間の相互作用が強くなり、粒子同士の凝集が起こりやすくなることで、スラリー粘度が増大する傾向にある。
また、水系中で得られるスラリーは、中性以下の領域においては雑菌が繁殖することにより腐敗が進行し、商品価値が損なわれるため、高いｐＨ値を維持しなければならない。However, in recent years, there has been a demand for higher concentration dispersion and fine particle dispersion as compared with the prior art, and the suppression of thickening over time with respect to inorganic pigment slurries has been demanded more than ever.
In particular, an inorganic pigment having a small particle size tends to increase the slurry viscosity because the surface area increases and the interaction between particles becomes strong and the particles tend to aggregate.
In addition, the slurry obtained in the aqueous system must maintain a high pH value because spoilage progresses due to the propagation of germs in a neutral or lower region and the commercial value is impaired.
このような要求に対して、上記に示したような従来技術の分散剤では、満足できる性能が得られていない。例えば、特許文献１に記載されたポリカルボン酸（塩）からなる分散剤や、特許文献２に記載されたカルボン酸（塩）を含む単量体と炭素数が１〜４である（メタ）アクリル酸エステル単量体との共重合体から成る分散剤では、経時的な分散液粘度の増大を十分に抑制しているとは言い難く、また、特許文献３に記載された無機顔料分散剤では、樹脂構成単位や中和剤について特に最適化されておらず、無機顔料分散剤として分散安定化に十分適合しているとは言い難く、ｐＨに関する記述も一切なされていない。 In response to such demands, the conventional dispersants as described above do not provide satisfactory performance. For example, the dispersing agent which consists of the polycarboxylic acid (salt) described in patent document 1, the monomer containing the carboxylic acid (salt) described in patent document 2, and C1-C4 (meta) In the dispersant composed of a copolymer with an acrylate monomer, it is difficult to say that the increase in dispersion viscosity over time is sufficiently suppressed, and the inorganic pigment dispersant described in Patent Document 3 However, the resin structural unit and the neutralizing agent are not particularly optimized, and it is difficult to say that they are well suited for dispersion stabilization as an inorganic pigment dispersant, and there is no description regarding pH.
本発明の目的は、近年の分散剤に要求されている、高いｐＨの領域において、粒径の小さな高濃度無機顔料スラリーの経時分散安定効果ならびにスラリーｐＨ低下抑制効果に優れる分散剤を提供することにある。 An object of the present invention is to provide a dispersant that is excellent in the effect of stabilizing dispersion over time of a high-concentration inorganic pigment slurry having a small particle size and the effect of suppressing the decrease in slurry pH, which is required for a dispersant in recent years, in a high pH region. It is in.
本発明者らは、上記課題を解決するために鋭意検討した結果、下記の構成を持つ分散剤が、そのｐＨが低いにもかかわらず、無機顔料、特に炭酸カルシウムの分散に使用した場合に、驚くべきことに分散液スラリーを強アルカリ領域に維持できるのみならず、経時安定性やスラリーの流動性、ろ過性にも優れることを見出し、本発明に到達した。 As a result of intensive studies to solve the above problems, the present inventors have found that a dispersant having the following constitution is used for dispersing inorganic pigments, particularly calcium carbonate, despite its low pH. Surprisingly, it has been found that not only can the dispersion slurry be maintained in the strong alkali region, but also stability over time, fluidity of the slurry, and filterability are excellent, and the present invention has been achieved.
すなわち、本発明の第一は、α,β-不飽和カルボン酸単量体（ａ）の重合体（Ａ）、又は、α,β-不飽和カルボン酸単量体（ａ）単位８０〜９９モル％、及び（メタ）アクリル酸エステル単量体（ｂ）とポリアルキレングリコールの（メタ）アクリル酸エステルの単量体（ｃ）の両方若しくは片方の単位１〜２０モル％（ただし（ａ）+（ｂ）+（ｃ）=１００モル％になる）よりなる共重合体（Ｂ）のいずれかの部分中和物であって、酸基の２０〜３０モル％がアンモニア又は有機アミンで部分中和されたものであり、さらに前記α,β-不飽和カルボン酸単量体（ａ）に由来するカルボキシル基の５０〜７０モル％が遊離の酸基となるよう中和することを特徴とする、３９．９〜４３．４質量％水溶液のｐＨが６．０以下の無機顔料用分散剤である。
また、本発明の第二は、共重合体（Ｂ）を構成する単量体（ｂ）単位が、炭素数１〜８である（メタ）アクリル酸エステル、単量体（ｃ）単位が下記一般式（Ｉ）で表されるポリアルキレングリコールの（メタ）アクリル酸エステル、である第一の発明に記載の炭酸カルシウム用分散剤である。
また、本発明の第三は、重合体（Ａ）又は共重合体（Ｂ）の単量体（ａ）単位中の酸基が有機アミン塩の形態であることを特徴とする第一又は第二の発明に記載の炭酸カルシウム用分散剤である。
また、本発明の第四は、重合体（Ａ）又は共重合体（Ｂ）のポリアクリル酸を基準物質としたゲルパーミエーションクロマトグラフィーによる重量平均分子量（Ｍｗ）が４０００〜８０００であって、Ｍｗ／Ｍｎ（重量平均分子量／数平均分子量）が２．７以下、である第一〜第三の発明のいずれかに記載の炭酸カルシウム用分散剤である。
また、本発明の第五は、共重合体（Ｂ）であることを特徴とする第一〜第四の発明のいずれかに記載の炭酸カルシウム用分散剤である。
また、本発明の第六は、共重合体（Ｂ）を構成する単量体（ａ）単位がアクリル酸であり、単量体（ｂ）単位がアクリル酸ブチル、単量体（ｃ）単位が一般式（１）中のＲ2がプロピレン基であるポリプロピレングリコールモノ（メタ）アクリレート、である第一〜第五の発明のいずれかに記載の炭酸カルシウム用分散剤である。
また、本発明の第七は、有機アミンがモノエタノールアミンである第一〜第六の発明のいずれかに記載の炭酸カルシウム用分散剤である。
また、本発明の第八は、第一〜第七の発明のいずれかに記載の炭酸カルシウム用分散剤を用いて湿式粉砕により調整した、ｐＨ＝９．５以上の炭酸カルシウム分散液である。
また、本発明の第九は、炭酸カルシウムが重質炭酸カルシウムである第八の発明に記載の炭酸カルシウム分散液である。
That is, the first of the present invention is a polymer (A) of α, β-unsaturated carboxylic acid monomer (a) or α, β-unsaturated carboxylic acid monomer (a) units 80 to 99. 1% to 20% by mole of (meth) acrylic acid ester monomer (b) and polyalkylene glycol (meth) acrylic acid ester monomer (c) or one or both units (however, (a) + (B) + (c) = 100 mol%) of the partially neutralized product of the copolymer (B), wherein 20 to 30 mol% of the acid groups are partially ammonia or organic amine It is neutralized and further neutralized so that 50 to 70 mol% of the carboxyl groups derived from the α, β-unsaturated carboxylic acid monomer (a) are free acid groups. The dispersant for inorganic pigments has a pH of 39.9 to 43.4 mass% aqueous solution of 6.0 or less.
Moreover, the 2nd of this invention is a (meth) acrylic acid ester whose monomer (b) unit which comprises a copolymer (B) is C1-C8, and a monomer (c) unit is the following. The dispersant for calcium carbonate according to the first invention, which is a (meth) acrylic acid ester of a polyalkylene glycol represented by the general formula (I).
A third aspect of the present invention is that the acid group in the monomer (a) unit of the polymer (A) or the copolymer (B) is in the form of an organic amine salt. It is a dispersing agent for calcium carbonate as described in two inventions.
Moreover, the 4th of this invention is the weight average molecular weight (Mw) by the gel permeation chromatography which used the polyacrylic acid of the polymer (A) or the copolymer (B) as a reference material, and is 4000-8000, The dispersant for calcium carbonate according to any one of the first to third inventions, wherein Mw / Mn (weight average molecular weight / number average molecular weight) is 2.7 or less.
The fifth aspect of the present invention is the calcium carbonate dispersant according to any one of the first to fourth aspects, which is a copolymer (B).
The sixth aspect of the present invention is that the monomer (a) unit constituting the copolymer (B) is acrylic acid, the monomer (b) unit is butyl acrylate, and the monomer (c) unit. Is a dispersant for calcium carbonate according to any one of the first to fifth inventions, wherein R 2 in the general formula (1) is a polypropylene glycol mono (meth) acrylate having a propylene group.
A seventh aspect of the present invention is the calcium carbonate dispersant according to any one of the first to sixth aspects, wherein the organic amine is monoethanolamine.
The eighth aspect of the present invention is a calcium carbonate dispersion having a pH of 9.5 or more, which is adjusted by wet pulverization using the dispersant for calcium carbonate according to any one of the first to seventh aspects.
A ninth aspect of the present invention is the calcium carbonate dispersion according to the eighth aspect, wherein the calcium carbonate is heavy calcium carbonate.
本発明の（メタ）アクリル酸（塩）系（共）重合体は、主に、炭酸カルシウム、カオリン、サチンホワイト、酸化チタン、タルク、リン酸カルシウム、セメント、石膏などの無機顔料の分散剤として使用するものであるが、特に炭酸カルシウムに用いたときに効果を発揮する。
すなわち、本発明の（メタ）アクリル酸（塩）系（共）重合体からなる炭酸カルシウム用分散剤を用いて炭酸カルシウムの分散液を調整すると、炭酸カルシウムの濃度が高くても、また炭酸カルシウムの粒径が極めて小さくても、粘度が低くて取り扱い性に優れ、さらに分散液の粘度が経時的に増粘することなく、低い粘度を長期にわたって維持することができ、凝集のない経時安定性に優れる炭酸カルシウム分散液を円滑に得ることができる。
また、本発明の（メタ）アクリル酸（塩）系（共）重合体からなる炭酸カルシウム用分散剤を用いて炭酸カルシウムの分散液を調整すると、上記のような低粘度分散液が得られるほか、流動性、ろ過性などのハンドリング性に優れる炭酸カルシウム分散液を得ることもでき、さらに炭酸カルシウム分散液のｐＨに対しては、細菌の繁殖を抑制できる強アルカリ領域を長期間保持することができるため、特に有用である。
本発明の炭酸カルシウム用分散剤は、上記した特性を活かして、製紙工業、プラスチック、ゴム、塗料、インキ、接着剤、シーラントなどに用いられる炭酸カルシウムの分散安定剤として有効に使用することができる。The (meth) acrylic acid (salt) -based (co) polymer of the present invention is mainly used as a dispersant for inorganic pigments such as calcium carbonate, kaolin, satin white, titanium oxide, talc, calcium phosphate, cement and gypsum. Although effective, it is particularly effective when used in calcium carbonate.
That is, when a calcium carbonate dispersion is prepared using a calcium carbonate dispersant comprising the (meth) acrylic acid (salt) -based (co) polymer of the present invention, the calcium carbonate concentration is high even when the calcium carbonate concentration is high. Even when the particle size of the particles is extremely small, the viscosity is low and the handling is excellent, and the viscosity of the dispersion does not increase over time, so that a low viscosity can be maintained over a long period of time, and there is no aggregation over time. Can be obtained smoothly.
In addition, by adjusting the calcium carbonate dispersion using the calcium carbonate dispersant comprising the (meth) acrylic acid (salt) -based (co) polymer of the present invention, a low-viscosity dispersion as described above can be obtained. In addition, it is possible to obtain a calcium carbonate dispersion having excellent handling properties such as fluidity and filterability. Furthermore, the pH of the calcium carbonate dispersion can maintain a strong alkali region that can suppress bacterial growth for a long period of time. It is particularly useful because it can.
The dispersant for calcium carbonate of the present invention can be effectively used as a dispersion stabilizer for calcium carbonate used in the paper industry, plastics, rubber, paints, inks, adhesives, sealants, etc., taking advantage of the above-described properties. .
以下、本発明の実施形態について詳細に説明する。
本発明において、α，β−不飽和カルボン酸（ａ）としては、例えば（メタ）アクリル酸、マレイン酸、フマル酸、イタコン酸、クロトン酸、シトラコン酸などが挙げられる。無水フタル酸や無水イタコン酸をアルキルアルコールでハーフエステル化したものでも良い。これらは単独で使用しても良く、また２種以上を併用しても良い。
これらのうち好ましいものは、（メタ）アクリル酸である。なお、本発明において（メタ）アクリル酸とはアクリル酸またはメタクリル酸のことをいう。より好ましくは、スラリーの安定性と重合のし易さからアクリル酸である。Hereinafter, embodiments of the present invention will be described in detail.
In the present invention, examples of the α, β-unsaturated carboxylic acid (a) include (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, and citraconic acid. Phthalic anhydride or itaconic anhydride may be half-esterified with alkyl alcohol. These may be used alone or in combination of two or more.
Of these, preferred is (meth) acrylic acid. In the present invention, (meth) acrylic acid means acrylic acid or methacrylic acid. More preferred is acrylic acid because of the stability of the slurry and ease of polymerization.
本発明の（メタ）アクリル酸エステル単量体（ｂ）としては、アルキル基が炭素数１〜２０の直鎖状、分岐状、環状の（メタ）アクリル酸アルキル類：例えば（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、（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）アクリル酸ステアリル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸イソボルニル等が挙げられる。
また、（メタ）アクリル酸ヒドロキシアルキル類：例えば（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸３−ヒドロキシプロピル、（メタ）アクリル酸４−ヒドロキシブチル、（メタ）アクリル酸ω−ヒドロキシポリアルキレングリコール（ｎ＝２〜３０）等が挙げられる。
さらに、（メタ）アクリル酸３−スルホプロピル、モノ（２−ヒドロキシエチルアクリレート）アシッドホスフェート、モノ（２−ヒドロキシエチルメタクリレート）アシッドホスフェート、モノ（２−ヒドロキシプロピルアクリレート）アシッドホスフェート、モノ（３−ヒドロキシエチルアクリレート）アシッドホスフェート、モノ（３−ヒドロキシエチルメタクリレート）アシッドホスフェート等のスルホン酸やリン酸基含有（メタ）アクリル酸エステルも挙げられる。
炭酸カルシウムの分散性と、スラリーの安定性の面から、好ましくは、炭素数１〜８の（メタ）アクリル酸アルキル類であり、より好ましくはアクリル酸ブチルである。As the (meth) acrylic acid ester monomer (b) of the present invention, the alkyl group is a linear, branched or cyclic alkyl (meth) acrylate having 1 to 20 carbon atoms: for example, (meth) acrylic acid Methyl, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic Examples include cyclohexyl acid and isobornyl (meth) acrylate.
Also, hydroxyalkyl (meth) acrylates: for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, ω-hydroxy (meth) acrylate Examples include polyalkylene glycol (n = 2 to 30).
Further, 3-sulfopropyl (meth) acrylate, mono (2-hydroxyethyl acrylate) acid phosphate, mono (2-hydroxyethyl methacrylate) acid phosphate, mono (2-hydroxypropyl acrylate) acid phosphate, mono (3-hydroxy Examples thereof also include sulfonic acid and phosphoric acid group-containing (meth) acrylic acid esters such as ethyl acrylate) acid phosphate and mono (3-hydroxyethyl methacrylate) acid phosphate.
From the viewpoint of the dispersibility of calcium carbonate and the stability of the slurry, alkyl (meth) acrylates having 1 to 8 carbon atoms are preferred, and butyl acrylate is more preferred.
ポリアルキレングリコールの（メタ）アクリル酸エステルの単量体（ｃ）としては、下記一般式（１）で表されるものが好ましい。
ポリアルキレングリコール鎖の分子量は１００〜２０００が好ましい。より好ましくは、一般式（１）中のＲ２がプロピレン基であるポリプロピレングリコールモノ（メタ）アクリレートである。As the monomer (c) of the (meth) acrylic acid ester of polyalkylene glycol, those represented by the following general formula (1) are preferable.
The molecular weight of the polyalkylene glycol chain is preferably 100 to 2000. More preferably, it is a polypropylene glycol mono (meth) acrylate in which R2 in the general formula (1) is a propylene group.
本発明においては、共重合体の物性を損なわない範囲でその他の単量体を共重合することもできる。このような単量体としては、特に限定されないが、例えば、アミド含有エチレン性不飽和単量体：（メタ）アクリルアミド、Ｎ−メチロール（メタ）アクリルアミド等、芳香族エチレン性不飽和単量体：スチレン、α−メチルスチレン、ビニルトルエン、ヒドロキシスチレン等のスチレン類、ビニルナフタレン類等、スルホン酸基含有単量体：（メタ）アリルスルホン酸、スチレンスルホン酸、α-メチルスチレンスルホン酸、イソプレンスルホン酸、ビニルトルエンスルホン酸、（メタ）アリルオキシベンゼンスルホン酸、（メタ）アリルオキシ２−ヒドロキシプロピルスルホン酸、イタコン酸ビス（３−スルホプロピル）等、が挙げられる。 In the present invention, other monomers can be copolymerized as long as the physical properties of the copolymer are not impaired. Such a monomer is not particularly limited. For example, an aromatic ethylenically unsaturated monomer such as an amide-containing ethylenically unsaturated monomer: (meth) acrylamide, N-methylol (meth) acrylamide, or the like: Styrenes such as styrene, α-methylstyrene, vinyltoluene and hydroxystyrene, vinylnaphthalene and the like, sulfonic acid group-containing monomers: (meth) allylsulfonic acid, styrenesulfonic acid, α-methylstyrenesulfonic acid, isoprenesulfone Acid, vinyltoluenesulfonic acid, (meth) allyloxybenzenesulfonic acid, (meth) allyloxy 2-hydroxypropylsulfonic acid, bis (3-sulfopropyl) itaconate, and the like.
本発明の分散剤には、単量体（ａ）からなる重合体（Ａ）または単量体（ａ）と単量体（ｂ）及び／又は単量体（ｃ）からなる共重合体（Ｂ）が使用することができる。共重合体（Ｂ）の構成は、（ａ）が８０〜９９モル％、（ｂ）及び／又は（ｃ）が１〜２０モル％（（ａ）＋（ｂ）＋（ｃ）＝１００モル％）である。炭酸カルシウムの分散性、スラリーの安定性、流動性やろ過性のバランスから共重合体（Ｂ）が好ましい。共重合体（Ｂ）において、（ｂ）及び／又は（ｃ）が１モル％未満では、前記のバランスが十分でなく、８０モル％を越えると高ｐＨ領域での安定性が不十分になる。 The dispersant of the present invention includes a polymer (A) comprising the monomer (a) or a copolymer comprising the monomer (a) and the monomer (b) and / or the monomer (c) ( B) can be used. The composition of the copolymer (B) is that (a) is 80 to 99 mol%, (b) and / or (c) is 1 to 20 mol% ((a) + (b) + (c) = 100 mol) %). The copolymer (B) is preferred from the balance of calcium carbonate dispersibility, slurry stability, fluidity and filterability. In copolymer (B), when (b) and / or (c) is less than 1 mol%, the above balance is not sufficient, and when it exceeds 80 mol%, the stability in the high pH region becomes insufficient. .
本発明の重合体（Ａ）または共重合体（Ｂ）の製造方法は特に限定されず、溶液重合、乳化重合、懸濁重合などのいずれも使用することができる。そのうちでも好ましくは溶液重合である。
溶液重合の溶剤としては、水、アルコール類（メタノール、エタノール、イソプロパノール等）、ケトン類（アセトン、メチルエチルケトン等）、エーテル類（テトラヒドロフラン等）、脂肪族炭化水素類（ヘキサン、ヘプタン等）、芳香族炭化水素類（トルエン、キシレン等）及びこれらの混合物等が挙げられるが、これらのうち好ましいものは、アルコールと水の混合溶剤であり、更に好ましくはイソプロパノールと水の混合溶剤である。
アルコールと水の混合溶剤の混合比率としては、質量比で、アルコール／水＝９０／１０〜１０／９０であることが好ましく、７０／３０〜３０／７０であることがより好ましい。水の割合が９０質量％を超えると、単量体（ｂ）及び／又は（ｃ）に属するうちのいくつかは溶解し難くなるため好ましくない。一方、水の割合が１０質量％未満であると、分散剤として使用する際にアルコールを水に置換する必要があり、コストと手間が掛かるため好ましくない。The production method of the polymer (A) or copolymer (B) of the present invention is not particularly limited, and any of solution polymerization, emulsion polymerization, suspension polymerization and the like can be used. Of these, solution polymerization is preferred.
Solvents for solution polymerization include water, alcohols (methanol, ethanol, isopropanol, etc.), ketones (acetone, methyl ethyl ketone, etc.), ethers (tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, heptane, etc.), aromatic Examples include hydrocarbons (toluene, xylene, etc.) and mixtures thereof. Among these, preferred is a mixed solvent of alcohol and water, and more preferred is a mixed solvent of isopropanol and water.
The mixing ratio of the mixed solvent of alcohol and water is, by mass ratio, preferably alcohol / water = 90/10 to 10/90, and more preferably 70/30 to 30/70. When the ratio of water exceeds 90% by mass, some of the monomers belonging to the monomer (b) and / or (c) are difficult to dissolve, which is not preferable. On the other hand, if the ratio of water is less than 10% by mass, it is not preferable because alcohol needs to be replaced with water when used as a dispersant, which is costly and labor intensive.
本発明の重合体（Ａ）または共重合体（Ｂ）の製造に用いるラジカル重合開始剤としては、一般に用いられている過酸化物系のラジカル重合開始剤を用いることができる。具体例としては、過硫酸ナトリウム、過硫酸カリウム、過硫酸アンモニウムなどの過硫酸塩類、ｔ−ブチルハイドロパーオキサイド、クメンハイドロパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、ｐ−メンタンハイドロパーオキサイド、２，５−ジメチルヘキサン−２，５−ジハイドロパーオキサイド、１，１，３，３−テトラメチルブチルハイドロパーオキサイドなどのハイドロパーオキサイド類、過酸化水素などの水溶性過酸化物；メチルエチルケトンパーオキサイド、シクロヘキサノンパーオキサイドなどのケトンパーオキサイド類、ジ−ｔ−ブチルパーオキサイド、ｔ−ブチルクミルパーオキサイド、ジクミルパーオキサイド、α，α'−ビス（ｔ−ブチルパーオキシ）−ｐ−ジイソプロピルベンゼン、α，α'−ビス（ｔ−ブチルパーオキシ）−ｎ−ジイソプロピルヘキシンなどのジアルキルパーオキサイド類、ｔ−ブチルパーオキシアセテート、ｔ−ブチルパーオキシラウレート、ｔ−ブチルパーオキシベンゾエート、ジ−ｔ−ブチルパーオキシイソフタレート、２，５−ジメチル−２，５−ジ（ベンゾイルパーオキシ）ヘキサン、ｔ−ブチルパーオキシイソプロピルカーボネートなどのパーオキシエステル類、ｎ−ブチル−４，４−ビス（ｔ−ブチルパーオキシ）バレエート、２，２−ビス（ｔ−ブチルパーオキシ）ブタンなどのパーオキシケタール類、ジベンゾイルパーオキサイドなどのジアシルパーオキサイド等の油溶性の過酸化物などを挙げることができる。
上記した過酸化物系のラジカル重合開始剤は１種類のみを使用してもまたは２種以上を併用してもよい。また、上記した過酸化物系ラジカル重合開始剤のうちでは、分子量の制御が行い易い、分解温度の低い過酸化水素や過硫酸塩類系の過酸化物であることがより好ましい。As the radical polymerization initiator used for the production of the polymer (A) or copolymer (B) of the present invention, a peroxide radical polymerization initiator generally used can be used. Specific examples include persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 2,5- Hydroperoxides such as dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, water-soluble peroxides such as hydrogen peroxide; methyl ethyl ketone peroxide, cyclohexanone peroxide Ketone peroxides such as oxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α, α′-bis (t-butylperoxy) -p-diisopropylbenzene, α, α '-Bi Dialkyl peroxides such as bis (t-butylperoxy) -n-diisopropylhexyne, t-butylperoxyacetate, t-butylperoxylaurate, t-butylperoxybenzoate, di-t-butylperoxy Peroxyesters such as isophthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyisopropyl carbonate, n-butyl-4,4-bis (t-butylperoxy) ) Peroxyketals such as valerate, 2,2-bis (t-butylperoxy) butane, and oil-soluble peroxides such as diacyl peroxide such as dibenzoyl peroxide.
The above peroxide-based radical polymerization initiators may be used alone or in combination of two or more. Of the peroxide radical polymerization initiators described above, hydrogen peroxide and persulfate peroxides having a low decomposition temperature that can easily control the molecular weight are more preferable.
ラジカル重合開始剤の使用量は特に制限されないが、重合体（Ａ）又は共重合体（Ｂ）の製造に用いる全単量体の合計質量に基づいて、０．１０〜１５質量％、特に０．１〜５質量％の割合で使用することが好ましい。ラジカル重合開始剤の使用量が少なすぎると、重合率が低下し、一方、多すぎると重合後でも、重合体（Ａ）又は共重合体（Ｂ）の中に残留して、安定性を損なったり、分散剤としての性能に悪影響を及ぼすことがある。 Although the usage-amount of a radical polymerization initiator is not restrict | limited in particular, 0.10-15 mass% based on the total mass of all the monomers used for manufacture of a polymer (A) or a copolymer (B), especially 0 It is preferable to use it in the ratio of 1-5 mass%. If the amount of radical polymerization initiator used is too small, the polymerization rate decreases, while if too large, the polymer (A) or copolymer (B) remains in the polymer (A) or copolymer (B) even after polymerization, and the stability is impaired. Or may adversely affect the performance as a dispersant.
重合体（Ａ）又は共重合体（Ｂ）の製造に当っては、分子量を調整するために連鎖移動剤を重合系に適量添加してもよい。使用可能な連鎖移動剤としては、例えば、亜リン酸ナトリウム、次亜リン酸ナトリウム、重亜硫酸ナトリウム、メルカプト酢酸、メルカプトプロピオン酢酸、２−プロパンチオール、２−メルカプトエタノール、チオフェノール、ドデシルメルカプタン、チオグリセロール、チオリンゴ酸などを挙げることができる。 In producing the polymer (A) or the copolymer (B), an appropriate amount of a chain transfer agent may be added to the polymerization system in order to adjust the molecular weight. Usable chain transfer agents include, for example, sodium phosphite, sodium hypophosphite, sodium bisulfite, mercaptoacetic acid, mercaptopropionic acetic acid, 2-propanethiol, 2-mercaptoethanol, thiophenol, dodecyl mercaptan, thio Examples thereof include glycerol and thiomalic acid.
重合体（Ａ）又は共重合体（Ｂ）を製造する際の重合温度は、５０〜１５０℃が好ましく、７０〜１００℃がより好ましい。重合温度が５０℃よりも低いと共重合率が低下し易く、一方、１５０℃よりも高いと、単量体（ａ）がダイマー化反応を起こしたり単量体（ｂ）や（ｃ）が熱分解したりする。また、生成した重合体（Ａ）又は共重合体（Ｂ）自身の熱分解などが生ずる恐れがある。
重合時間は、３〜２０時間、特に３〜１０時間程度が好ましい。50-150 degreeC is preferable and, as for the polymerization temperature at the time of manufacturing a polymer (A) or a copolymer (B), 70-100 degreeC is more preferable. When the polymerization temperature is lower than 50 ° C., the copolymerization rate tends to decrease. On the other hand, when the polymerization temperature is higher than 150 ° C., the monomer (a) causes a dimerization reaction or the monomers (b) and (c) Pyrolysis. Moreover, there exists a possibility that the thermal decomposition of the produced | generated polymer (A) or copolymer (B) itself may arise.
The polymerization time is preferably 3 to 20 hours, particularly about 3 to 10 hours.
重合体（Ａ）又は共重合体（Ｂ）を製造するための上記した重合反応は、重合前および重合段階では単量体（ａ）の酸基の少なくとも４０モル％以上、更には７０〜１００モル％、特に９０〜１００モル％が未中和の状態であるようにして重合を行うことが、重合反応が均一に進行する点から好ましい。 The above-described polymerization reaction for producing the polymer (A) or the copolymer (B) is performed at least 40 mol% or more of the acid groups of the monomer (a) before polymerization and in the polymerization stage, and more preferably 70-100. The polymerization is preferably carried out so that the mol%, particularly 90 to 100 mol%, is in an unneutralized state from the viewpoint that the polymerization reaction proceeds uniformly.
重合体（Ａ）又は共重合体（Ｂ）の重量平均分子量（Ｍｗ）（ポリアクリル酸を標準物質とした、ゲルパーミエーションクロマトグラフィーによる測定値）は、通常２，０００〜１０，０００であり、好ましくは４，０００〜８，０００である。重量平均分子量（Ｍｗ）が２０００未満であると、炭酸カルシウムへの経時的な吸着力が低くなり、一方、Ｍｗが１００００を越えると、炭酸カルシウム粒子間の結合（架橋）を引き起こし、炭酸カルシウムスラリーの経時的な増粘を引き起こすので好ましくない。
また、重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）の比で表される分子量分布（Ｍｗ／Ｍｎ）が２．７以下であることが好ましく、２．５以下であることがより好ましく、２．４以下であることが更に好ましい。Ｍｗ／Ｍｎが２．７を超えると、炭酸カルシウムへの経時的な吸着性の低い低分子量成分の量が増加し、また同時に炭酸カルシウム粒子同士の結合（架橋）を引き起こす原因となる高分子量成分の量も増加するため、結果として炭酸カルシウムスラリーの経時的な増粘を引き起こしやすくなるので、好ましくない。The weight average molecular weight (Mw) of the polymer (A) or copolymer (B) (measured by gel permeation chromatography using polyacrylic acid as a standard substance) is usually 2,000 to 10,000. , Preferably 4,000 to 8,000. When the weight average molecular weight (Mw) is less than 2000, the adsorption power to calcium carbonate with time decreases, whereas when the Mw exceeds 10,000, the calcium carbonate particles are bonded (crosslinked), resulting in a calcium carbonate slurry. This is not preferable because it causes thickening over time.
Further, the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is preferably 2.7 or less, more preferably 2.5 or less, More preferably, it is 2.4 or less. When Mw / Mn exceeds 2.7, the amount of low molecular weight components having low adsorptivity to calcium carbonate with time increases, and at the same time, high molecular weight components that cause the bonding (crosslinking) of calcium carbonate particles to each other. This also increases the amount of water, and as a result, it tends to cause thickening of the calcium carbonate slurry over time, which is not preferable.
本発明の（メタ）アクリル系（共）重合体塩を得る方法としては、上記で得られる重合体（Ａ）又は共重合体（Ｂ）を含む溶液から、必要により蒸留、真空蒸留、乾燥などの操作によって有機溶媒を除去した後、重合体（Ａ）又は共重合体（Ｂ）を構成する単量体単位（ａ）が有するカルボキシル基を塩基性化合物で中和して塩の形態にして、水溶化することにより得ることができる。
該中和に使用する塩基性化合物は、アンモニア又は有機アミンである。
中和の程度は、アンモニア又は有機アミンから選ばれる少なくとも１種の塩基性化合物によって、単量体単位（ａ）が有するカルボキシル基の２０〜３０モル％が塩の形態になるようにして行い、さらに構造単位（ａ）が有するカルボキシル基の５０〜７０モル％が遊離の酸基となるよう中和することで、炭酸カルシウムスラリーに対して良好な分散性及びｐＨ低下抑制効果に優れる分散剤を調整することができる。
必要により、アンモニア及び有機アミンの数種類を用いても良いし、物性を損なわない範囲で、その他の塩基性化合物を併用しても良い。
また、重合体（Ａ）及び／又は共重合体（Ｂ）の水溶液と、（Ａ）及び／又は（Ｂ）のアンモニウム塩水溶液若しくは有機アミン塩水溶液と、必要に応じて（Ａ）及び／又は（Ｂ）をその他の塩基性化合物で中和した水溶液とを、上記のような中和比率になるように配合して得ることもできる。
As a method for obtaining the (meth) acrylic (co) polymer salt of the present invention, from the solution containing the polymer (A) or copolymer (B) obtained above, if necessary, distillation, vacuum distillation, drying, etc. After removing the organic solvent by the above operation, the carboxyl group of the monomer unit (a) constituting the polymer (A) or copolymer (B) is neutralized with a basic compound to form a salt. It can be obtained by water-solubilization.
The basic compound used for the neutralization is ammonia or an organic amine.
The degree of neutralization, by at least one basic compound selected from ammonia or organic amines, performed 20-30 mol% of the carboxyl groups monomer unit (a) has is set to be in the form of a salt, Further, by neutralizing 50 to 70 mol% of the carboxyl groups of the structural unit (a) to be free acid groups, a dispersant excellent in dispersibility and pH lowering suppression effect on the calcium carbonate slurry is obtained. Can be adjusted.
If necessary, several kinds of ammonia and organic amines may be used, and other basic compounds may be used in combination as long as the physical properties are not impaired.
Further, an aqueous solution of the polymer (A) and / or the copolymer (B), an aqueous ammonium salt solution or an organic amine salt aqueous solution of (A) and / or (B), and (A) and / or An aqueous solution obtained by neutralizing (B) with another basic compound can also be blended so as to have the neutralization ratio as described above.
本発明の重合体（Ａ）及び／又は共重合体（Ｂ）（本発明では（メタ）アクリル酸系（共）重合体という）中のアンモニウム塩及び有機アミン塩の割合が８０％を超えると、分散性が悪化するため好ましくなく、またコストや臭気の点から工業的にも好ましくない。一方、これらの割合が２０％未満であると、炭酸カルシウムスラリーの経時的なｐＨ低下抑制効果が弱まるために好ましくない。
また、（メタ）アクリル酸系（共）重合体中の酸基の中和率が２０％未満であると、炭酸カルシウムスラリーの粉砕直後のｐＨが低下するうえ、上記のように経時的なｐＨ低下抑制効果も弱まるために好ましくない。
それに加えて、本発明の分散剤は、３９．９〜４３．４質量％水溶液のｐＨが６．０以下になるように塩基性化合物を調整する必要がある。ｐＨが６．０を超えると、分散液スラリーの流動性や濾過性等の物性が不十分である。
When the ratio of ammonium salt and organic amine salt in the polymer (A) and / or copolymer (B) of the present invention (referred to as (meth) acrylic acid-based (co) polymer in the present invention) exceeds 80% Further, it is not preferable because dispersibility deteriorates, and it is not preferable industrially from the viewpoint of cost and odor. On the other hand, it is not preferable that these proportions are less than 20% because the effect of suppressing the decrease in pH over time of the calcium carbonate slurry is weakened.
Moreover, when the neutralization rate of the acid group in the (meth) acrylic acid-based (co) polymer is less than 20%, the pH immediately after the pulverization of the calcium carbonate slurry is lowered, and the pH over time as described above. This is not preferable because the effect of suppressing the decrease is weakened.
In addition, it is necessary for the dispersant of the present invention to adjust the basic compound so that the pH of the 39.9 to 43.4% by mass aqueous solution is 6.0 or less. When the pH exceeds 6.0, physical properties such as fluidity and filterability of the dispersion slurry are insufficient.
本発明に使用する塩基性化合物は、アンモニアまたは有機アミンであり、有機アミンは、一級アミン、二級アミン、三級アミンが含まれる。
一級アミン及び二級アミンとしては、例えば脂肪族アミンでは炭素数１〜２０のアルキル基を有する低級アルキルアミンとして、メチルアミン、エチルアミン、ｎ−ブチルアミン、オクチルアミン、ドデシルアミン、ジメチルアミン、ジエチルアミン、ジブチルアミン、ジオクチルアミン、ジドデシルアミン等が挙げられるほか、アルカノールアミン（モノエタノールアミン、ジエタノールアミン等）、（ポリ）アルキレンポリアミン（エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン）、もしくはその誘導体（アルキル化物、アルキレンオキシド付加物）等が挙げられる。
三級アミンの場合は、三級アミンまたはそれを四級化した第四級アンモニウム塩が含まれる。かかるアミンとしては、脂肪族アミン（トリメチルアミン、トリエチルアミン、イソプロピルエチルアミン、オクチルジメチルアミン、ドデシルジメチルアミン等）、脂環族アミン（Ｎ−メチルピロリジン、Ｎ−エチルピロリジン、Ｎ−メチルピペリジン、Ｎ−エチルピペリジン等）、芳香族アミン（Ｎ，Ｎ−ジメチルアニリン、Ｎ，Ｎ−ジエチルアニリン等）などの三級アミンが挙げられ、それを炭酸ジアルキル等で四級化した第四級アンモニウム塩が挙げられる。
塩基性化合物としては、アンモニアは刺激臭が強いので、好ましくは有機アミンであり、より好ましくはアルカノールアミン又は低級アルキルアミンである。低臭気であり環境にやさしい点から、特に好ましくはモノエタノールアミンである。The basic compound used in the present invention is ammonia or an organic amine, and the organic amine includes a primary amine, a secondary amine, and a tertiary amine.
Examples of primary amines and secondary amines include, for example, aliphatic amines having lower alkyl amines having 1 to 20 carbon atoms, methylamine, ethylamine, n-butylamine, octylamine, dodecylamine, dimethylamine, diethylamine, diamine. In addition to butylamine, dioctylamine, didodecylamine, etc., alkanolamines (monoethanolamine, diethanolamine, etc.), (poly) alkylene polyamines (ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine), or their derivatives (alkyl) Compound, alkylene oxide adduct) and the like.
In the case of a tertiary amine, a tertiary amine or a quaternary ammonium salt obtained by quaternizing it is included. Such amines include aliphatic amines (trimethylamine, triethylamine, isopropylethylamine, octyldimethylamine, dodecyldimethylamine, etc.), alicyclic amines (N-methylpyrrolidine, N-ethylpyrrolidine, N-methylpiperidine, N-ethylpiperidine). Etc.), and tertiary amines such as aromatic amines (N, N-dimethylaniline, N, N-diethylaniline, etc.), and quaternary ammonium salts obtained by quaternizing it with dialkyl carbonate or the like.
As the basic compound, ammonia has a strong irritating odor, and is preferably an organic amine, more preferably an alkanolamine or a lower alkylamine. Monoethanolamine is particularly preferred from the viewpoint of low odor and environmental friendliness.
（メタ）アクリル酸（系）共重合体中の酸基を中和するために併用できるその他の塩基性化合物としては、アルカリ金属水酸化物又はアルカリ土類金属水酸化物などが挙げられる。アルカリ金属としては、リチウム、ナトリウム、カリウムなどが好ましく、アルカリ土類金属としてはカルシウム、マグネシウム、バリウムなどが好ましい。これらは単独で用いても良いし、２種以上の混合物として用いても良い。これらのうち特に好ましくは、水酸化ナトリウムである。
ただし、アルカリ金属水酸化物又はアルカリ土類金属水酸化物のみを使用することは、分散液スラリーのｐＨが低下するため、避けるべきである。Examples of other basic compounds that can be used in combination to neutralize the acid group in the (meth) acrylic acid (based) copolymer include alkali metal hydroxides and alkaline earth metal hydroxides. As the alkali metal, lithium, sodium, potassium and the like are preferable, and as the alkaline earth metal, calcium, magnesium, barium and the like are preferable. These may be used alone or as a mixture of two or more. Of these, sodium hydroxide is particularly preferred.
However, the use of only alkali metal hydroxides or alkaline earth metal hydroxides should be avoided because the pH of the dispersion slurry decreases.
本発明の分散剤は、無機顔料、特に炭酸カルシウムに対して特に優れた効果を発揮する。本発明の分散剤の使用量は、通常炭酸カルシウムに対して０．０１〜１０質量％であり、好ましくは０．０５〜５質量％、特に好ましくは０．１〜３質量％である。０．０１質量％未満では分散効果が不十分であり、また、１０質量％を超えると分散液が増粘傾向になるため好ましくない。
また、本発明の炭酸カルシウム分散液のｐＨは８．０以上が好ましい。これ未満では、スラリーに雑菌が繁殖しやすく、腐敗臭の原因となったり、性能が低下する。より好ましくは、ｐＨが９．５以上である。The dispersant of the present invention exhibits a particularly excellent effect on inorganic pigments, particularly calcium carbonate. The usage-amount of the dispersing agent of this invention is 0.01-10 mass% normally with respect to calcium carbonate, Preferably it is 0.05-5 mass%, Most preferably, it is 0.1-3 mass%. If it is less than 0.01% by mass, the dispersion effect is insufficient, and if it exceeds 10% by mass, the dispersion tends to increase in viscosity.
The pH of the calcium carbonate dispersion of the present invention is preferably 8.0 or higher. If it is less than this, miscellaneous bacteria will propagate easily in a slurry, and it will become a cause of rot odor or performance will fall. More preferably, the pH is 9.5 or higher.
本発明に使用する炭酸カルシウムとしては、軽質炭酸カルシウム、コロイド炭酸カルシウム、重質炭酸カルシウム等が例示されるが、重質炭酸カルシウムが、コスト等の面から好ましい。４００〜４０メッシュ程度（約０．０４ｍｍ〜０．４ｍｍ）の粗粉重質炭酸カルシウムを用いると、本発明の炭酸カルシウム用分散剤の性能が最大限発揮される。 Examples of the calcium carbonate used in the present invention include light calcium carbonate, colloidal calcium carbonate, and heavy calcium carbonate. Heavy calcium carbonate is preferable from the viewpoint of cost and the like. When coarse powder heavy calcium carbonate of about 400 to 40 mesh (about 0.04 mm to 0.4 mm) is used, the performance of the dispersant for calcium carbonate of the present invention is maximized.
本発明の分散剤は、上記無機顔料用分散剤以外にも、シリカ粒子やセリア（酸化セリウム）粒子及びアルミナ粒子等の各種無機粒子用分散剤としても優れた効果を発揮する。 The dispersant of the present invention exhibits an excellent effect as a dispersant for various inorganic particles such as silica particles, ceria (cerium oxide) particles, and alumina particles, in addition to the dispersant for inorganic pigments.
一般に、シリカ分散液は、製紙用途、金属加工用途、繊維用途、塗料用途、光学材料用途及びケミカルメカニカルポリッシング（以下、「ＣＭＰ」という）用途に使用されている。 In general, silica dispersions are used in papermaking applications, metal processing applications, fiber applications, paint applications, optical material applications, and chemical mechanical polishing (hereinafter referred to as “CMP”) applications.
ＣＭＰは半導体デバイスの製造工程において、ウェハー表面の平坦化仕上げ等に用いられる技術であり、研磨定盤上に研磨パッドを貼り付け、研磨パッド表面を研磨剤で浸し、被研磨面を押し付け加圧した状態で研磨定盤を回し、研磨剤と被研磨体の凸部との機械的摩擦によって凸部を除去し平滑化する。
このＣＭＰにおける研磨剤としては、シリカ粒子又はセリア粒子を分散剤を使用して分散させたものが知られている。CMP is a technique used for flattening the surface of a wafer in the manufacturing process of semiconductor devices. A polishing pad is attached to a polishing surface plate, the polishing pad surface is immersed in an abrasive, and the surface to be polished is pressed and pressed. In this state, the polishing surface plate is rotated, and the convex portions are removed and smoothed by mechanical friction between the abrasive and the convex portions of the object to be polished.
As an abrasive in this CMP, one obtained by dispersing silica particles or ceria particles using a dispersant is known.
シリカ粒子の分散液を製造する場合、シリカ粒子１００重量部に対して、分散剤を固形分で０．０１〜２．０重量部使用するのが好ましい。 In the case of producing a dispersion of silica particles, it is preferable to use 0.01 to 2.0 parts by weight of a dispersant in solid content with respect to 100 parts by weight of silica particles.
シリカ粒子の平均粒径は、目的に応じて適宜設定すれば良いが、ＣＭＰ研磨剤として使用する場合には、０．００５〜０．５μｍが好ましい。
平均粒子径を０．００５μｍ以上とすることで、分散液をＣＭＰ工程に使用した場合、研磨速度が速いものとなり、一方、０．５μｍ以下とすることで、粒子の沈降を抑制することができる。
シリカ粒子の配合量は分散液に対して０．１〜５０重量％が好ましい。０．１重量％以上とすることで、分散液をＣＭＰ工程に使用した場合、研磨速度が速いものとなり、一方、５０重量％以下とすることで、粒子の凝集を抑制することができる。The average particle diameter of the silica particles may be appropriately set according to the purpose, but when used as a CMP abrasive, 0.005 to 0.5 μm is preferable.
By setting the average particle size to 0.005 μm or more, when the dispersion is used in the CMP process, the polishing rate is high, and by setting the average particle size to 0.5 μm or less, sedimentation of particles can be suppressed. .
The amount of silica particles is preferably 0.1 to 50% by weight based on the dispersion. By setting the content to 0.1% by weight or more, when the dispersion is used in the CMP process, the polishing rate becomes high. On the other hand, by setting the content to 50% by weight or less, aggregation of particles can be suppressed.
一方、セリア分散液は、排ガス浄化触媒用途、ガスセンサ用途、光学材料用途及びＣＭＰ用途に使用されている。 On the other hand, ceria dispersions are used in exhaust gas purification catalyst applications, gas sensor applications, optical material applications, and CMP applications.
セリア粒子の分散液を製造する場合、セリア粒子１００重量部に対して、分散剤を固形分で０．０１〜２．０重量部使用するのが好ましい。 When producing a dispersion of ceria particles, it is preferable to use 0.01 to 2.0 parts by weight of a dispersant in solid content with respect to 100 parts by weight of ceria particles.
セリア粒子の平均粒径は、目的に応じて適宜設定すれば良いが、ＣＭＰ研磨剤として使用する場合には０．０１〜１．０μｍが好ましい。
平均粒子径を０．０１μｍ以上とすることで、分散液をＣＭＰ工程に使用した場合、研磨速度が速いものとなり、一方、１．０μｍ以下とすることで、粒子の沈降を抑制することができる。
セリア粒子の配合量は、分散液に対して０．１〜５０重量％が好ましい。０．１重量％以上とすることで、分散液をＣＭＰ工程に使用した場合、研磨速度が速いものとなり、一方、５０重量％以下とすることで、粒子の凝集を抑制することができる。The average particle diameter of the ceria particles may be appropriately set according to the purpose, but is preferably 0.01 to 1.0 μm when used as a CMP abrasive.
By setting the average particle size to 0.01 μm or more, when the dispersion is used in the CMP process, the polishing rate is high, and by setting the average particle size to 1.0 μm or less, particle sedimentation can be suppressed. .
The blending amount of ceria particles is preferably 0.1 to 50% by weight with respect to the dispersion. By setting the content to 0.1% by weight or more, when the dispersion is used in the CMP process, the polishing rate becomes high. On the other hand, by setting the content to 50% by weight or less, aggregation of particles can be suppressed.
アルミナ分散液は、製紙用途、金属加工用途、繊維用途、塗料用途、光学材料用途及びセラミック用途に使用されている。 Alumina dispersions are used in papermaking applications, metalworking applications, textile applications, paint applications, optical material applications and ceramic applications.
アルミナ粒子の分散液を製造する場合、アルミナ粒子１００重量部に対して、分散剤を固形分で０．０１〜５．０重量部使用するのが好ましい。 In the case of producing a dispersion of alumina particles, it is preferable to use 0.01 to 5.0 parts by weight of a dispersant in solid content with respect to 100 parts by weight of alumina particles.
アルミナ粒子の平均粒径は、目的に応じて適宜設定すれば良いが、０．０１〜５．０μｍが好ましい。
平均粒子径を０．０１μｍ以上とすることで、コスト的に有利なものとなり、一方、５．０μｍ以下とすることで、アルミナ粒子からセラミックを製造する場合にセラミックが強靭性に優れるものとなる。
アルミナ粒子の配合量は、分散液に対して４０〜８５重量％が好ましい。４０重量％以上とすることで、アルミナ粒子からセラミックを製造する場合にセラミックの寸法精度に優れるものとすることができる。一方、８５重量％以下とすることで、分散液が低粘度となり、取り扱いが容易なものとなる。The average particle diameter of the alumina particles may be appropriately set according to the purpose, but is preferably 0.01 to 5.0 μm.
By making the average particle diameter 0.01 μm or more, it becomes advantageous in terms of cost. On the other hand, by making it 5.0 μm or less, the ceramic becomes excellent in toughness when producing ceramic from alumina particles. .
The blending amount of the alumina particles is preferably 40 to 85% by weight with respect to the dispersion. By setting the content to 40% by weight or more, the ceramic can be excellent in dimensional accuracy when the ceramic is produced from the alumina particles. On the other hand, when the content is 85% by weight or less, the dispersion liquid has a low viscosity and is easy to handle.
本発明の分散剤を使用して得られたアルミナ粒子を含む分散液は種々の用途に使用することができ、特にセラミック製造用分散液として好ましく使用することができる。
この場合、アルミナ以外のセラミック原料粉末と併用することができる。
セラミック原料粉末としては、無機粉末が使用可能であり、チタニア、マグネシア及びジルコニア等の金属酸化物、炭化ケイ素等の金属炭化物、窒化アルミニウム及び窒化ケイ素等の窒化物、炭酸カルシウム及び炭酸バリウム等の炭酸塩、並びにチタン酸バリウム等が挙げられる。The dispersion containing alumina particles obtained by using the dispersant of the present invention can be used for various applications, and can be particularly preferably used as a dispersion for producing a ceramic.
In this case, it can be used together with ceramic raw material powder other than alumina.
As the ceramic raw material powder, inorganic powder can be used, metal oxides such as titania, magnesia and zirconia, metal carbides such as silicon carbide, nitrides such as aluminum nitride and silicon nitride, carbonates such as calcium carbonate and barium carbonate. Examples thereof include salts and barium titanate.
以下、実施例により本発明を更に詳細に説明するが、本発明は以下の実施例に限定されるものではない。
以下の例において、「％」および「部」は、それぞれ「質量％」および「質量部」を示す。
また、以下の例において、（メタ）アクリル酸系（共）重合体の重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）の測定、並びに炭酸カルシウムに対する分散特性の測定または評価は次のようにして行った。EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example.
In the following examples, “%” and “part” indicate “% by mass” and “part by mass”, respectively.
In the following examples, the measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the (meth) acrylic acid-based (co) polymer, and the measurement or evaluation of the dispersion characteristics with respect to calcium carbonate are as follows. I went.
［１］（メタ）アクリル酸系共重合体の重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）
製造例で得られた中和後の（メタ）アクリル酸系（共）重合体の水溶液から採取して、濃度を０．４ｗt／ｖｏｌ％に調整した試料１００μＬを、カラム［東ソー（株）製のカラム「ＴＳＫｇｅｌ Ｇ３０００ＰＷＸＬ −ＴＳＫｇｅｌ Ｇ４０００ＰＷＸＬ −ＴＳＫｇｅｌ Ｇ６０００ＰＷＸＬ」（各々長さ３００ｍｍ、内径７．８ｍｍ）の３本を直列に連結したもの］に注入し、カラム温度３５℃にて、溶離液［０．１Ｍ ＮａＣｌ、０．１Ｍ リン酸緩衝液（リン酸１Ｎ ２水和物７．７０ｇ、リン酸２Ｎ １２水和物３６．３ｇ、ＮａＣｌ８．６３ｇ、脱イオン水１４７６．４ｇ）］を流速０．８ｍＬ／分でカラムに通して、カラムに吸着した成分を溶離させる水系のゲルパーミエーションクロマトグラフー（ＧＰＣ）法を採用して、（メタ）アクリル酸系（共）重合体の重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）を測定した。その際に、（メタ）アクリル酸系（共）重合体の重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）は、重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）およびピークトップ分子量（Ｍｐ）が明らかなポリアクリル酸ナトリウム（ＡＭＥＲＩＣＡＮ ＰＯＬＹＭＥＲ ＳＴＡＮＤＡＲＤＳ ＣＯＲＰ．製の分子量９００万、５５５万、１１４万、４４万、１３万１２００、７万９００、２４００のもの）を基準物質として予め作成しておいた検量線から算出した。[1] Weight average molecular weight (Mw) and number average molecular weight (Mn) of (meth) acrylic acid copolymer
100 μL of a sample collected from the neutralized (meth) acrylic acid (co) polymer aqueous solution obtained in the production example and adjusted to a concentration of 0.4 wt / vol% was added to a column [manufactured by Tosoh Corporation]. Column “TSKgel G3000PWXL-TSKgel G4000PWXL-TSKgel G6000PWXL” (each having a length of 300 mm and an inner diameter of 7.8 mm) connected in series to a column temperature of 35 ° C. and an eluent [0.1 M NaCl, 0.1 M phosphate buffer (phosphoric acid 1N dihydrate 7.70 g, phosphoric acid 2N 12 hydrate 36.3 g, NaCl 8.63 g, deionized water 1476.4 g)] at a flow rate of 0.8 mL / A water-based gel permeation chromatograph (GPC) method that elutes the components adsorbed on the column through Acrylic acid-based (co) weight average molecular weight (Mw) of the polymer and the number average molecular weight (Mn) were measured. At that time, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the (meth) acrylic acid (co) polymer are the weight average molecular weight (Mw), the number average molecular weight (Mn), and the peak top molecular weight (Mp). ) With clear polyacrylate (with molecular weights of 9 million, 5550, 1.14 million, 440,000, 131200, 7900, 2400 manufactured by AMERICA POLYMER STANDARDS CORP.) It was calculated from the calibration curve.
［２］炭酸カルシウムに対する分散特性
［２−ａ］重質炭酸カルシウムの湿式粉砕処理
分散機［サンドグラインダー（五十嵐機械製）］に、粗粉の重質炭酸カルシウム［丸尾カルシウム社製「Ｎｏ．Ａ 重炭」（４２メッシュ残渣１％以下、１００メッシュ残渣９０％以上）］を９００ｇおよびアルミナビーズ（平均直径１．０ｍｍ；粉砕媒体）を２９７０ｇの量で充填し、更に以下の製造例で製造された中和された（メタ）アクリル酸系（共）重合体の水溶液を、重質炭酸カルシウム９００ｇに対して（メタ）アクリル酸系（共）重合体の固形分として０．７５質量％の量で充填し、それに蒸留水を加えて、重質炭酸カルシウムの濃度が７５質量％の重質炭酸カルシウムスラリーを分散機内で調製した後、分散機内の撹拌翼を１０００ｒｐｍの回転速度で回転させて５０分間湿式粉砕処理を行った。[2] Dispersion characteristics for calcium carbonate [2-a] Wet pulverization treatment of heavy calcium carbonate Disperser [Sand grinder (manufactured by Igarashi Machinery Co., Ltd.)] "Heavy coal" (42 mesh residue 1% or less, 100 mesh residue 90% or more)] is filled with 900 g and alumina beads (average diameter 1.0 mm; grinding media) in an amount of 2970 g. A neutralized (meth) acrylic acid-based (co) polymer aqueous solution was added in an amount of 0.75% by mass as a solid content of the (meth) acrylic acid-based (co) polymer based on 900 g of heavy calcium carbonate. And then adding distilled water to prepare a heavy calcium carbonate slurry with a heavy calcium carbonate concentration of 75 mass% in the disperser, and then stirring the stirring blade in the disperser to 1000 rp. Rotated at a rotational speed was 50 min wet grinding process.
［２−ｂ］湿式粉砕処理中の重質炭酸カルシウムスラリーの流動性の評価
上記［２−ａ］の湿式粉砕処理時に、重質炭酸カルシウムスラリーの流動性を以下の評価基準にしたがって評価した。
○：粉砕初期〜後期を通して、分散機の撹拌翼への付着物がなく、流動性に極めて優れている。
△：粉砕初期〜後期を通して、分散機の撹拌翼への付着物が少なく、流動性に優れている。
×：粉砕初期〜後期を通して（特に粉砕初期に）、分散機の撹拌翼への付着物がかなりあり、流動性（特に粉砕初期における流動性）が低い。[2-b] Evaluation of fluidity of heavy calcium carbonate slurry during wet pulverization treatment During the wet pulverization treatment of [2-a], the fluidity of heavy calcium carbonate slurry was evaluated according to the following evaluation criteria.
○: There is no adhering matter to the stirring blade of the disperser throughout the pulverization initial stage to the latter stage, and the fluidity is extremely excellent.
(Triangle | delta): There are few deposits to the stirring blade of a disperser through the pulverization initial stage-late stage, and it is excellent in fluidity.
X: Throughout the pulverization period to the latter period (particularly in the pulverization period), there is considerable adhesion to the stirring blades of the disperser, and the fluidity (particularly the fluidity in the pulverization period) is low.
［２−ｃ］重質炭酸カルシウムスラリー中の重質炭酸カルシウム粒子の平均粒径
上記［２−ａ］の湿式粉砕処理によって得られた湿式粉砕後の重質炭酸カルシウムスラリーを光散乱強度が適切になるように大量の脱イオン水に分散させ、それを試料として用いて、レーザー光散乱型粒度分布計（堀場製作所製「ＬＡ−９２０型」）を使用して、重質炭酸カルシウムスラリー中の重質炭酸カルシウム粒子の平均粒径を測定した。[2-c] Average particle diameter of heavy calcium carbonate particles in heavy calcium carbonate slurry Light scattering intensity is appropriate for the heavy calcium carbonate slurry after wet pulverization obtained by the wet pulverization treatment of [2-a] above. In a heavy calcium carbonate slurry using a laser light scattering particle size distribution meter ("LA-920 type" manufactured by Horiba, Ltd.) The average particle size of the heavy calcium carbonate particles was measured.
［２−ｄ］重質炭酸カルシウムスラリーの濾過性
上記［２−ａ］の湿式粉砕処理によって得られた湿式粉砕後の重質炭酸カルシウムスラリーとアルミナビーズを含む全量を試料として用いて、それを、２００目濾布を取り付けた円筒形の濾過装置（濾過部分は直径２５ｃｍ）に平らに注ぎ込み、濾過開始から５分が経過した時点でのスラリーの濾過量（ｇ）を測定して、下記の評価基準に従って濾過性を評価した。
○：試料の４０質量％以上が濾布を通過し、濾過性に極めて優れている。
△：試料の３０質量％以上４０質量％未満が濾布を通過し、濾過性に優れている。
×：試料の３０質量％未満しか濾布を通過せず、濾過性に劣っている。[2-d] Filterability of Heavy Calcium Carbonate Slurry Using the total amount of wet calcium pulverized slurry and alumina beads obtained by wet pulverization of [2-a] as a sample, , Pour flatly into a cylindrical filtration apparatus (filter part is 25 cm in diameter) with a 200-mesh filter cloth, and measure the amount of filtration (g) of the slurry after 5 minutes from the start of filtration. Filterability was evaluated according to the evaluation criteria.
○: 40% by mass or more of the sample passes through the filter cloth, and the filterability is extremely excellent.
(Triangle | delta): 30 mass% or more and less than 40 mass% of a sample passes a filter cloth, and is excellent in filterability.
X: Less than 30% by mass of the sample passes through the filter cloth, and the filterability is poor.
［２−ｅ］重質炭酸カルシウムスラリーの経時安定性
上記［２−ｄ］で得られた、２００目濾布を通過した濾過物を試料として用い、当該試料中の重質炭酸カルシウムの濃度が７５質量％よりも高くなっている場合は蒸留水で希釈して重質炭酸カルシウムの濃度が７５質量％の試料を調製した。この試料を温度２５℃で静置した状態に保ち、当初（試料の調製直後）と静置７日後の粘度を、ＢＭ型粘度計（トキメック社製）を使用して、温度２５℃で、＃３ローターまたは＃４ローターを使用（＃３ローターは試料の粘度が１０００ｍＰａ・ｓ以下のときに、＃４ローターは試料の粘度が１０００〜１０００ｍＰａ・ｓのときに使用）して、回転速度６０ｒｐｍで重質炭酸カルシウムスラリーの粘度を測定した。[2-e] Stability over time of heavy calcium carbonate slurry Using the filtrate obtained through the above [2-d] that passed through the 200th filter cloth as a sample, the concentration of heavy calcium carbonate in the sample is When the concentration was higher than 75% by mass, the sample was diluted with distilled water to prepare a sample having a heavy calcium carbonate concentration of 75% by mass. The sample was kept standing at a temperature of 25 ° C., and the viscosity at the beginning (immediately after preparation of the sample) and after 7 days of standing was measured using a BM viscometer (manufactured by Tokimec) at a temperature of 25 ° C. 3 rotor or # 4 rotor is used (# 3 rotor is used when sample viscosity is 1000 mPa · s or less, # 4 rotor is used when sample viscosity is 1000 to 1000 mPa · s), and rotation speed is 60 rpm. The viscosity of the heavy calcium carbonate slurry was measured.
［２−ｆ］重質炭酸カルシウムスラリーのｐＨ
上記［２−ｅ］で調整した重質炭酸カルシウムの濃度が７５質量％のスラリーを試料として用い、当初（試料の調製直後）と静置７日後のｐＨ値を、温度２５℃に温調した状態でｐＨメーター（堀場製作所製「Ｄ−１２型」）を使用して測定し、下記の評価基準に従って評価した。
○：当初（試料の調製直後）と静置７日後のｐＨ値が、共に９．５以上である。
×：当初（試料の調製直後）と静置７日後のｐＨ値が、共に９．５を下回っている。[2-f] pH of heavy calcium carbonate slurry
Using a slurry having a heavy calcium carbonate concentration of 75% by mass adjusted in [2-e] as a sample, the pH value at the beginning (immediately after preparation of the sample) and after 7 days of standing was adjusted to a temperature of 25 ° C. It measured using the pH meter (Horiba Seisakusho "D-12 type") in the state, and evaluated according to the following evaluation criteria.
○: The pH value at the beginning (immediately after preparation of the sample) and after 7 days of standing are both 9.5 or more.
X: The pH value at the beginning (immediately after preparation of the sample) and after 7 days of standing are both lower than 9.5.
○製造例１［（メタ）アクリル酸系共重合体（Ｂ−１）の製造］
（１）４つ口フラスコに、イソプロパノール１１４．８ｇおよび脱イオン水１３８．０ｇを充填し、フラスコの内容物を２００ｒｐｍで回転撹拌しながら、内温を７８℃まで昇温した。内温が一定になった後、過硫酸アンモニウム０．８７ｇおよび脱イオン水４．０５ｇを一度に添加し、その一分後から、アクリル酸２３２．２ｇとアクリル酸ブチル３７．８ｇと脱イオン水４４．６ｇからなる単量体混合水溶液（合計３１４．６ｇ）と、過硫酸アンモニウム７．８３ｇと脱イオン水５６．５ｇからなる重合開始剤水溶液（合計６４．３ｇ）を、それぞれ６時間かけて連続的に供給した。連続供給終了後、内温を７８℃に保って熟成を１．５時間行った後に、内温が５０℃になるまで冷却した。反応液の５００ｍｇを採取してガスクロマトグラフィー分析を行ったところ、未反応のアクリル酸およびアクリル酸ブチルは検出されなかった。
（２） 次いで、圧力制御装置および真空ポンプによりフラスコ内の圧力を８０ｍｍＨｇに制御してイソプロパノールを連続的に留去した。イソプロパノールとの共沸で失われた量の脱イオン水をフラスコに追加した。○ Production Example 1 [Production of (Meth) acrylic acid copolymer (B-1)]
(1) A four-necked flask was charged with 114.8 g of isopropanol and 138.0 g of deionized water, and the internal temperature was raised to 78 ° C. while rotating and stirring the contents of the flask at 200 rpm. After the internal temperature became constant, 0.87 g of ammonium persulfate and 4.05 g of deionized water were added all at once. One minute later, 232.2 g of acrylic acid, 37.8 g of butyl acrylate, and deionized water 44 A monomer mixed aqueous solution consisting of 1.6 g (total 314.6 g) and a polymerization initiator aqueous solution consisting of 7.83 g ammonium persulfate and 56.5 g deionized water (total 64.3 g) were continuously added over 6 hours each. Supplied to. After completion of continuous supply, the inner temperature was maintained at 78 ° C. and aging was performed for 1.5 hours, and then the inner temperature was cooled to 50 ° C. When 500 mg of the reaction solution was collected and analyzed by gas chromatography, unreacted acrylic acid and butyl acrylate were not detected.
(2) Next, the pressure in the flask was controlled to 80 mmHg by a pressure controller and a vacuum pump, and isopropanol was continuously distilled off. The amount of deionized water lost to azeotrope with isopropanol was added to the flask.
（３）続いて、フラスコの内容物（（メタ）アクリル酸系共重合体、以下「Ｂ−１」という）を１５５℃で４５分間加熱して秤量を行った後、加熱後の水溶液中の（メタ）アクリル系共重合体量を測定し、測定値に基づいて脱イオン水を加えて、固形分濃度（Ｂ−１含有量）が４５％の水溶液を調製した。
（４）上記（３）で得られた固形分濃度（Ｂ−１含有量）が４５％の水溶液を用いて、水溶液中に含まれているＢ−１の重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）を上記［１］の方法で測定したところ、重量平均分子量（Ｍｗ）＝５２００、数平均分子量（Ｍｎ）＝２３００、分子量分布（Ｍｗ／Ｍｎ）＝２．２６であった。(3) Subsequently, the contents of the flask ((meth) acrylic acid copolymer, hereinafter referred to as “B-1”) were heated at 155 ° C. for 45 minutes and weighed, and then in the heated aqueous solution. The amount of (meth) acrylic copolymer was measured, and deionized water was added based on the measured value to prepare an aqueous solution having a solid content concentration (B-1 content) of 45%.
(4) Weight average molecular weight (Mw) and number average of B-1 contained in the aqueous solution using an aqueous solution having a solid content concentration (B-1 content) obtained in (3) of 45% When the molecular weight (Mn) was measured by the above method [1], the weight average molecular weight (Mw) = 5200, the number average molecular weight (Mn) = 2300, and the molecular weight distribution (Mw / Mn) = 2.26.
○製造例２［（メタ）アクリル酸系共重合体（Ｂ−２）の製造］
（１） 製造例１（Ｂ−１）の（１）において、単量体混合水溶液をアクリル酸２２０．３ｇとポリプロピレングリコールモノアクリレート［ポリプロピレンオキサイドの付加モル数ｎ＝３、末端水酸基（Ｒ３＝Ｈ）］４９．７ｇと脱イオン水４４．６ｇからなる単量体混合水溶液（合計３１４．６ｇ）に変えた以外は、製造例１の（１）と同じ重合操作を行った。反応終了後、反応液の５００ｍｇを採取してガスクロマトグラフィー分析を行ったところ、未反応のアクリル酸およびポリプロピレングリコールモノアクリレートは検出されなかった。
（２） 次いで、Ｂ−１の（２）および（３）と同じ操作を行って、固形分濃度［（メタ）アクリル酸系共重合体含有量］が４５％の水溶液を調製した（得られた（メタ）アクリル酸系共重合体を、以下「Ｂ−２」という）。
（３） 上記（２）で得られた固形分濃度（Ｂ−２含有量）が４５％の水溶液を用いて、水溶液中に含まれているＢ−２の重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）を上記［１］の方法で測定したところ、重量平均分子量（Ｍｗ）＝４８００、数平均分子量（Ｍｎ）＝２３００、分子量分布（Ｍｗ／Ｍｎ）＝２．０５であった。○ Production Example 2 [Production of (Meth) acrylic acid copolymer (B-2)]
(1) In (1) of Production Example 1 (B-1), the monomer mixed aqueous solution was mixed with acrylic acid 220.3 g and polypropylene glycol monoacrylate [number of added moles of polypropylene oxide n = 3, terminal hydroxyl group (R 3 = H)] The same polymerization operation as in Production Example 1 (1) was carried out except that the monomer mixture was changed to 49.7 g and 44.6 g of deionized water (total 314.6 g). After completion of the reaction, 500 mg of the reaction solution was collected and analyzed by gas chromatography. As a result, unreacted acrylic acid and polypropylene glycol monoacrylate were not detected.
(2) Next, the same operation as (2) and (3) of B-1 was performed to prepare an aqueous solution having a solid content concentration [(meth) acrylic acid copolymer content] of 45% (obtained). (Meth) acrylic acid copolymer is hereinafter referred to as “B-2”).
(3) The weight average molecular weight (Mw) and number average of B-2 contained in the aqueous solution using an aqueous solution having a solid content concentration (B-2 content) of 45% obtained in (2) above When the molecular weight (Mn) was measured by the above method [1], the weight average molecular weight (Mw) = 4800, the number average molecular weight (Mn) = 2300, and the molecular weight distribution (Mw / Mn) = 2.05.
○製造例３［（メタ）アクリル酸系重合体（Ａ−１）の製造］
（１） 製造例１（Ｂ−１）の（１）において、単量体混合水溶液をアクリル酸２７０．０ｇと脱イオン水４４．６ｇからなる単量体水溶液（合計３１４．６ｇ）に変えた以外は、Ｂ−１の（１）と同じ重合操作を行った。反応終了後、反応液の５００ｍｇを採取してガスクロマトグラフィー分析を行ったところ、未反応のアクリル酸は検出されなかった。
（２） 次いで、製造例１の（２）および（３）と同じ操作を行って、固形分濃度［（メタ）アクリル酸系重合体含有量］が４５％の水溶液を調製した（得られた（メタ）アクリル酸系重合体を、以下「Ａ−１」という）。
（３） 上記（２）で得られた固形分濃度（Ａ−１含有量）が４５％の水溶液を用いて、水溶液中に含まれているＡ−１の重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）を上記［１］の方法で測定したところ、重量平均分子量（Ｍｗ）＝５３００、数平均分子量（Ｍｎ）＝２４００、分子量分布（Ｍｗ／Ｍｎ）＝２．２１であった。○ Production Example 3 [Production of (Meth) acrylic acid polymer (A-1)]
(1) In (1) of Production Example 1 (B-1), the monomer mixed aqueous solution was changed to a monomer aqueous solution (314.6 g in total) consisting of 270.0 g of acrylic acid and 44.6 g of deionized water. Except for the above, the same polymerization operation as in (1) of B-1 was performed. After completion of the reaction, 500 mg of the reaction solution was collected and analyzed by gas chromatography. As a result, unreacted acrylic acid was not detected.
(2) Next, the same operation as in Production Example 1 (2) and (3) was performed to prepare an aqueous solution having a solid content concentration [(meth) acrylic acid polymer content] of 45% (obtained) The (meth) acrylic acid polymer is hereinafter referred to as “A-1”).
(3) The weight average molecular weight (Mw) and number average of A-1 contained in the aqueous solution using an aqueous solution having a solid content concentration (A-1 content) of 45% obtained in (2) above When the molecular weight (Mn) was measured by the above method [1], the weight average molecular weight (Mw) = 5300, the number average molecular weight (Mn) = 2400, and the molecular weight distribution (Mw / Mn) = 2.21.
製造例１〜３で得られた（メタ）アクリル酸系（共）重合体（Ｂ−１）、（Ｂ−２）及び（Ａ−１）を用いて、下記の各実施例に示す中和方法に従って、（Ｂ−１）、（Ｂ−２）及び（Ａ−１）の酸基の一部または全部を中和して分散剤を調整し、上記［２−ａ］に記載した方法で重質炭酸カルシウムの湿式粉砕処理を行った。そして、湿式粉砕処理中の重質炭酸カルシウムスラリーの流動性を上記［２−ｂ］の方法で評価した。
また、当該湿式粉砕処理により得られた重質炭酸カルシウムスラリーについて、当該スラリーに含まれる重質炭酸カルシウム粒子の平均粒径を上記［２−ｃ］の方法で測定し、当該スラリーの濾過性を上記［２−ｄ］の方法で評価し、更に当該スラリーの経時安定性を上記［２−ｅ］の方法で評価し、最後に当該スラリーのｐＨ値を上記［２−ｆ］の方法で評価した。
以下、各実施例の評価結果を表１に、各比較例の評価結果を表２に示す。Using the (meth) acrylic acid (co) polymers (B-1), (B-2), and (A-1) obtained in Production Examples 1 to 3, neutralization shown in the following examples. According to the method, a dispersant is prepared by neutralizing some or all of the acid groups of (B-1), (B-2) and (A-1), and the method described in [2-a] above. Wet grinding of heavy calcium carbonate was performed. The fluidity of the heavy calcium carbonate slurry during the wet pulverization treatment was evaluated by the method [2-b].
Moreover, about the heavy calcium carbonate slurry obtained by the said wet grinding process, the average particle diameter of the heavy calcium carbonate particle contained in the said slurry is measured by the method of said [2-c], and the filterability of the said slurry is measured. Evaluated by the above method [2-d], further evaluated the temporal stability of the slurry by the method [2-e], and finally evaluated the pH value of the slurry by the method [2-f]. did.
The evaluation results of each example are shown in Table 1, and the evaluation results of each comparative example are shown in Table 2.
○実施例１
（メタ）アクリル酸系共重合体Ｂ−１の水溶液を用いて、氷水でフラスコを冷却し、ｐＨを測定しながら４８％水酸化ナトリウム水溶液を供給してアクリル酸由来のカルボキシル基の２０％を中和し、更にモノエタノールアミンを供給してアクリル酸由来のカルボキシル基の３０％を中和して固形分濃度が４２．０％、ｐＨ＝５．０の中和共重合体を調整した。
この中和共重合体を用いて、上記［２−ａ］に記載した方法で重質炭酸カルシウムの湿式粉砕処理を行い、分散液スラリーの粘度を測定したところ、湿式粉砕当日の粘度は６１０ｍＰａ・ｓ、７日後の粘度は９３０ｍＰａ・ｓであった。製造直後の分散液のメジアン径を測定すると、メジアン径は０．６０４μｍ、１．３２μアンダー値は９８％であった。分散液スラリーのｐＨを測定したところ、湿式粉砕当日のｐＨは９．８、７日後のｐＨも９．８であった。○ Example 1
Using an aqueous solution of (meth) acrylic acid-based copolymer B-1, the flask was cooled with ice water, and a 48% sodium hydroxide aqueous solution was supplied while measuring pH to remove 20% of the carboxyl group derived from acrylic acid. Neutralization was further performed, and monoethanolamine was further supplied to neutralize 30% of carboxyl groups derived from acrylic acid to prepare a neutralized copolymer having a solid content concentration of 42.0% and pH = 5.0.
Using this neutralized copolymer, wet pulverization of heavy calcium carbonate was performed by the method described in [2-a] above, and the viscosity of the dispersion slurry was measured. The viscosity on the wet pulverization day was 610 mPa · s, the viscosity after 7 days was 930 mPa · s. When the median diameter of the dispersion immediately after production was measured, the median diameter was 0.604 μm, and the 1.32 μ under value was 98%. When the pH of the dispersion slurry was measured, the pH on the wet grinding day was 9.8, and the pH after 7 days was 9.8.
○実施例２
実施例１において、使用する（メタ）アクリル酸系共重合体を、Ｂ−１からＢ−２に変更した以外は、実施例１と同様にして、中和を行った。このようにして、固形分濃度が４１．２％、ｐＨが５．１の顔料用分散剤を得た。この中和重合体を用いて、上記［２−ａ］に記載した方法で重質炭酸カルシウムの湿式粉砕処理を行い、分散液スラリーの各分散特性を評価した。Example 2
In Example 1, neutralization was performed in the same manner as in Example 1 except that the (meth) acrylic acid copolymer used was changed from B-1 to B-2. Thus, a pigment dispersant having a solid content concentration of 41.2% and a pH of 5.1 was obtained. Using this neutralized polymer, wet pulverization of heavy calcium carbonate was performed by the method described in [2-a] above, and each dispersion characteristic of the dispersion slurry was evaluated.
○実施例３
実施例１において、中和率をモノエタノールアミン２０％と４８％水酸化ナトリウム水溶液３０％に変更した以外は、実施例１と同様にして中和を行った。このようにして、固形分濃度が４２．１％、ｐＨが５．０の顔料用分散剤を得た。この中和重合体を用いて、上記［２−ａ］に記載した方法で重質炭酸カルシウムの湿式粉砕処理を行い、分散液スラリーの各分散特性を評価した。Example 3
In Example 1, neutralization was performed in the same manner as in Example 1 except that the neutralization rate was changed to 20% monoethanolamine and 30% 48% aqueous sodium hydroxide. Thus, a pigment dispersant having a solid content concentration of 42.1% and a pH of 5.0 was obtained. Using this neutralized polymer, wet pulverization of heavy calcium carbonate was performed by the method described in [2-a] above, and each dispersion characteristic of the dispersion slurry was evaluated.
○実施例４
実施例１において、中和率をモノエタノールアミン３０％のみに変更した以外は、実施例１と同様にして中和を行った。このようにして、固形分濃度が４２．９％、ｐＨが４．４の顔料用分散剤を得た。この中和重合体を用いて、上記［２−ａ］に記載した方法で重質炭酸カルシウムの湿式粉砕処理を行い、分散液スラリーの各分散特性を評価した。Example 4
In Example 1, neutralization was performed in the same manner as in Example 1 except that the neutralization rate was changed to only monoethanolamine 30%. In this way, a pigment dispersant having a solid content concentration of 42.9% and a pH of 4.4 was obtained. Using this neutralized polymer, wet pulverization of heavy calcium carbonate was performed by the method described in [2-a] above, and each dispersion characteristic of the dispersion slurry was evaluated.
○比較例６
実施例１において、中和率をモノエタノールアミン３０％と４８％水酸化ナトリウム水溶液５０％に変更した以外は、実施例１と同様にして中和を行った。このようにして、固形分濃度が４１．２％、ｐＨが５．９の顔料用分散剤を得た。この中和重合体を用いて、上記［２−ａ］に記載した方法で重質炭酸カルシウムの湿式粉砕処理を行い、分散液スラリーの各分散特性を評価した。
○ Comparative Example 6
In Example 1, neutralization was performed in the same manner as in Example 1 except that the neutralization rate was changed to 30% monoethanolamine and 50% 48% aqueous sodium hydroxide. Thus, a pigment dispersant having a solid content concentration of 41.2% and a pH of 5.9 was obtained. Using this neutralized polymer, wet pulverization of heavy calcium carbonate was performed by the method described in [2-a] above, and each dispersion characteristic of the dispersion slurry was evaluated.
○比較例７
実施例１において、中和率をモノエタノールアミン５０％のみに変更した以外は、実施例１と同様にして中和を行った。このようにして、固形分濃度が４３．０％、ｐＨが５．２の顔料用分散剤を得た。この中和重合体を用いて、上記［２−ａ］に記載した方法で重質炭酸カルシウムの湿式粉砕処理を行い、分散液スラリーの各分散特性を評価した。
○ Comparative Example 7
In Example 1, neutralization was performed in the same manner as in Example 1 except that the neutralization rate was changed to only monoethanolamine 50%. In this manner, a pigment dispersant having a solid content concentration of 43.0% and a pH of 5.2 was obtained. Using this neutralized polymer, wet pulverization of heavy calcium carbonate was performed by the method described in [2-a] above, and each dispersion characteristic of the dispersion slurry was evaluated.
○比較例８
実施例１において、中和率をモノエタノールアミン８０％のみに変更した以外は、実施例１と同様にして中和を行った。このようにして、固形分濃度が４３．４％、ｐＨが５．９の顔料用分散剤を得た。この中和重合体を用いて、上記［２−ａ］に記載した方法で重質炭酸カルシウムの湿式粉砕処理を行い、分散液スラリーの各分散特性を評価した。
○ Comparative Example 8
In Example 1, neutralization was performed in the same manner as in Example 1 except that the neutralization rate was changed to only monoethanolamine 80%. Thus, a pigment dispersant having a solid content concentration of 43.4% and a pH of 5.9 was obtained. Using this neutralized polymer, wet pulverization of heavy calcium carbonate was performed by the method described in [2-a] above, and each dispersion characteristic of the dispersion slurry was evaluated.
○比較例９
実施例１において、中和率をアンモニア５０％のみに変更した以外は、実施例１と同様にして中和を行った。このようにして、固形分濃度が４０％、ｐＨが４．９の顔料用分散剤を得た。この中和重合体を用いて、上記［２−ａ］に記載した方法で重質炭酸カルシウムの湿式粉砕処理を行い、分散液スラリーの各分散特性を評価した。
○ Comparative Example 9
In Example 1, neutralization was carried out in the same manner as in Example 1 except that the neutralization rate was changed to only 50% ammonia. Thus, a pigment dispersant having a solid content concentration of 40% and a pH of 4.9 was obtained. Using this neutralized polymer, wet pulverization of heavy calcium carbonate was performed by the method described in [2-a] above, and each dispersion characteristic of the dispersion slurry was evaluated.
○実施例５
実施例１において、使用する（メタ）アクリル酸系（共）重合体を、Ｂ−１からＡ−１に変更した以外は、実施例１と同様にして中和を行った。このようにして、固形分濃度が４２．３％、ｐＨが５．１の顔料用分散剤を得た。この中和重合体を用いて、上記［２−ａ］に記載した方法で重質炭酸カルシウムの湿式粉砕処理を行い、分散液スラリーの各分散特性を評価した。
Example 5
In Example 1, neutralization was performed in the same manner as in Example 1 except that the (meth) acrylic acid-based (co) polymer used was changed from B-1 to A-1. In this manner, a pigment dispersant having a solid content concentration of 42.3% and a pH of 5.1 was obtained. Using this neutralized polymer, wet pulverization of heavy calcium carbonate was performed by the method described in [2-a] above, and each dispersion characteristic of the dispersion slurry was evaluated.
○比較例１
実施例１において、中和率を４８％水酸化ナトリウム水溶液により９７％中和に変更した以外は、実施例１と同様にして中和を行った。このようにして、固形分濃度が４０％、ｐＨが８．０の顔料用分散剤を得た。この中和重合体を用いて、上記［２−ａ］に記載した方法で重質炭酸カルシウムの湿式粉砕処理を行い、分散液スラリーの各分散特性を評価した。○ Comparative Example 1
In Example 1, neutralization was performed in the same manner as in Example 1 except that the neutralization rate was changed to 97% neutralization with a 48% sodium hydroxide aqueous solution. Thus, a pigment dispersant having a solid content concentration of 40% and a pH of 8.0 was obtained. Using this neutralized polymer, wet pulverization of heavy calcium carbonate was performed by the method described in [2-a] above, and each dispersion characteristic of the dispersion slurry was evaluated.
○比較例２
実施例１において、中和率をモノエタノールアミンにより３０％、４８％水酸化ナトリウム水溶液により６７％中和するように変更した以外は、実施例１と同様にして中和を行った。このようにして、固形分濃度が４０．７％、ｐＨが８．１の顔料用分散剤を得た。この中和重合体を用いて、上記［２−ａ］に記載した方法で重質炭酸カルシウムの湿式粉砕処理を行い、分散液スラリーの各分散特性を評価した。○ Comparative Example 2
Neutralization was performed in the same manner as in Example 1 except that the neutralization rate was changed to 30% with monoethanolamine and 67% with 48% sodium hydroxide aqueous solution. In this way, a pigment dispersant having a solid content concentration of 40.7% and a pH of 8.1 was obtained. Using this neutralized polymer, wet pulverization of heavy calcium carbonate was performed by the method described in [2-a] above, and each dispersion characteristic of the dispersion slurry was evaluated.
○比較例３
実施例１において、中和率を４８％水酸化ナトリウム水溶液により５０％中和するように変更した以外は、実施例１と同様にして中和を行った。このようにして、固形分濃度が４０．５％、ｐＨが５．１の顔料用分散剤を得た。この中和重合体を用いて、上記［２−ａ］に記載した方法で重質炭酸カルシウムの湿式粉砕処理を行い、分散液スラリーの各分散特性を評価した。○ Comparative Example 3
In Example 1, neutralization was performed in the same manner as in Example 1 except that the neutralization rate was changed to 50% neutralization with a 48% sodium hydroxide aqueous solution. Thus, a pigment dispersant having a solid content concentration of 40.5% and a pH of 5.1 was obtained. Using this neutralized polymer, wet pulverization of heavy calcium carbonate was performed by the method described in [2-a] above, and each dispersion characteristic of the dispersion slurry was evaluated.
○比較例４
実施例１において、中和率をモノエタノールアミンにより９７．０％中和するように変更した以外は、実施例１と同様にして中和を行った。このようにして、固形分濃度が４３．２％、ｐＨが８．２の顔料用分散剤を得た。この中和重合体を用いて、上記［２−ａ］に記載した方法で重質炭酸カルシウムの湿式粉砕処理を行い、分散液スラリーの各分散特性を評価した。○ Comparative Example 4
In Example 1, neutralization was performed in the same manner as in Example 1 except that the neutralization rate was changed to 97.0% neutralization with monoethanolamine. In this manner, a pigment dispersant having a solid content concentration of 43.2% and a pH of 8.2 was obtained. Using this neutralized polymer, wet pulverization of heavy calcium carbonate was performed by the method described in [2-a] above, and each dispersion characteristic of the dispersion slurry was evaluated.
○比較例５
実施例１において、使用する（メタ）アクリル酸系（共）重合体を、Ｂ−１からＡ−１に変更し、中和率をモノエタノールアミンにより３０％、４８％水酸化ナトリウム水溶液により６７％中和するように変更した以外は、実施例１と同様にして中和を行った。このようにして、固形分濃度が３９．９％、ｐＨが８．０の顔料用分散剤を得た。この中和重合体を用いて、上記［２−ａ］に記載した方法で重質炭酸カルシウムの湿式粉砕処理を行い、分散液スラリーの各分散特性を評価した。○ Comparative Example 5
In Example 1, the (meth) acrylic acid (co) polymer used was changed from B-1 to A-1, and the neutralization rate was 30% with monoethanolamine and 67% with 48% aqueous sodium hydroxide. % Neutralization was carried out in the same manner as in Example 1 except that the amount was changed to neutralize. Thus, a pigment dispersant having a solid content concentration of 39.9% and a pH of 8.0 was obtained. Using this neutralized polymer, wet pulverization of heavy calcium carbonate was performed by the method described in [2-a] above, and each dispersion characteristic of the dispersion slurry was evaluated.
本発明によれば、無機顔料用分散剤、特に、高濃度の顔料スラリーや、粒径の小さな顔料スラリーに有用な炭酸カルシウム用分散剤が提供できる。
かかる分散剤を使用すれば、分散顔料の安定化効果が高く、微粒子状で良好な流動性を維持しながら分散させることができるので、スラリーの経時的な増粘やｐＨが長期間に渡って安定な分散液が得られる。該分散液は、製紙工業、プラスチック、ゴム、塗料、インキ、接着剤、シーラントなどに最適である。ADVANTAGE OF THE INVENTION According to this invention, the dispersing agent for calcium carbonate useful for the dispersing agent for inorganic pigments, especially a high concentration pigment slurry, and a pigment slurry with a small particle diameter can be provided.
If such a dispersant is used, the dispersion pigment has a high stabilizing effect and can be dispersed while maintaining good fluidity in the form of fine particles, so that the viscosity and pH of the slurry over time can be increased over a long period of time. A stable dispersion is obtained. The dispersion is optimal for the paper industry, plastics, rubber, paints, inks, adhesives, sealants and the like.
Claims (9)
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| JP2011518446A JP5776549B2 (en) | 2009-06-11 | 2010-06-01 | Dispersant for pigment and use thereof |
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| PCT/JP2010/059239 WO2010143554A1 (en) | 2009-06-11 | 2010-06-01 | Dispersant for pigment and use thereof |
| JP2011518446A JP5776549B2 (en) | 2009-06-11 | 2010-06-01 | Dispersant for pigment and use thereof |
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| JP5422797B2 (en) * | 2009-06-29 | 2014-02-19 | サンノプコ株式会社 | Fluidity improver for inorganic particle slurry |
| PT2363435E (en) * | 2010-01-27 | 2012-02-02 | Omya Development Ag | Use of polyethylenimines as additive in aqueous suspensions of calcium carbonate-comprising materials |
| JP5873009B2 (en) * | 2010-04-07 | 2016-03-01 | 株式会社日本触媒 | Poly (meth) acrylic acid polymer aqueous solution and method for producing the same |
| JP5455797B2 (en) * | 2010-06-07 | 2014-03-26 | 株式会社日本触媒 | Poly (meth) acrylic acid polymer aqueous solution and method for producing the same |
| SI2392622T1 (en) * | 2010-06-07 | 2013-07-31 | Omya Development Ag | Use of 2-aminoethanol as additive in aqueous suspensions of calcium carbonate comprising materials |
| ES2625878T3 (en) | 2010-10-29 | 2017-07-20 | Bellandtechnology Ag | Water soluble or water disintegrable copolymer |
| US9074067B2 (en) * | 2011-12-22 | 2015-07-07 | Rohm And Haas Company | Calcium carbonate slurries |
| JP6186564B2 (en) * | 2012-11-22 | 2017-08-30 | サンノプコ株式会社 | Thickener, slurry for exhaust gas purification catalyst, method for producing the same, and internal combustion engine |
| JP2015150530A (en) * | 2014-02-18 | 2015-08-24 | 株式会社日本触媒 | inorganic particulate dispersant |
| US10358560B2 (en) * | 2015-04-10 | 2019-07-23 | Lubrizol Advanced Materials, Inc. | Modified polyacrylate dispersants for the decorative ceramic market |
| CN105777973B (en) * | 2016-03-04 | 2018-01-12 | 山东德胜精细化工研究院有限公司 | A kind of amphipathic copolymer dispersant, preparation method and application |
| WO2018081964A1 (en) * | 2016-11-02 | 2018-05-11 | Basf Se | Acrylic acid polymers neutralized with sodium and calcium ions and having a narrow molecular weight distribution |
| JP6704151B1 (en) * | 2019-04-15 | 2020-06-03 | 株式会社Ｔｂｍ | Inorganic substance powder-filled resin composition and molded article |
| CN116003680B (en) * | 2022-12-26 | 2024-07-09 | 天集化工助剂（沧州）有限公司 | Polymeric anti-light aging multifunctional additive and preparation method and application thereof |
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| CN100582128C (en) * | 2005-08-31 | 2010-01-20 | 株式会社日本触媒 | Continuous production method of water-soluble polymer and water-soluble polymer |
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- 2010-06-01 WO PCT/JP2010/059239 patent/WO2010143554A1/en not_active Ceased
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| CN102458633A (en) | 2012-05-16 |
| JPWO2010143554A1 (en) | 2012-11-22 |
| WO2010143554A1 (en) | 2010-12-16 |
| SG175086A1 (en) | 2011-11-28 |
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