JPH0453813B2 - - Google Patents
Info
- Publication number
- JPH0453813B2 JPH0453813B2 JP62263678A JP26367887A JPH0453813B2 JP H0453813 B2 JPH0453813 B2 JP H0453813B2 JP 62263678 A JP62263678 A JP 62263678A JP 26367887 A JP26367887 A JP 26367887A JP H0453813 B2 JPH0453813 B2 JP H0453813B2
- Authority
- JP
- Japan
- Prior art keywords
- calcium carbonate
- water
- soluble
- polyvinyl alcohol
- modified polyvinyl
- 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
Links
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 130
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 65
- 239000006185 dispersion Substances 0.000 claims description 63
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 51
- 239000002270 dispersing agent Substances 0.000 claims description 39
- 229920001577 copolymer Polymers 0.000 claims description 32
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 22
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 125000000129 anionic group Chemical group 0.000 claims description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 11
- 230000004048 modification Effects 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 9
- 239000012736 aqueous medium Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000007127 saponification reaction Methods 0.000 claims description 7
- 239000004711 α-olefin Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 230000000052 comparative effect Effects 0.000 description 25
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 23
- 239000007787 solid Substances 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 230000000694 effects Effects 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 230000032683 aging Effects 0.000 description 10
- -1 ethylene, propylene, 1-butene Chemical class 0.000 description 10
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 239000011976 maleic acid Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920003169 water-soluble polymer Polymers 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 239000001023 inorganic pigment Substances 0.000 description 3
- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical compound CC(=C)CCO CPJRRXSHAYUTGL-UHFFFAOYSA-N 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 2
- BZAZNULYLRVMSW-UHFFFAOYSA-N 3-methylbut-2-en-2-ol Chemical compound CC(C)=C(C)O BZAZNULYLRVMSW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 description 1
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- KUIZKZHDMPERHR-UHFFFAOYSA-N 1-phenylprop-2-en-1-one Chemical compound C=CC(=O)C1=CC=CC=C1 KUIZKZHDMPERHR-UHFFFAOYSA-N 0.000 description 1
- WGLLSSPDPJPLOR-UHFFFAOYSA-N 2,3-dimethylbut-2-ene Chemical compound CC(C)=C(C)C WGLLSSPDPJPLOR-UHFFFAOYSA-N 0.000 description 1
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- GIXFALHDORQSOQ-UHFFFAOYSA-J 2,4,6,8-tetraoxido-1,3,5,7,2$l^{5},4$l^{5},6$l^{5},8$l^{5}-tetraoxatetraphosphocane 2,4,6,8-tetraoxide Chemical compound [O-]P1(=O)OP([O-])(=O)OP([O-])(=O)OP([O-])(=O)O1 GIXFALHDORQSOQ-UHFFFAOYSA-J 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- FBKXAAKPCYUMLM-UHFFFAOYSA-N 2-(2,5-dioxopyrrol-3-yl)ethanesulfonic acid Chemical compound OS(=O)(=O)CCC1=CC(=O)NC1=O FBKXAAKPCYUMLM-UHFFFAOYSA-N 0.000 description 1
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 1
- NSPPRYXGGYQMPY-UHFFFAOYSA-N 3-Methylbuten-2-ol-1 Natural products CC(C)C(O)=C NSPPRYXGGYQMPY-UHFFFAOYSA-N 0.000 description 1
- IYMZEPRSPLASMS-UHFFFAOYSA-N 3-phenylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC=CC=2)=C1 IYMZEPRSPLASMS-UHFFFAOYSA-N 0.000 description 1
- VXVUDUCBEZFQGY-UHFFFAOYSA-N 4,4-dimethylpentanenitrile Chemical compound CC(C)(C)CCC#N VXVUDUCBEZFQGY-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-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
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 201000001880 Sexual dysfunction Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229940091181 aconitic acid Drugs 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- BRXCDHOLJPJLLT-UHFFFAOYSA-N butane-2-sulfonic acid Chemical compound CCC(C)S(O)(=O)=O BRXCDHOLJPJLLT-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 description 1
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 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
- 239000004927 clay Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- AZSFNUJOCKMOGB-UHFFFAOYSA-K cyclotriphosphate(3-) Chemical compound [O-]P1(=O)OP([O-])(=O)OP([O-])(=O)O1 AZSFNUJOCKMOGB-UHFFFAOYSA-K 0.000 description 1
- 230000003247 decreasing effect Effects 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
- 230000000668 effect on calcium Effects 0.000 description 1
- NHOGGUYTANYCGQ-UHFFFAOYSA-N ethenoxybenzene Chemical compound C=COC1=CC=CC=C1 NHOGGUYTANYCGQ-UHFFFAOYSA-N 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 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
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229940005740 hexametaphosphate Drugs 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium 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
- 239000004576 sand Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon 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
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Landscapes
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Colloid Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Paper (AREA)
Description
（産業上の利用分野）
本発明は、炭酸カルシウムを効率よく水性媒体
中に分散して水分散液を製造する方法に関し、詳
しくは、特定の水溶性共重合体と特定の水溶性ア
ニオン化変性ポリビニルアルコールとを分散剤と
して併用することを特徴とする炭酸カルシウム水
分散液の製造方法に関する。
（従来の技術）
炭酸カルシウムは安価であり他の無機顔料と比
べて優れた白色度、インキ受理性、光沢、印刷適
性を有するため、製紙業界で賞用されている顔料
の１つである。また中性抄紙の普及によりその使
用量は急激に増えてきている。
従来、炭酸カルシウムは平均粒子径1μ前後の
いわゆる重質炭酸カルシウムが多用されてきた
が、近年紙質の高級化に伴い平均粒子径0.1〜
0.5μの沈降性軽質炭酸カルシウムの使用比率が増
大しつつある。しかるに、平均粒子径が小さくな
ればなるほど水性媒体中への分散が困難になり、
また凝集しやすく、水分散液の経日安定性にも問
題が生じやすくなる。
従来使用されている炭酸カルシウム用分散剤に
は、無機系ではピロリン酸塩、トリポリリン酸
塩、トリメタリン酸塩、テトラメタリン酸塩、ヘ
キサメタリン酸塩などの縮合リン酸塩、亜鉛塩、
珪酸塩などがある。しかし、これら無機系分散剤
は、得られた水分散液の経日安定性に問題があ
り、また微粒子状の沈降性軽質炭酸カルシウムの
分散には多量の添加を必要とする結果塗膜の耐水
性が悪くなるという重大な欠点があつた。
一方、有機系の分散剤では、ポリアクリル酸
塩・ポリメタクリル酸塩・ポリマレイン酸塩・マ
レイン酸／イソブチレン共重合体塩などのポリカ
ルボン酸塩やポリビニルアルコールなどが公知で
ある。
しかし、ポリカルボン酸塩例えばポリアクリル
酸ナトリウムやマレイン酸／イソブチレン共重合
体ナトリウム塩は、平均粒子系1μ前後の重質炭
酸カルシウムの分散には比較的良好な評価を得て
いるが、0.1〜0.5μ前後の極めて微粒子状の炭酸
カルシウムの分散には得られた水分散液の粘度が
高くまた経日安定性などに問題があつた。また、
ポリビニルアルコールは例えは特開昭60−262862
号などに無機顔料に対して分散効果があることが
記載されている。しかし、特開昭60−262862号に
記載の分散剤は水不溶性であり、炭酸カルシウム
に対する分散効果の不充分なものであり、また、
それ単独使用では得られた水分散液の粘度が異常
に高く、高濃度炭酸カルシウム水分散液製造には
全く不向きであつた。
このような公知の分散剤の欠点を克服するた
め、特公昭54−36166号、特公昭56−47131号、特
開昭53−144499号、特開昭57−168906号などにマ
レイン酸共重合体を使用する方法が提案されてい
る。特公昭54−36166号記載の分散剤は、得られ
る炭酸カルシウム水分散液の流動特性が良く（ハ
イシエアー粘度が低く）比較的良好な評価をされ
ているが、固形分65重量％以上という高濃度での
分散には問題が残るものである。特公昭56−
47131号記載の分散剤は、微粒子状炭酸カルシウ
ム水分散液の粘度は低くなるが、多量の添加量を
必要とする結果コスト上昇や塗膜の耐水性に問題
がある。特開昭53−144499号記載の分散剤は、固
形分濃度70重量％という極めて高い濃度の炭酸カ
ルシウム水分散液が得られているが、やはり1.4
％（対炭酸カルシウム）という高添加量を必要と
している。特開昭57−168906号記載の分散剤は、
得られる炭酸カルシウム水分散液の流動特性が悪
い（ハイシエアー粘度が高い）という重大な欠点
がある。
（発明が解決しようとする問題点）
本発明は、従来の分散剤が有する分散性能不足
に伴う上記問題点を解消するものであり、重質〜
軽質のあらゆる炭酸カルシウムに対して少ない量
の分散剤で低粘度・高流動性かつそれらの経日安
定性の良好な高濃度炭酸カルシウム水分散液の製
造を可能ならしめる方法を提供するものである。
（問題点を解決するための手段および作用）
本発明者らは、それぞれを単独で使用した場
合、軽質炭酸カルシウムの水性媒体中への分散効
果が著しく劣つているポリカルボン酸系共重合体
の中和物と水溶性アニオン化変性ポリビニルアル
コールとを、特定分子量の共重合体の中和物と特
定重合度、特性ケン化度で且つ特定アニオン化変
性度の水溶性ポリビニルアルコールとを選択して
特定の割合で併用することにより、上記分散効果
を従来の分散剤では得られなかつた水準にまで著
しく向上できることを見い出し、本発明を完成さ
せたものである。
即ち、本発明は、炭酸カルシウムを水性媒体中
に分散して水分散液を製造するに際し、分散剤と
して、無水マレイン酸及び無水マレイン酸１モル
に対して0.7〜1.2モルの比率の炭素数２〜７のα
−オレフインを共重合して得られる平均分子量
2000〜80000の共重合体の中和物（）と重合度
30〜700、ケン化度30〜100モル％で且つアニオン
化変性度0.5〜20モル％の水溶性アニオン化変性
ポリビニルアルコール（）とを、炭酸カルシウ
ム100重量部に対して、該共重合体の中和物（）
0.1〜２重量部、水溶性アニオン化変性ポリビニ
ルアルコール（）0.03〜１重量部の範囲の割合
で併用することを特徴とする炭酸カルシウム水分
散液の製造方法に関するものである。
該共重合体の中和物（）（以下、単に中和物
（）ということがある。）と水溶性アニオン化変
性ポリビニルアルコール（）とを前記の範囲の
割合で併用した場合にすぐれた炭酸カルシウム分
散能が発現する作用機構は必ずしも明らかではな
いが、次のように推察されている。すなわち、中
和物（）は炭酸カルシウム粒子表面上に強固に
吸着するため、水溶性アニオン化変性ポリビニル
アルコール（）は炭酸カルシウム粒子表面上に
吸着形態で存在しないか又は少ない量しか存在し
えなくなり、水性媒体中での水溶性アニオン化変
性ポリビニルアルコール（）の濃度が中和物
（）を用いない場合に比べ増加する。本発明者
らはこの現象を鋭意検討した結果、炭酸カルシウ
ム粒子表面上に吸着した中和物（）と水性媒体
中に存在する水溶性アニオン化変性ポリビニルア
ルコール（）との相乗作用により、得られた炭
酸カルシウム水分散液の粘度が大きく低下するこ
と及び経日安定性が極めて改善されることを見い
出し、本発明に到達した。
本発明に用いられる中和物（）を得るには、
無水マレイン酸と炭素数２〜７のα−オレフイン
とを無水マレイン酸１モルに対してα−オレフイ
ン0.7〜1.2モルの比率で用いて公知の技術で重合
し、得られた共重合体をアルカリ性物質により中
和すればよい。
炭素数２〜７のα−オレフインとしては、例え
ばエチレン、プロピレン、１−ブテン、イソブチ
レン、α−アミレン、２−メチル−１−ブテン、
３−メチル−１−ブテン（α−イソアミレン）、
１−ヘキセン、１−ヘプテンなどを単独あるいは
２種以上を併用して用いることができる。
無水マレイン酸とα−オレフインの重合は、例
えばベンゼン、トルエン、キシレン、エチルベン
ゼン、イソプロピルベンゼン等の芳香族炭化水素
系；ジメチルホルムアミド、ジメチルアセトアミ
ド等のアミド系；酢酸メチル、酢酸エチル、酢酸
イソプロピル等の酢酸エステル系；メタノール、
エタノール、ターシヤリーブタノール等のアルコ
ール系；ｎ−ヘキサン、ｎ−ヘプタン等の脂肪族
炭化水素；シクロヘキサン等の脂環式炭化水素系
等の溶媒を単独あるいは混合して重合溶媒として
用い、過酸化ベンゾイル、過酸化ラウロイル、過
酢酸等の有機過酸化物系；アゾビスイソブチロニ
トリル、２，2′−アゾビス（４−メトキシ−２，
４−ジメチルバレロニトリル）等の油溶性アゾ化
合物などを重合触媒として用いて、常法により行
うことができる。
中和物（）を得るに際し、無水マレイン酸と
α−オレフインの共重合比率は無水マレイン酸１
モルに対してα−オレフイン0.7〜1.2モルの範囲
の比率であり、また重合して得られた中和前の共
重合体の平均分子量は2000〜80000の範囲である。
この単量体の使用比率や平均分子量の範囲を外れ
たものは、水溶性アニオン化変性ポリビニルアル
コール（）と併用した際の分散効果が不充分で
ある。
中和物（）は、前記した重合方法によつて得
られた共重合体をアルカリ性物質により中和して
得られるが、得られる中和物（）を水溶性アニ
オン化変性ポリビニルアルコール（）と併用し
た際の分散効果を考慮すれば、共重合体中の全カ
ルボキシル基の少なくとも30モル％を中和するの
が望ましい。このようなアルカリ性物質として
は、例えばナトリウム、カリウム、リチウム等の
水酸化物や炭酸塩；アンモニア；有機アミン；無
機アミン；カルシウム、マクネシウム、アルミニ
ウム、亜鉛等の水酸化物や炭酸塩などを挙げるこ
とができる。中でも安価で工業的に入手しやすい
水酸化ナトリウムが特に好ましい。
また、中和物（）を得るに際して、前記した
アルカリ性物質を用い重合時に使用した溶媒を留
去することにより粉状として得ることも、また
水／溶媒共沸性質を利用し、溶媒を水に置換して
水溶液として得ることもできる。
さらに、中和物（）を得るための重合に際
し、本発明の効果を損なわない範囲で無水マレイ
ン酸及び前記α−オレインと共重合可能な他の単
量体を共重合することは勿論可能である。共重合
可能な他の単量体としては、例えば（メタ）アク
リル酸および（メタ）アクリル酸エチル、（メタ）
アクリル酸ブチル、（メタ）アクリル酸オクチル
（メタ）アクリル酸ドデシルなどの（メタ）アク
リル酸エステル類；（メタ）アリルアルコール、
３−メチル−２−ブテン−１−オール（プレノー
ル）、３−メチル−２−ブテン−２−オール（イ
ソプレンアルコール）、３−メチル−３−ブテン
−１−オール（イソプレノール）などの不飽和ア
ルコール類；スチレン、２−メチルスチレン、ス
チレンスルホン酸などの芳香族ビニル化合物類；
フエニルマレイミド、スルホエチルマレイミドな
どのマレイミド類；フマール酸およびフマール酸
エステル類；イタコン酸およびイタコン酸エステ
ル類；マレイン酸エステル類；クロトン酸および
そのエステル類；cis−ブテン、trans−ブテン、
２−ペンテン、２−メチル−２−ブテン、２，３
−ジメチル−２−ブテン、１−オクテン、１−ノ
ネン、１−デセン、ジイソブチレンなどのオレフ
イン類、（メタ）アクリルアミド、ｔ−ブチル
（メタ）アクリルアミドなどの不飽和アミド類；
酢酸ビニル、ギ酸ビニル、メチルビニルケトン、
フエニルビニルケトンなどのケトン類；メチルビ
ニルエーテル、フエニルビニルエーテルなどのエ
ーテル類などを挙げることができる。
本発明に用いられる水溶性アニオン化変性ポリ
ビニルアルコール（）は、例えば酢酸ビニル／
アニオン性単量体共重合体を公知の技術でケン化
して得られるような分子中にアニオン性基を有す
るポリビニルアルコールであり、重合度が30〜
700、好ましくは100〜300で、ケン化度が30〜100
モル％、好ましくは65〜100モル％である且つア
ニオン化変性度0.5〜20モル％、好ましくは１〜
10モル％の範囲のものが有効に用いられる。水溶
性アニオン化変性ポリビニルアルコール（）の
重合度、ケン化度およびアニオン化変性度のいず
れか一つでも前記の範囲を外れたものは、中和物
（）と併用した際の分散効果が不充分である。
特に、水溶性アニオン化変性ポリビニルアルコー
ル（）のアニオン化変性度が0.5モル％未満の
ものでは、未変性のポリビニルアルコールと実質
的に同じになり、得られた炭酸カルシウム水分散
液の経日安定性に問題が生じてくる。逆にアニオ
ン化変性度が20モル％を越えるものでは、多量の
添加量を必要とし好ましくない。
水溶性アニオン化変性ポリビニルアルコール
（）を得るに際してアニオン化変性のため用い
られるアニオン性単量体の例としては、アリルス
ルホン酸、メタリルスルホン酸、スチレンスルホ
ン酸、ビニルスルホン酸、３−アリルロキシ−２
−ヒドロキシプロパンスルホン酸、スルホエチル
（メタ）アクリレート、２−アクリルアミド−２
−メチルプロパンスルホン酸、スルホエチルマレ
ミド、スルホアルキルマレエートあるいはそれら
の１価金属塩、アンモニウム塩、アミン塩などの
スルホン酸系単量体；アクリル酸、メタアクリル
酸、α−ヒドロキシアクリル酸、（無水）マレイ
ン酸、イタコン酸、フマール酸、クロトン酸、シ
トラコン酸、アコニツト酸あるいはそれらの１価
金属塩、アンモニウム塩、アミン塩などのカルボ
ン酸系単量体；（メタ）アクリルアミドメタンホ
スホン酸、２−（メタ）アクリルアミド−２−メ
チルプロパンホスホン酸、モノ〔２−ヒドロキシ
エチル（メタ）アクリレート〕アシツドホスフエ
ート、モノ〔３−クロロ−２−ヒドロキシプロピ
ル（メタ）アクリレート〕アシツドホスフエート
あるいはそれらの１価金属塩、アンモニウム塩、
アミン塩などのホスホン酸系単量体などを挙げる
ことができる。
水溶性アニオン化変性ポリビニルアルコール
（）を得るには、酢酸ビニル／アニオン性単量
体共重合体をケン化して得られるものに限定され
るものではない。例えばポリビニルアルコールを
臭素、ヨウ素等で処理したのち酸性亜硫酸ナトリ
ウム等のスルホン化剤を用いてスルホン化変性す
ることも、またポリビニルアルコールを濃厚な硫
酸水溶液中で硫酸エステル化変性をすることも、
さらには酢酸ビニル／（メタ）アクリル酸エステ
ル共重合体などをケン化してカルボキシル化変性
することも勿論可能である。
このような水溶性アニオン化変性ポリビニルア
ルコール（）の中でも、安価かつ工業的に容易
に製造できる水溶性スルホン化変性ポリビニルア
ルコールまたは水溶性カルボキシル化変性ポリビ
ニルアルコールが特に好ましい。
本発明では、中和物（）は炭酸カルシウム
100重量部に対して0.1〜２重量部、水溶性アニオ
ン化変性ポリビニルアルコール（）は炭酸カル
シウム100重量部に対して0.03〜１重量部の範囲
の割合で併用される。中和物（）又は水溶性ア
ニオン化変性ポリビニルアルコール（）の使用
量が前記範囲より少ないと、低粘度でその経日安
定性の良好な炭酸カルシウム水分散液が得られな
い。また、これらの使用量を前記範囲より多くし
ても増量に見合つた分散効果は得られず、逆に得
られた炭酸カルシウム水分散液を使用した塗膜の
耐水性が低下するため好ましくない。
本発明において、中和物（）と水溶性アニオ
ン化変性ポリビニルアルコール（）とを分散剤
として併用する際の添加順序には特別の制限はな
い。即ち、中和物（）で炭酸カルシウムを水性
媒体中に粗分散した後に水溶性アニオン化変性ポ
リビニルアルコール（）を添加して微分散する
ことも、逆に水溶性アニオン化変性ポリビニルア
ルコール（）で粗分散した後に中和物（）を
添加して微分散することもできる。また、中和物
（）と水溶性アニオン化変性ポリビニルアルコ
ール（）とを同時に添加して併用することも可
能である。
さらに、本発明の効果を損なわない範囲で、公
知の有機系分散剤例えばポリアクリル酸塩、ポリ
メタクリル酸塩、ポリマレイン酸塩、（メタ）ア
クリル酸／マレイン酸共重合体、（メタ）アクリ
ル酸／イタコン酸共重合体などや、公知の無機系
分散剤例えばカルシウム・マグネシウム・アルミ
ニウム・亜鉛などの多価金属の水酸化物、炭酸塩
あるいはハロゲン化物や、ピロリン酸塩、トリポ
リリン酸液、ヘキサメタリン酸塩などの縮合リン
酸塩などを併用することは勿論可能である。
（発明の効果）
本発明の方法によれば、特定の共重合体の中和
物と特定の水溶性アニオン化変性ポリビニルアル
コールとを分散剤として特定の割合で併用してい
ることから、重質〜軽質のあらゆる炭酸カルシウ
ムに対して少ない量の分散剤で高濃度炭酸カルシ
ウム水分酸液とすることができる。また、本発明
の方法で得られた炭酸カルシウム水分散液は、低
粘度・高流動性でそれらの経日安定性にも優れて
いるため、得られる塗膜の耐水性に悪影響を及ぼ
すことなく、塗料のその他の用途に有効に使用で
きる。
また、本発明で得られた分散剤は、他の無機顔
料例えばクレー、酸化チタン、サチンホワイト、
水酸化アルミニウム、消石灰、ベンガラ、セメン
ト、アルキナ、ジルコニア、シリカ、炭化ケイ
素、チツ化ケイ素などにも有効に用いられる。
（実施例）
以下、実施例をあげて本発明を具体的に説明す
るが、本発明はこれらの例により限定されるもの
ではない。尚、例中の部および％はそれぞれ重量
部および重量％を示す。また、例中の対炭酸カル
シウム％は炭酸カルシウム固形分に対する分散剤
〔共重合体の中和物（）や水溶性アニオン化変
性ポリビニルアルコール（）〕の固形分重量比
率を示す。
実施例 １
容量１（材質SUS 304、内径90mm、高さ160
mm）のビーカーに、カルサイト系立方体状の軽質
炭酸カルシウム（一次粒子径0.15μ）のフイルタ
ープレス脱水ケーキ（固形分65.3％）400部をと
り、そこへ分散剤としての数平均分子量が6000で
あるイソブチレン／無水マレイン酸＝0.9／１（モ
ル比）共重合体のナトリウム塩20％水溶液6.52部
（対炭酸カルシウム0.5％）、重合度が250でケン化
度が88モル％で且つｐ−スチレンスルホン酸の共
重合体によるスルホン化度が３モル％のアニオン
化変性ポリビニルアルコール20％水溶液2.61部
（対炭酸カルシウム0.2％）及び固形分濃度調整用
の水1.9部を加え、デイゾルバー撹拌羽根（50mm
φ）にて低速で３分間混練後、3000rpmで10分間
分散し、固形分濃度64％の水分散液(1)を得た。
得られた水分散液(1)の粘度（Ｂ型粘度計・25℃
で測定）及び経日安定性の試験結果を第１表に示
した。また、製造直後の水分散液(1)の流動特性を
ハーキユレス粘度計（熊谷理機工業(株)製、HR−
801C型）で測定（ボブＢ、スイープタイム20秒）
し、得られたオレグラムを第１図に示した。
実施例 ２〜７
分散剤として第１表に示した所定量の共重合体
の中和物（）及び水溶性アニオン化変性ポリビ
ニルアルコール（）と所定量の固形分濃度調整
水とを用いた他は実施例１と同様にして、固形分
濃度64％の水分散液(2)〜(7)を得た。
得られた水分散液(2)〜(7)の粘度及び経日安定性
を実施例１と同様にして測定し、その試験結果を
第１表に示した。
(Industrial Application Field) The present invention relates to a method for efficiently dispersing calcium carbonate in an aqueous medium to produce an aqueous dispersion. The present invention relates to a method for producing an aqueous calcium carbonate dispersion, characterized in that polyvinyl alcohol is used in combination as a dispersant. (Prior Art) Calcium carbonate is one of the pigments prized in the paper industry because it is inexpensive and has superior whiteness, ink receptivity, gloss, and printability compared to other inorganic pigments. Furthermore, with the spread of neutral paper making, its usage is rapidly increasing. Traditionally, so-called heavy calcium carbonate with an average particle size of around 1 μm has been frequently used as calcium carbonate, but in recent years, with the advancement of paper quality, the average particle size has increased from 0.1 to 1 μm.
The proportion of use of 0.5μ precipitated light calcium carbonate is increasing. However, the smaller the average particle size, the more difficult it becomes to disperse in an aqueous medium.
In addition, it tends to aggregate, which tends to cause problems in the stability of the aqueous dispersion over time. Conventionally used dispersants for calcium carbonate include inorganic condensed phosphates such as pyrophosphate, tripolyphosphate, trimetaphosphate, tetrametaphosphate, and hexametaphosphate, zinc salts,
Silicates, etc. However, these inorganic dispersants have problems with the stability of the resulting aqueous dispersion over time, and they require a large amount to be added to disperse the finely divided precipitated light calcium carbonate, resulting in the water resistance of the coating film. It had a serious drawback: it made it worse. On the other hand, known organic dispersants include polycarboxylic acid salts such as polyacrylates, polymethacrylates, polymaleates, maleic acid/isobutylene copolymer salts, and polyvinyl alcohol. However, polycarboxylate salts such as sodium polyacrylate and maleic acid/isobutylene copolymer sodium salt have been relatively well evaluated for dispersing heavy calcium carbonate with an average particle size of around 1μ, but When dispersing calcium carbonate in the form of extremely fine particles of around 0.5 μm, the resulting aqueous dispersion had a high viscosity and had problems with stability over time. Also,
Polyvinyl alcohol is an example of JP-A-60-262862.
It is stated that it has a dispersing effect on inorganic pigments. However, the dispersant described in JP-A-60-262862 is water-insoluble and has insufficient dispersing effect on calcium carbonate.
When used alone, the resulting aqueous dispersion had an abnormally high viscosity and was completely unsuitable for producing a highly concentrated calcium carbonate aqueous dispersion. In order to overcome the drawbacks of such known dispersants, maleic acid copolymers have been developed in Japanese Patent Publication No. 54-36166, Japanese Patent Publication No. 56-47131, Japanese Patent Application Laid-open No. 144499-1982, Japanese Patent Application Laid-open No. 168906-1987, etc. A method using . The dispersant described in Japanese Patent Publication No. 54-36166 has been evaluated as relatively good because the resulting aqueous calcium carbonate dispersion has good flow characteristics (low shear viscosity), but it has a high solid content of 65% by weight or more. There remains a problem with the dispersion. Special Public Service 1976-
The dispersant described in No. 47131 lowers the viscosity of the aqueous fine-particle calcium carbonate dispersion, but requires a large amount to be added, resulting in increased costs and problems with water resistance of the coating film. The dispersant described in JP-A No. 53-144499 yields an aqueous calcium carbonate dispersion with an extremely high solid content of 70% by weight, but it also has a solid content of 1.4% by weight.
% (relative to calcium carbonate). The dispersant described in JP-A-57-168906 is
A serious drawback is that the resulting aqueous calcium carbonate dispersion has poor flow properties (high shear viscosity). (Problems to be Solved by the Invention) The present invention solves the above-mentioned problems associated with insufficient dispersion performance of conventional dispersants.
The present invention provides a method that enables the production of highly concentrated aqueous calcium carbonate dispersions with low viscosity, high fluidity, and good stability over time using a small amount of dispersant for all types of light calcium carbonate. . (Means and effects for solving the problem) The present inventors have discovered that polycarboxylic acid copolymers have a significantly poor dispersion effect of light calcium carbonate in an aqueous medium when used alone. A neutralized product and a water-soluble anionized modified polyvinyl alcohol are selected, and a neutralized product of a copolymer with a specific molecular weight and a water-soluble polyvinyl alcohol with a specific degree of polymerization, a specific degree of saponification, and a specific degree of anionized modification are selected. The present invention has been completed based on the discovery that, by using them together in a specific ratio, the above-mentioned dispersion effect can be significantly improved to a level that could not be obtained with conventional dispersants. That is, in the present invention, when dispersing calcium carbonate in an aqueous medium to produce an aqueous dispersion, maleic anhydride and a carbon number of 2 at a ratio of 0.7 to 1.2 mole per mole of maleic anhydride are used as a dispersant. ~7 α
−Average molecular weight obtained by copolymerizing olefins
Neutralized product of copolymer (2000-80000) and degree of polymerization
30 to 700, a degree of saponification of 30 to 100 mol%, and a degree of anionic modification of 0.5 to 20 mol%. Neutralized product ()
The present invention relates to a method for producing an aqueous calcium carbonate dispersion, characterized in that it is used in combination in a proportion ranging from 0.1 to 2 parts by weight and from 0.03 to 1 part by weight of water-soluble anionized modified polyvinyl alcohol (). When the neutralized product () of the copolymer (hereinafter sometimes simply referred to as the neutralized product (2)) and the water-soluble anionized modified polyvinyl alcohol (2) are used together in the ratio within the above range, excellent carbonic acid can be produced. Although the mechanism of action by which calcium dispersion ability is expressed is not necessarily clear, it is speculated as follows. In other words, since the neutralized product () is strongly adsorbed on the surface of the calcium carbonate particles, the water-soluble anionized modified polyvinyl alcohol () does not exist in an adsorbed form on the surface of the calcium carbonate particles, or can only exist in a small amount. , the concentration of the water-soluble anionized modified polyvinyl alcohol () in the aqueous medium increases compared to when the neutralized product () is not used. As a result of intensive studies by the present inventors on this phenomenon, we found that a synergistic effect between the neutralized product ( ) adsorbed on the surface of calcium carbonate particles and the water-soluble anionized modified polyvinyl alcohol ( ) present in the aqueous medium resulted in The inventors have discovered that the viscosity of an aqueous calcium carbonate dispersion is significantly reduced and the stability over time is significantly improved, and the present invention has been achieved. To obtain the neutralized product () used in the present invention,
Maleic anhydride and an α-olefin having 2 to 7 carbon atoms are polymerized using a known technique using a ratio of 0.7 to 1.2 mol of α-olefin per 1 mol of maleic anhydride, and the resulting copolymer is made alkaline. It can be neutralized with a substance. Examples of the α-olefin having 2 to 7 carbon atoms include ethylene, propylene, 1-butene, isobutylene, α-amylene, 2-methyl-1-butene,
3-methyl-1-butene (α-isoamylene),
1-hexene, 1-heptene, etc. can be used alone or in combination of two or more. The polymerization of maleic anhydride and α-olefin can be carried out using, for example, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and isopropylbenzene; amide systems such as dimethylformamide and dimethylacetamide; and methyl acetate, ethyl acetate, and isopropyl acetate. Acetate ester; methanol,
Alcohols such as ethanol and tertiary-butanol; aliphatic hydrocarbons such as n-hexane and n-heptane; and alicyclic hydrocarbons such as cyclohexane are used alone or in combination as polymerization solvents to produce benzoyl peroxide. , lauroyl peroxide, peracetic acid and other organic peroxides; azobisisobutyronitrile, 2,2'-azobis(4-methoxy-2,
The polymerization can be carried out by a conventional method using an oil-soluble azo compound such as (4-dimethylvaleronitrile) as a polymerization catalyst. When obtaining the neutralized product (), the copolymerization ratio of maleic anhydride and α-olefin is 1 maleic anhydride and 1
The ratio is in the range of 0.7 to 1.2 moles to α-olefin, and the average molecular weight of the copolymer obtained by polymerization before neutralization is in the range of 2,000 to 80,000.
If the monomer usage ratio or average molecular weight is out of this range, the dispersion effect will be insufficient when used in combination with water-soluble anionized modified polyvinyl alcohol (). The neutralized product () is obtained by neutralizing the copolymer obtained by the above polymerization method with an alkaline substance, and the neutralized product () obtained is mixed with water-soluble anionized modified polyvinyl alcohol (). Considering the dispersion effect when used in combination, it is desirable to neutralize at least 30 mol% of all carboxyl groups in the copolymer. Examples of such alkaline substances include hydroxides and carbonates of sodium, potassium, lithium, etc.; ammonia; organic amines; inorganic amines; hydroxides and carbonates of calcium, magnesium, aluminum, zinc, etc. Can be done. Among them, sodium hydroxide is particularly preferred because it is inexpensive and industrially easily available. In addition, when obtaining the neutralized product (), it is also possible to obtain it in powder form by distilling off the solvent used during polymerization using the alkaline substance described above, or by using the water/solvent azeotrope property to convert the solvent into water. It can also be obtained as an aqueous solution by substitution. Furthermore, during the polymerization to obtain the neutralized product (), it is of course possible to copolymerize other monomers that can be copolymerized with maleic anhydride and the α-olein within a range that does not impair the effects of the present invention. be. Examples of other copolymerizable monomers include (meth)acrylic acid and ethyl (meth)acrylate, (meth)
(meth)acrylic acid esters such as butyl acrylate, octyl (meth)acrylate, and dodecyl (meth)acrylate; (meth)allyl alcohol;
Unsaturated alcohols such as 3-methyl-2-buten-1-ol (prenol), 3-methyl-2-buten-2-ol (isoprene alcohol), 3-methyl-3-buten-1-ol (isoprenol) Aromatic vinyl compounds such as styrene, 2-methylstyrene, styrene sulfonic acid;
Maleimides such as phenylmaleimide and sulfoethylmaleimide; fumaric acid and fumaric acid esters; itaconic acid and itaconic esters; maleic acid esters; crotonic acid and its esters; cis-butene, trans-butene,
2-pentene, 2-methyl-2-butene, 2,3
- Olefins such as dimethyl-2-butene, 1-octene, 1-nonene, 1-decene, and diisobutylene; unsaturated amides such as (meth)acrylamide and t-butyl (meth)acrylamide;
Vinyl acetate, vinyl formate, methyl vinyl ketone,
Examples include ketones such as phenyl vinyl ketone; ethers such as methyl vinyl ether and phenyl vinyl ether. The water-soluble anionized modified polyvinyl alcohol () used in the present invention is, for example, vinyl acetate/
It is a polyvinyl alcohol having an anionic group in the molecule, which is obtained by saponifying an anionic monomer copolymer using a known technique, and has a degree of polymerization of 30 to 30.
700, preferably 100-300, saponification degree 30-100
mol%, preferably 65 to 100 mol%, and degree of anionic modification 0.5 to 20 mol%, preferably 1 to 100 mol%
A range of 10 mol% is effectively used. If any one of the degree of polymerization, degree of saponification, and degree of anionic modification of the water-soluble anionized modified polyvinyl alcohol () is outside the above range, the dispersion effect will be poor when used in combination with the neutralized product (). That's enough.
In particular, when the degree of anionic modification of water-soluble anionized modified polyvinyl alcohol () is less than 0.5 mol%, it becomes substantially the same as unmodified polyvinyl alcohol, and the obtained calcium carbonate aqueous dispersion is stable over time. Sexual problems arise. On the other hand, if the degree of anionic modification exceeds 20 mol %, a large amount is required to be added, which is not preferable. Examples of anionic monomers used for anionic modification when obtaining water-soluble anionized modified polyvinyl alcohol () include allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-allyloxy- 2
-Hydroxypropanesulfonic acid, sulfoethyl (meth)acrylate, 2-acrylamide-2
- Sulfonic acid monomers such as methylpropanesulfonic acid, sulfoethyl malemide, sulfoalkyl maleate, or their monovalent metal salts, ammonium salts, and amine salts; acrylic acid, methacrylic acid, α-hydroxyacrylic acid, Carboxylic acid monomers such as (anhydrous) maleic acid, itaconic acid, fumaric acid, crotonic acid, citraconic acid, aconitic acid, or their monovalent metal salts, ammonium salts, and amine salts; (meth)acrylamide methanephosphonic acid, 2-(meth)acrylamido-2-methylpropanephosphonic acid, mono[2-hydroxyethyl (meth)acrylate] acid phosphate, mono[3-chloro-2-hydroxypropyl (meth)acrylate] acid phosphate or their monovalent metal salts, ammonium salts,
Examples include phosphonic acid monomers such as amine salts. In order to obtain water-soluble anionized modified polyvinyl alcohol (), it is not limited to that obtained by saponifying a vinyl acetate/anionic monomer copolymer. For example, polyvinyl alcohol may be treated with bromine, iodine, etc. and then sulfonated using a sulfonating agent such as acidic sodium sulfite, or polyvinyl alcohol may be sulfuric acid esterified in a concentrated sulfuric acid aqueous solution.
Furthermore, it is of course possible to saponify a vinyl acetate/(meth)acrylic acid ester copolymer or the like to modify it by carboxylation. Among such water-soluble anionized modified polyvinyl alcohols, water-soluble sulfonated modified polyvinyl alcohols or water-soluble carboxylated modified polyvinyl alcohols, which are inexpensive and easily produced industrially, are particularly preferred. In the present invention, the neutralized product () is calcium carbonate
0.1 to 2 parts by weight per 100 parts by weight, and water-soluble anionized modified polyvinyl alcohol () is used in an amount of 0.03 to 1 part by weight per 100 parts by weight of calcium carbonate. If the amount of the neutralized product () or the water-soluble anionized modified polyvinyl alcohol () used is less than the above range, an aqueous calcium carbonate dispersion with low viscosity and good stability over time cannot be obtained. Further, even if the amount used is increased beyond the above range, a dispersion effect commensurate with the increased amount cannot be obtained, and on the contrary, the water resistance of the coating film using the obtained calcium carbonate aqueous dispersion is decreased, which is not preferable. In the present invention, there is no particular restriction on the order of addition when the neutralized product () and the water-soluble anionized modified polyvinyl alcohol () are used together as a dispersant. That is, calcium carbonate can be roughly dispersed in an aqueous medium using a neutralized product () and then finely dispersed by adding water-soluble anionized modified polyvinyl alcohol (), or conversely, calcium carbonate can be dispersed finely by adding water-soluble anionized modified polyvinyl alcohol (). After coarsely dispersing, a neutralized product () can be added to finely disperse. It is also possible to add the neutralized product (2) and the water-soluble anionized modified polyvinyl alcohol (2) at the same time for use in combination. Additionally, known organic dispersants, such as polyacrylates, polymethacrylates, polymaleates, (meth)acrylic acid/maleic acid copolymers, (meth)acrylic acid, may be used within a range that does not impair the effects of the present invention. / Itaconic acid copolymer, etc., known inorganic dispersants, such as hydroxides, carbonates, or halides of polyvalent metals such as calcium, magnesium, aluminum, and zinc, pyrophosphate, tripolyphosphate liquid, hexametaphosphoric acid It is of course possible to use condensed phosphates such as salts in combination. (Effects of the Invention) According to the method of the present invention, since a neutralized product of a specific copolymer and a specific water-soluble anionized modified polyvinyl alcohol are used together as a dispersant in a specific ratio, heavy -A high-concentration calcium carbonate water-acid solution can be obtained with a small amount of dispersant for all types of light calcium carbonate. In addition, the calcium carbonate aqueous dispersion obtained by the method of the present invention has low viscosity, high fluidity, and excellent stability over time, so it does not adversely affect the water resistance of the resulting coating film. , it can be effectively used for other applications of paint. In addition, the dispersant obtained in the present invention can be used with other inorganic pigments such as clay, titanium oxide, satin white,
It can also be effectively used for aluminum hydroxide, slaked lime, red iron oxide, cement, alkina, zirconia, silica, silicon carbide, silicon titanide, etc. (Examples) Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples. Note that parts and % in the examples indicate parts by weight and % by weight, respectively. In addition, the % to calcium carbonate in the examples indicates the solid content weight ratio of the dispersant [neutralized copolymer (2) or water-soluble anionized modified polyvinyl alcohol (2)] to the solid content of calcium carbonate. Example 1 Capacity 1 (Material SUS 304, inner diameter 90mm, height 160mm)
400 parts of a filter press dehydrated cake (solid content 65.3%) of calcite-based cubic light calcium carbonate (primary particle size 0.15μ) is placed in a beaker with a number average molecular weight of 6000 as a dispersant. 6.52 parts of a 20% aqueous solution of sodium salt (based on calcium carbonate: 0.5%) of a certain isobutylene/maleic anhydride = 0.9/1 (mole ratio) copolymer, the degree of polymerization is 250, the degree of saponification is 88 mol%, and p-styrene Add 2.61 parts of a 20% aqueous solution of anionized modified polyvinyl alcohol with a degree of sulfonation of 3 mol% by a copolymer of sulfonic acid (based on calcium carbonate: 0.2%) and 1.9 parts of water for adjusting the solid content concentration, and add a dissolver stirring blade (50 mm).
After kneading at low speed for 3 minutes at φ), the mixture was dispersed at 3000 rpm for 10 minutes to obtain an aqueous dispersion (1) with a solid content concentration of 64%. Viscosity of the obtained aqueous dispersion (1) (B type viscometer, 25℃
Table 1 shows the test results for stability over time (measured by In addition, the flow characteristics of the aqueous dispersion (1) immediately after production were measured using a Hercules viscometer (manufactured by Kumagai Riki Kogyo Co., Ltd., HR-
801C type) (Bob B, sweep time 20 seconds)
The obtained olegram is shown in FIG. Examples 2 to 7 Predetermined amounts of neutralized copolymers () and water-soluble anionized modified polyvinyl alcohol () shown in Table 1 as dispersants and predetermined amounts of solid content adjustment water were used. In the same manner as in Example 1, aqueous dispersions (2) to (7) having a solid content concentration of 64% were obtained. The viscosity and aging stability of the obtained aqueous dispersions (2) to (7) were measured in the same manner as in Example 1, and the test results are shown in Table 1.
【表】【table】
【表】
比較例 １
分散剤として平均分子量が4000であるアクリル
酸／マレイン酸＝60／40（モル比）の共重合体の
ナトリウム塩40％水溶液4.57部（対炭酸カルシウ
ム0.7％）及び固形分濃度調整用の水6.4部を用い
た他は実施例１と同様にして、固形分濃度64％の
比較用水分散液(1)を得た。
得られた比較用水分散液(1)の粘度及び経日安定
性を実施例１と同様にして測定しその試験結果を
第２表に示した、また製造直後の比較用水分散液
(1)の流動特性をハーキユレス粘度計で測定（ボブ
Ｂ、スイープタイプ20秒）し、得られたオレグラ
ムを第１図に示した。
比較例 ２〜５
分散剤として第２表に示した水溶性重合体また
は共重合体の中和物（）を0.7％（対炭酸カル
シウム）及び所定量の固形分濃度調整水を用いた
他は実施例１と同様にして、固形分濃度64％の比
較用水分散液(2)〜(5)を得た。
得られた比較用水分散液(2)〜(5)の粘度及び経日
安定性を実施例１と同様にして測定し、その試験
結果を第２表に示した。
比較例 ６〜８
分散剤として第２表に示した水溶性アニオン化
変性ポリビニルアルコール（）を0.7％（対炭
酸カルシウム）及び所定量の固形分濃度調整水を
用いた他は実施例１と同様にして、固形分濃度64
％の比較用水分散液(6)〜(8)を得た。
得られた比較用水分散液(6)〜(8)の粘度及び経日
安定性を実施例１と同様にして測定し、その試験
結果を第２表に示した。
比較例 ９〜21
分散剤として第２表に示した水溶性重合体また
は共重合体の中和物（）及び水溶性ポリビニル
アルコールまたは水溶性アニオン化変性ポリビニ
ルアルコール（）並びに所定量の固形分濃度調
整水を用いた他は実施例１と同様にして、固形分
濃度64％の比較用水分散液(9)〜（21）を得た。
得られた比較用水分散液(9)〜（21）の粘度及び
経日安定性を実施例１と同様にして測定し、その
試験結果を第２表に示した。[Table] Comparative Example 1 4.57 parts of a 40% aqueous solution of sodium salt of a copolymer of acrylic acid/maleic acid = 60/40 (mole ratio) with an average molecular weight of 4000 as a dispersant (based on calcium carbonate 0.7%) and solid content A comparative aqueous dispersion (1) having a solid content concentration of 64% was obtained in the same manner as in Example 1 except that 6.4 parts of water for concentration adjustment was used. The viscosity and aging stability of the obtained comparative aqueous dispersion (1) were measured in the same manner as in Example 1, and the test results are shown in Table 2.
The flow characteristics of (1) were measured using a Hercules viscometer (Bob B, sweep type 20 seconds), and the obtained oleogram is shown in Figure 1. Comparative Examples 2 to 5 Except for using 0.7% (based on calcium carbonate) of a neutralized product () of a water-soluble polymer or copolymer shown in Table 2 as a dispersant and a predetermined amount of solid content concentration-adjusted water. Comparative aqueous dispersions (2) to (5) having a solid content concentration of 64% were obtained in the same manner as in Example 1. The viscosity and aging stability of the obtained comparative aqueous dispersions (2) to (5) were measured in the same manner as in Example 1, and the test results are shown in Table 2. Comparative Examples 6 to 8 Same as Example 1 except that 0.7% (based on calcium carbonate) of water-soluble anionized modified polyvinyl alcohol () shown in Table 2 as a dispersant and a predetermined amount of solid content adjustment water were used. and solid content concentration 64
% comparative aqueous dispersions (6) to (8) were obtained. The viscosity and aging stability of the obtained comparative aqueous dispersions (6) to (8) were measured in the same manner as in Example 1, and the test results are shown in Table 2. Comparative Examples 9 to 21 Neutralized water-soluble polymers or copolymers shown in Table 2 as dispersants () and water-soluble polyvinyl alcohol or water-soluble anionized modified polyvinyl alcohol () and a predetermined amount of solid content concentration Comparative aqueous dispersions (9) to (21) having a solid content concentration of 64% were obtained in the same manner as in Example 1 except that adjusted water was used. The viscosity and aging stability of the obtained comparative aqueous dispersions (9) to (21) were measured in the same manner as in Example 1, and the test results are shown in Table 2.
【表】【table】
【表】
実施例 ８〜14
実施例１で用いた容量１のビーカーに分散剤
として第３表に示した共重合体の中和物（）
2.5部（対炭酸カルシウム0.5％）及び水溶性アニ
オン化変性ポリビニルアルコール（）0.5部
（対炭酸カルシウム0.1％）とり、水を加えて全量
を170.7部とした。得られた分散剤水溶液に、実
施例１で用いた撹拌羽根にて1000rpm撹拌下、重
質炭酸カルシウム（平均粒子径10μ）500部を２
分間で添加し、プレミツクス液を作成した。次い
で、このプレミツクス液をベツセル容量１のサ
ンドグラインダー（メジアとしてガラスビーズ
（1.0〜1.5mmφ）0.35、撹拌回転数3000rpm）に
て粒子径2μ以下のものの割合が90％で平均粒子
径が0.8μになるまで分散し、固形分濃度75％の炭
酸カルシウム水分散液(8)〜(14)を得た。
得られた水分散液(8)〜(14)の粘度及び経日安定性
を実施例１と同様にして測定し、その試験結果を
第３表に示した。[Table] Examples 8 to 14 Neutralized product of the copolymer shown in Table 3 as a dispersant in the beaker with a capacity of 1 used in Example 1 ()
2.5 parts (based on calcium carbonate: 0.5%) and 0.5 parts of water-soluble anionized modified polyvinyl alcohol (based on calcium carbonate: 0.1%) were added, and water was added to make the total amount 170.7 parts. 500 parts of heavy calcium carbonate (average particle size 10μ) was added to the obtained aqueous dispersant solution while stirring at 1000 rpm using the stirring blade used in Example 1.
The mixture was added within minutes to create a premix solution. Next, this premix liquid was processed using a sand grinder with a Vessel capacity of 1 (glass beads (1.0 to 1.5 mmφ) as media, 0.35, stirring rotation speed 3000 rpm) until the proportion of particles with a particle diameter of 2 μ or less was 90% and the average particle diameter was 0.8 μ. Aqueous calcium carbonate dispersions (8) to (14) having a solid content concentration of 75% were obtained. The viscosity and aging stability of the obtained aqueous dispersions (8) to (14) were measured in the same manner as in Example 1, and the test results are shown in Table 3.
【表】【table】
【表】
比較例 22〜26
分散剤として第４表に示した水溶性重合体また
は共重合体の中和物（）を3.0部（対炭酸カル
シウム0.6％）及び所定量の水を用いた他は実施
例７〜12と同様にして、固形分濃度75％の比較用
水分散液（22）〜（26）を得た。
得られた比較用水分散液（22）〜（26）の粘度
及び経日安定性を実施例１と同様にして測定し、
その試験結果を第４表に示した。
比較例 27〜29
分散剤として第４表に示した水溶性アニオン化
変性ポリビニルアルコール（）を0.3部（対炭
酸カルシウム0.6％）及び所定量の水を用いた他
は実施例８〜14と同様にして、固形分濃度75％の
比較用水分散液（27）〜（29）を得た。
得られた比較用水分散液（27）〜（29）の粘度
及び経日安定性を実施例１と同様にして測定し、
その試験結果を第４表に示した。
比較例 30〜42
分散剤として第４表に示した水溶性重合体また
は共重合体の中和物（）2.5部（対炭酸カルシ
ウム0.5％）及び水溶性ポリビニルアルコールま
たは水溶性アニオン化変性ポリビニルアルコール
（）0.5部（対炭酸カルシウム0.1％）並びに所
定量の水を用いた他は実施例８〜14と同様にし
て、固形分濃度75％の比較用水分散液（30）〜
（42）を得た。
得られた比較用水分散液（30）〜（42）の粘度
及び経日安定性を実施例１と同様にして測定し、
その試験結果を第４表に示した。[Table] Comparative Examples 22 to 26 Using 3.0 parts (0.6% of calcium carbonate) of the neutralized water-soluble polymer or copolymer shown in Table 4 as a dispersant and a predetermined amount of water, etc. Comparative aqueous dispersions (22) to (26) having a solid content concentration of 75% were obtained in the same manner as in Examples 7 to 12. The viscosity and aging stability of the obtained comparative aqueous dispersions (22) to (26) were measured in the same manner as in Example 1,
The test results are shown in Table 4. Comparative Examples 27-29 Same as Examples 8-14 except that 0.3 parts of water-soluble anionized modified polyvinyl alcohol () shown in Table 4 (0.6% to calcium carbonate) and a predetermined amount of water were used as a dispersant. Comparative aqueous dispersions (27) to (29) having a solid content concentration of 75% were obtained. The viscosity and aging stability of the obtained comparative aqueous dispersions (27) to (29) were measured in the same manner as in Example 1,
The test results are shown in Table 4. Comparative Examples 30 to 42 2.5 parts of neutralized water-soluble polymer or copolymer shown in Table 4 as a dispersant (0.5% to calcium carbonate) and water-soluble polyvinyl alcohol or water-soluble anionized modified polyvinyl alcohol A comparative aqueous dispersion (30) with a solid content concentration of 75% was prepared in the same manner as in Examples 8 to 14, except that 0.5 part () (based on calcium carbonate: 0.1%) and a predetermined amount of water were used.
(42) was obtained. The viscosity and aging stability of the obtained comparative aqueous dispersions (30) to (42) were measured in the same manner as in Example 1,
The test results are shown in Table 4.
【表】【table】
【表】
実施例 15〜21
実施例１で用いた容量１のビーカーに、分散
剤として第５表に示した共重合体の中和物（）
0.8部（対炭酸カルシウム0.2％）及び水溶性アニ
オン化変性ポリビニルアルコール（）0.4部
（対炭酸カルシウム0.1％）とり、水を加えて全量
を183.5部とした。得られた分散剤水溶液に、デ
イゾルバー撹拌羽根（50mmφ）にて低速撹拌下、
カルサイト系立方体状の軽質炭酸カルシウム微粉
末（一次粒子径0.2μ）400部を３分間で添加した
後、3000rpmで10分間撹拌して分散した。次い
で、分散剤水溶液を調製する際に用いたのと同じ
水溶性アニオン化変性ポリビニルアルコール
（）の10％水溶液８部（対炭酸カルシウム0.2
％）を添加し、さらに3000rpmで２分間撹拌し、
固形分濃度68％の炭酸カルシウム水分散液(15)〜
（21）を得た。
得られた水分散液(15)〜（21）の粘度及び経日安
定性を実施例１と同様に測定し、その試験結果を
第５表に示した。[Table] Examples 15 to 21 Into the beaker with a capacity of 1 used in Example 1, the neutralized product of the copolymer shown in Table 5 as a dispersant () was added.
0.8 parts (0.2% relative to calcium carbonate) and 0.4 parts (0.1% relative to calcium carbonate) of water-soluble anionized modified polyvinyl alcohol were taken, and water was added to make the total amount 183.5 parts. The obtained dispersant aqueous solution was stirred at low speed using a dissolver stirring blade (50 mmφ).
After adding 400 parts of calcite cubic light calcium carbonate fine powder (primary particle size 0.2 μm) over 3 minutes, the mixture was stirred at 3000 rpm for 10 minutes to disperse. Next, 8 parts of a 10% aqueous solution of the same water-soluble anionized modified polyvinyl alcohol () used in preparing the dispersant aqueous solution (0.2
%) and further stirred at 3000 rpm for 2 minutes.
Calcium carbonate aqueous dispersion with solid content concentration of 68% (15) ~
(21) was obtained. The viscosity and aging stability of the obtained aqueous dispersions (15) to (21) were measured in the same manner as in Example 1, and the test results are shown in Table 5.
【表】【table】
【表】
以上の結果より、分散剤として特定の平均分子
量を有する共重合体の中和物（）と特定重合
度・特定ケン化度及び特定アニオン化変性度を有
する水溶性アニオン化変性ポリビニルアルコール
（）とを併用して得られた炭酸カルシウム水分
散液は、それぞれの分散剤を単独で用いて得た比
較用水分散液や共重合体の中和物（）または水
溶性アニオン化変性ポリビニルアルコール（）
のいずれか１つまたは両方とも用いなかつた比較
用水分散液に比べ、低粘度であり、その経日安定
性にも優れていることがわかる。また、本発明の
方法によれば、従来使用されてきた分散剤のアク
リル酸／マレイン酸共重合体に比べ、低添加量で
低粘度かつ高流動特性を有する炭酸カルシウム水
分散液が得られることがわかる。[Table] From the above results, a neutralized copolymer () with a specific average molecular weight as a dispersant and a water-soluble anionized modified polyvinyl alcohol with a specific degree of polymerization, specific saponification degree, and specific degree of anionic modification Calcium carbonate aqueous dispersion obtained by using () in combination with aqueous dispersion of calcium carbonate, comparative aqueous dispersion obtained by using each dispersant alone, neutralized copolymer (), or water-soluble anionized modified polyvinyl alcohol ()
It can be seen that the viscosity is lower than that of the comparative aqueous dispersion in which either one or both of the above are not used, and the stability over time is also excellent. Furthermore, according to the method of the present invention, an aqueous calcium carbonate dispersion having low viscosity and high fluidity can be obtained with a lower additive amount than the conventionally used dispersant, acrylic acid/maleic acid copolymer. I understand.
第１図は実施例１で得られた水分散液(1)及び比
較例１で得られた比較用水分散液(1)の流動特性を
示すレオグラムである。
FIG. 1 is a rheogram showing the flow characteristics of the aqueous dispersion (1) obtained in Example 1 and the comparative aqueous dispersion (1) obtained in Comparative Example 1.
Claims (1)
散液を製造するに際し、分散剤として、無水マレ
イン酸及び無水マレイン酸１モルに対して0.7〜
1.2モルの比率の炭素数２〜７のα−オレフイン
を共重合して得られる平均分子量2000〜80000の
共重合体の中和物（）と重合度30〜700、ケン
化度30〜100モル％で且つアニオン化変性度0.5〜
20モル％の水溶性アニオン化変性ポリビニルアル
コール（）とを、炭酸カルシウム100重量部に
対して、該共重合体の中和物（）0.1〜２重量
部、水溶性アニオン化変性ポリビニルアルコール
（）0.03〜１重量部の範囲の割合で併用するこ
とを特徴とする炭酸カルシウム水分散液の製造方
法。 ２ 水溶性アニオン化変性ポリビニルアルコール
（）が水溶性スルホン化変性ポリビニルアルコ
ールである特許請求の範囲第１項記載の炭酸カル
シウム水分散液の製造方法。 ３ 水溶性アニオン化変性ポリビニルアルコール
（）が水溶性カルボキシル化変性ポリビニルア
ルコールである特許請求の範囲第１項記載の炭酸
カルシウム水分散液の製造方法。[Claims] 1. When dispersing calcium carbonate in an aqueous medium to produce an aqueous dispersion, as a dispersing agent, maleic anhydride and 0.7 to 0.7 to 1 mole of maleic anhydride are used.
Neutralized copolymer () with an average molecular weight of 2,000 to 80,000 obtained by copolymerizing α-olefins having 2 to 7 carbon atoms in a ratio of 1.2 mol and a degree of polymerization of 30 to 700 and a degree of saponification of 30 to 100 mol. % and degree of anionic modification 0.5~
20 mol% of water-soluble anionized modified polyvinyl alcohol (), 0.1 to 2 parts by weight of the neutralized product () of the copolymer, and water-soluble anionized modified polyvinyl alcohol () to 100 parts by weight of calcium carbonate. A method for producing an aqueous calcium carbonate dispersion, characterized in that the calcium carbonate aqueous dispersion is used in combination in a proportion ranging from 0.03 to 1 part by weight. 2. The method for producing an aqueous calcium carbonate dispersion according to claim 1, wherein the water-soluble anionized modified polyvinyl alcohol () is a water-soluble sulfonated modified polyvinyl alcohol. 3. The method for producing an aqueous calcium carbonate dispersion according to claim 1, wherein the water-soluble anionized modified polyvinyl alcohol () is a water-soluble carboxylated modified polyvinyl alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62263678A JPS6428215A (en) | 1987-04-13 | 1987-10-21 | Production of aqueous dispersion of calcium carbonate |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8870487 | 1987-04-13 | ||
| JP62263678A JPS6428215A (en) | 1987-04-13 | 1987-10-21 | Production of aqueous dispersion of calcium carbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6428215A JPS6428215A (en) | 1989-01-30 |
| JPH0453813B2 true JPH0453813B2 (en) | 1992-08-27 |
Family
ID=26430052
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62263678A Granted JPS6428215A (en) | 1987-04-13 | 1987-10-21 | Production of aqueous dispersion of calcium carbonate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6428215A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2264004A1 (en) * | 1997-06-20 | 1998-12-30 | Mitsui Chemicals, Incorporated | Aqueous dispersion composition and process for producing the same, and rust-preventive agent, rust preventive treatment method and rust-preventive treated metal product |
| JP5207097B2 (en) * | 2006-06-16 | 2013-06-12 | 星光Ｐｍｃ株式会社 | Filler modifier, filler slurry and paper making method |
| JP6731724B2 (en) * | 2015-12-24 | 2020-07-29 | 関西ペイント株式会社 | Pigment paste and coating material |
| PL3505574T3 (en) * | 2017-12-28 | 2022-01-03 | Imerys Usa, Inc. | Amphiphilic copolymers as surface modifiers for production of improved calcium carbonate powders |
| JP7441578B2 (en) * | 2021-10-27 | 2024-03-01 | 白石工業株式会社 | Calcium carbonate water slurry and method for producing calcium carbonate water slurry |
-
1987
- 1987-10-21 JP JP62263678A patent/JPS6428215A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6428215A (en) | 1989-01-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR930004292B1 (en) | Method for production of aqueous dispersion of inorganic pigment | |
| JPH08217505A (en) | Dispersant for aqueous gypsum slurry | |
| FR2766106A1 (en) | USE OF A SURFACE-ACTIVE STRUCTURE COPOLYMER AS DISPERSING AGENT AND / OR GRINDING AID | |
| CN102458633A (en) | Dispersant for pigment and use thereof | |
| US5380782A (en) | Polymeric dispersants for ceramic materials | |
| JPH0453813B2 (en) | ||
| JP3618540B2 (en) | Method for producing synthetic resin emulsion powder | |
| JPH0511490B2 (en) | ||
| JPS63233011A (en) | Production of calcium carbonate aqueous dispersion | |
| JPH0453814B2 (en) | ||
| JPH05125109A (en) | Preparation of powdery polymer of hydrolyzed n-vinylformamide and dehydrating agent, retaining agent and coagulator for paper making | |
| JPH0453812B2 (en) | ||
| JPH0453816B2 (en) | ||
| JP2004306022A (en) | Dispersion agent for light calcium carbonate | |
| JPH0453815B2 (en) | ||
| JPH11128715A (en) | Inorganic pigment-dispersing agent | |
| JPH09194669A (en) | Production of calcium carbonate slurry | |
| JP3970597B2 (en) | Inorganic pigment dispersant and paper coating pigment dispersion | |
| JPH0580255B2 (en) | ||
| JP3285675B2 (en) | Coated paper | |
| JPH01204911A (en) | Manufacture of maleic anhydride copolymer particle | |
| JPH01138118A (en) | Production of aqueous dispersion of talc | |
| JPH0620533B2 (en) | Method for producing calcium carbonate aqueous dispersion | |
| JP2588572B2 (en) | Dispersion stabilizer for powder-aqueous slurry | |
| JPH0469646B2 (en) |