JP2000053729A - Acrylic acid (salt)-maleic acid (salt)-based copolymer, its production and detergent composition - Google Patents
Acrylic acid (salt)-maleic acid (salt)-based copolymer, its production and detergent compositionInfo
- Publication number
- JP2000053729A JP2000053729A JP22600698A JP22600698A JP2000053729A JP 2000053729 A JP2000053729 A JP 2000053729A JP 22600698 A JP22600698 A JP 22600698A JP 22600698 A JP22600698 A JP 22600698A JP 2000053729 A JP2000053729 A JP 2000053729A
- Authority
- JP
- Japan
- Prior art keywords
- salt
- acrylic acid
- maleic acid
- acid
- 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.)
- Granted
Links
- 150000003839 salts Chemical class 0.000 title claims abstract description 101
- 239000011976 maleic acid Substances 0.000 title claims abstract description 60
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229920001577 copolymer Polymers 0.000 title claims abstract description 54
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 239000003599 detergent Substances 0.000 title claims abstract description 15
- 239000000203 mixture Substances 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000004927 clay Substances 0.000 claims abstract description 51
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 50
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 46
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 44
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 43
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 34
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 27
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 25
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 23
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 14
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 16
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 7
- 235000010216 calcium carbonate Nutrition 0.000 abstract description 7
- 239000006185 dispersion Substances 0.000 abstract description 4
- 230000002000 scavenging effect Effects 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 26
- 239000000243 solution Substances 0.000 description 20
- -1 alkali metal acrylates Chemical class 0.000 description 19
- 239000007864 aqueous solution Substances 0.000 description 16
- 238000006386 neutralization reaction Methods 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 229940048053 acrylate Drugs 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 229960005069 calcium Drugs 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 4
- 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 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229940047670 sodium acrylate Drugs 0.000 description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002280 amphoteric surfactant Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000011088 calibration curve Methods 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Substances Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L copper(II) hydroxide Inorganic materials [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- KEYZMFWOMWWJGZ-UHFFFAOYSA-N methylphosphonic acid;prop-2-enamide Chemical compound CP(O)(O)=O.NC(=O)C=C KEYZMFWOMWWJGZ-UHFFFAOYSA-N 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000000843 powder 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
- 239000002904 solvent Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- IMWCPTKSESEZCL-AHUNZLEGSA-H (Z)-but-2-enedioate iron(3+) Chemical compound [Fe+3].[Fe+3].[O-]C(=O)\C=C/C([O-])=O.[O-]C(=O)\C=C/C([O-])=O.[O-]C(=O)\C=C/C([O-])=O IMWCPTKSESEZCL-AHUNZLEGSA-H 0.000 description 1
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 description 1
- IMWCPTKSESEZCL-SPSNFJOYSA-H (e)-but-2-enedioate;iron(3+) Chemical compound [Fe+3].[Fe+3].[O-]C(=O)\C=C\C([O-])=O.[O-]C(=O)\C=C\C([O-])=O.[O-]C(=O)\C=C\C([O-])=O IMWCPTKSESEZCL-SPSNFJOYSA-H 0.000 description 1
- SHVRRGGZMBWAJT-ODZAUARKSA-N (z)-but-2-enedioic acid;copper Chemical compound [Cu].OC(=O)\C=C/C(O)=O SHVRRGGZMBWAJT-ODZAUARKSA-N 0.000 description 1
- JWTGRKUQJXIWCV-UHFFFAOYSA-N 1,2,3-trihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(O)C(O)CO JWTGRKUQJXIWCV-UHFFFAOYSA-N 0.000 description 1
- OOSZCNKVJAVHJI-UHFFFAOYSA-N 1-[(4-fluorophenyl)methyl]piperazine Chemical compound C1=CC(F)=CC=C1CN1CCNCC1 OOSZCNKVJAVHJI-UHFFFAOYSA-N 0.000 description 1
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 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
- 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
- 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
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-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
- HSXUNHYXJWDLDK-UHFFFAOYSA-N 2-hydroxypropane-1-sulfonic acid Chemical compound CC(O)CS(O)(=O)=O HSXUNHYXJWDLDK-UHFFFAOYSA-N 0.000 description 1
- DEQJBORXLQWRGV-UHFFFAOYSA-N 2-hydroxypropanoic acid;iron Chemical compound [Fe].CC(O)C(O)=O.CC(O)C(O)=O DEQJBORXLQWRGV-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
- VAPQAGMSICPBKJ-UHFFFAOYSA-N 2-nitroacridine Chemical compound C1=CC=CC2=CC3=CC([N+](=O)[O-])=CC=C3N=C21 VAPQAGMSICPBKJ-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
- IGDCJKDZZUALAO-UHFFFAOYSA-N 2-prop-2-enoxypropane-1,3-diol Chemical compound OCC(CO)OCC=C IGDCJKDZZUALAO-UHFFFAOYSA-N 0.000 description 1
- HNVRRHSXBLFLIG-UHFFFAOYSA-N 3-hydroxy-3-methylbut-1-ene Chemical compound CC(C)(O)C=C HNVRRHSXBLFLIG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- AFYORMHSCCAZHD-UHFFFAOYSA-N CC(CP(O)(=O)O)C.C(C=C)(=O)N Chemical compound CC(CP(O)(=O)O)C.C(C=C)(=O)N AFYORMHSCCAZHD-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 240000005561 Musa balbisiana Species 0.000 description 1
- 235000018290 Musa x paradisiaca Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 1
- LXASOGUHMSNFCR-UHFFFAOYSA-D [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O Chemical compound [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O LXASOGUHMSNFCR-UHFFFAOYSA-D 0.000 description 1
- JDDXEMPUSMULOC-UHFFFAOYSA-N acetyl acetate;iron Chemical compound [Fe].CC(=O)OC(C)=O JDDXEMPUSMULOC-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229940010514 ammonium ferrous sulfate Drugs 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- WPKYZIPODULRBM-UHFFFAOYSA-N azane;prop-2-enoic acid Chemical compound N.OC(=O)C=C WPKYZIPODULRBM-UHFFFAOYSA-N 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229960002713 calcium chloride Drugs 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- LLSDKQJKOVVTOJ-UHFFFAOYSA-L calcium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ca+2] LLSDKQJKOVVTOJ-UHFFFAOYSA-L 0.000 description 1
- 229940052299 calcium chloride dihydrate Drugs 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000002738 chelating 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
- 238000004581 coalescence Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- SVOAENZIOKPANY-CVBJKYQLSA-L copper;(z)-octadec-9-enoate Chemical compound [Cu+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O SVOAENZIOKPANY-CVBJKYQLSA-L 0.000 description 1
- KZBRSTGECTWPFL-UHFFFAOYSA-N copper;acetyl acetate Chemical compound [Cu+2].CC(=O)OC(C)=O KZBRSTGECTWPFL-UHFFFAOYSA-N 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- DGLRDKLJZLEJCY-UHFFFAOYSA-L disodium hydrogenphosphate dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].OP([O-])([O-])=O DGLRDKLJZLEJCY-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229960004642 ferric ammonium citrate Drugs 0.000 description 1
- 239000011706 ferric diphosphate Substances 0.000 description 1
- 235000007144 ferric diphosphate Nutrition 0.000 description 1
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- CADNYOZXMIKYPR-UHFFFAOYSA-B ferric pyrophosphate Chemical compound [Fe+3].[Fe+3].[Fe+3].[Fe+3].[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O CADNYOZXMIKYPR-UHFFFAOYSA-B 0.000 description 1
- 229940036404 ferric pyrophosphate Drugs 0.000 description 1
- 239000004225 ferrous lactate Substances 0.000 description 1
- 235000013925 ferrous lactate Nutrition 0.000 description 1
- 229940037907 ferrous lactate Drugs 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000004313 iron ammonium citrate Substances 0.000 description 1
- 235000000011 iron ammonium citrate Nutrition 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical compound CC(=C)CCO CPJRRXSHAYUTGL-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- RECVMTHOQWMYFX-UHFFFAOYSA-N oxygen(1+) dihydride Chemical compound [OH2+] RECVMTHOQWMYFX-UHFFFAOYSA-N 0.000 description 1
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- 229940099427 potassium bisulfite Drugs 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 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
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 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
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229940074545 sodium dihydrogen phosphate dihydrate Drugs 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
- XZPVPNZTYPUODG-UHFFFAOYSA-M sodium;chloride;dihydrate Chemical compound O.O.[Na+].[Cl-] XZPVPNZTYPUODG-UHFFFAOYSA-M 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 229940117986 sulfobetaine Drugs 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- KJDNAUVRGACOHX-UHFFFAOYSA-N sulfuric acid;vanadium Chemical compound [V].OS(O)(=O)=O KJDNAUVRGACOHX-UHFFFAOYSA-N 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
- 239000012085 test solution Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- AUALKMYBYGCYNY-UHFFFAOYSA-E triazanium;2-hydroxypropane-1,2,3-tricarboxylate;iron(3+) Chemical compound [NH4+].[NH4+].[NH4+].[Fe+3].[Fe+3].[Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O AUALKMYBYGCYNY-UHFFFAOYSA-E 0.000 description 1
- STDMRMREKPZQFJ-UHFFFAOYSA-H tricopper;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O STDMRMREKPZQFJ-UHFFFAOYSA-H 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 1
- 239000008403 very hard water Substances 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Detergent Compositions (AREA)
- Polymerization Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、アクリル酸（塩）
−マレイン酸（塩）系共重合体、その製造方法および洗
剤組成物に関する。The present invention relates to an acrylic acid (salt)
The present invention relates to a maleic acid (salt) -based copolymer, a method for producing the same, and a detergent composition.
【０００２】[0002]
【従来の技術】従来から、多数のカルボキシル基を有す
るアクリル酸（塩）−マレイン酸（塩）系共重合体は、
優れたキレート作用および分散作用を示すことが知られ
ており、洗剤ビルダー、スケール防止剤、無機顔料分散
剤、繊維処理剤、キレート剤などの広範囲の用途で使用
されている。2. Description of the Related Art Conventionally, acrylic acid (salt) -maleic acid (salt) based copolymers having a large number of carboxyl groups have been
It is known to exhibit excellent chelating and dispersing effects, and is used in a wide range of applications such as detergent builders, scale inhibitors, inorganic pigment dispersants, fiber treatment agents, and chelating agents.
【０００３】該共重合体を洗剤ビルダーとして用いる場
合の基本性能はカルシウムイオン捕捉能とクレー分散能
である。カルシウムイオン捕捉能とは、過剰にカルシウ
ムイオンが存在する系において共重合体が捕捉できるカ
ルシウムイオンの量を定量するものである。一方、クレ
ー分散能とは、ある特定組成の水溶液にクレーと共重合
体を加えてクレーを分散させた後の上澄み液の濁度で表
されるものであり、濁度が高いほど共重合体のクレー分
散能が優れていることを表す。一般に、分子量が大きい
ほど、カルシウムイオン捕捉能は高くなるが、クレー分
散能は低くなり、分子量が小さいほど、クレー分散能は
高くなるが、カルシウムイオン捕捉能は低くなるとされ
る。そのため、両者をバランス良く改良することは難し
く、従来から多くの提案がなされている。例えば、特許
第２５７４１４４号公報では、カルシウムイオン捕捉能
が３００ｍｇＣａＣＯ3／ｇ以上、クレイ分散能が１．
２以上であるマレイン酸系共重合体がその製造方法とと
もに提案されている。この特許ではクレー分散能は姫路
市の上水を用いて測定されている。姫路市の上水を含め
日本の水は全体的に硬度が比較的低く炭酸カルシウム換
算で２０〜５０ｐｐｍ程度であり、分散能に関しては条
件が緩やかであるため、特許第２５７４１４４号公報で
は主にカルシウムイオン捕捉能に主眼をおいて検討が行
われている。[0003] When the copolymer is used as a detergent builder, its basic performance is calcium ion trapping ability and clay dispersing ability. The calcium ion trapping ability is to quantify the amount of calcium ions that can be trapped by the copolymer in a system in which calcium ions are excessively present. On the other hand, the clay dispersing ability is represented by the turbidity of a supernatant liquid obtained by adding clay and a copolymer to an aqueous solution having a specific composition and dispersing the clay. Indicates that the clay dispersibility is excellent. In general, the higher the molecular weight, the higher the calcium ion trapping ability, but the lower the clay dispersing ability. The smaller the molecular weight, the higher the clay dispersing ability, but the lower the calcium ion trapping ability. Therefore, it is difficult to improve both in a well-balanced manner, and many proposals have conventionally been made. For example, in Japanese Patent No. 2574144, calcium ion trapping ability is 300 mg CaCO 3 / g or more, and clay dispersing ability is 1.
Two or more maleic acid-based copolymers have been proposed along with their production methods. In this patent, the clay dispersing ability is measured using water from Himeji City. Japanese water including Himeji city water has a relatively low hardness as a whole, about 20 to 50 ppm in terms of calcium carbonate, and the conditions for the dispersibility are moderate. Therefore, Japanese Patent No. 2574144 mainly discloses calcium. Studies are being conducted with a focus on the ion trapping ability.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、日本以
外の外国の水は硬度の高いものも多く、例えば米国や中
国の水の硬度（炭酸カルシウム換算）は２００ｐｐｍ程
度と非常に高い。前記特許第２５７４１４４号公報の共
重合体は、日本のような低硬度水では優れた分散能を示
すが、このような高硬度水ではもはや優れた分散能を示
すことはできない。高硬度水でのクレー分散能に関して
は、低硬度水での分散性に比べて、はるかに技術的難度
が高く従来技術のカルシウムイオン捕捉能に主眼をおい
た特許第２５７４１４４号公報の共重合体では太刀打ち
できないのである。However, many foreign waters other than Japan have high hardness. For example, the water hardness (calculated as calcium carbonate) in the United States and China is as high as about 200 ppm. The copolymer disclosed in Japanese Patent No. 2574144 exhibits excellent dispersibility in low-hardness water as in Japan, but can no longer exhibit excellent dispersibility in such high-hardness water. Regarding the dispersibility of clay in high-hardness water, the copolymer disclosed in Japanese Patent No. 2574144 is much more technically difficult than the dispersibility in low-hardness water and focuses on the calcium ion trapping ability of the prior art. Then you cannot compete.
【０００５】特許第２５７４１４４号公報以外にも、多
くのアクリル酸（塩）−マレイン酸（塩）系共重合体製
造方法が提案されている。例えば、特開昭６３−２３５
３１３号公報には、アクリル酸（塩）とマレイン酸を１
００／２００〜１００／２５のモル比で含み、末端にス
ルホン酸基を有するマレイン酸共重合体の製造方法にお
いて、亜硫酸又は重亜硫酸又はそれらの塩を酸化剤と反
応させることにより生成する重合開始剤を用い、ｐＨ
２．５〜６．５に保った水溶液中で共重合させるという
方法が開示されている。しかしながら、この共重合体は
スケール抑制能には優れるものの、洗剤用途に用いた場
合には、マレイン酸の比率が高いために特に高硬度水下
でのクレー分散能が悪いという問題を有する。In addition to Japanese Patent No. 2574144, many methods for producing acrylic acid (salt) -maleic acid (salt) copolymers have been proposed. For example, JP-A-63-235
No. 313 discloses that acrylic acid (salt) and maleic acid contain 1
In a method for producing a maleic acid copolymer having a molar ratio of 00/200 to 100/25 and having a sulfonic acid group at a terminal, polymerization initiation generated by reacting sulfurous acid or bisulfite or a salt thereof with an oxidizing agent PH agent
A method of copolymerizing in an aqueous solution maintained at 2.5 to 6.5 is disclosed. However, although this copolymer is excellent in scale-inhibiting ability, it has a problem that when used for detergents, the clay dispersing ability is particularly poor under high-hardness water due to the high ratio of maleic acid.
【０００６】また特開昭５８−６７７０６号公報には、
アクリル酸等の不飽和モノカルボン酸（塩）とマレイン
酸等の不飽和ジカルボン酸（塩）を９０〜４０／１０〜
６０の重量比で用い、水溶性開始剤の存在下に重合する
方法が開示されている。しかしながら、実施例ではマレ
イン酸が高い比率で用いられており、また過酸化水素の
みが開始剤として用いられているため、洗剤用途に用い
た場合には特に高硬度水下でのクレー分散能が悪いとい
う問題を有する。Japanese Patent Application Laid-Open No. 58-67706 discloses that
An unsaturated monocarboxylic acid (salt) such as acrylic acid and an unsaturated dicarboxylic acid (salt) such as maleic acid are mixed at 90-40 / 10
A method of polymerizing in the presence of a water-soluble initiator using a weight ratio of 60 is disclosed. However, in the examples, maleic acid is used at a high ratio, and only hydrogen peroxide is used as an initiator, so that when used for detergents, the clay dispersing ability under high hardness water is particularly high. It has the problem of being bad.
【０００７】したがって、本発明の課題は、高硬度水で
のクレー分散能が高く、しかもカルシウムイオン捕捉能
も高いアクリル酸（塩）−マレイン酸（塩）系共重合
体、その製造方法および洗剤組成物を提供することにあ
る。Therefore, an object of the present invention is to provide an acrylic acid (salt) -maleic acid (salt) copolymer having high clay dispersing ability in high hardness water and high calcium ion capturing ability, a method for producing the same, and a detergent. It is to provide a composition.
【０００８】[0008]
【課題を解決するための手段】上記課題を解決するた
め、本発明は、以下の構成を提供する。 高硬度水でのクレー分散能が５０％以上であり、カル
シウムイオン捕捉能が２７０ｍｇＣａＣＯ3／ｇ以上で
ある、アクリル酸（塩）−マレイン酸（塩）系共重合
体。Means for Solving the Problems In order to solve the above problems, the present invention provides the following configurations. An acrylic acid (salt) -maleic acid (salt) copolymer having a clay dispersing ability of 50% or more in high hardness water and a calcium ion capturing ability of 270 mg CaCO 3 / g or more.
【０００９】水性溶媒中で、少なくとも重合開始剤の
存在下に、アクリル酸（塩）およびマレイン酸（塩）を
主成分として含む単量体成分を重合してアクリル酸
（塩）−マレイン酸（塩）系共重合体を製造する方法で
あって、単量体成分、重合開始剤、水性溶媒および必要
に応じて用いられるその他の原材料は、重合終了後の重
合体の理論固形分濃度が４０重量％以上となるような使
用量で用いられ、アクリル酸（塩）の使用量とマレイン
酸（塩）の使用量がモル比で９５〜８０／５〜２０の範
囲であり、重合開始剤として、(1) 過硫酸塩と重亜硫酸
塩とを併用するか、および／または、(2) 過酸化水素と
多価金属イオンとを併用する、ことを特徴とするアクリ
ル酸（塩）−マレイン酸（塩）系共重合体の製造方法。In an aqueous solvent, at least in the presence of a polymerization initiator, a monomer component containing acrylic acid (salt) and maleic acid (salt) as main components is polymerized to form acrylic acid (salt) -maleic acid ( A method for producing a salt) -based copolymer, wherein the monomer component, the polymerization initiator, the aqueous solvent, and other raw materials used as required have a theoretical solid content concentration of the polymer of 40 after the polymerization. % By weight, and the amount of acrylic acid (salt) and the amount of maleic acid (salt) are in the range of 95 to 80/5 to 20 in molar ratio. (1) acrylic acid (salt) -maleic acid, wherein persulfate and bisulfite are used in combination, and / or (2) hydrogen peroxide and polyvalent metal ions are used in combination. A method for producing a (salt) -based copolymer.
【００１０】[0010]
【発明の実施の形態】以下に本発明の共重合体を製造方
法とともに詳細に説明する。本発明のアクリル酸−マレ
イン酸系共重合体は、高硬度水でのクレー分散能が５０
％以上であり、カルシウムイオン捕捉能が２７０ｍｇＣ
ａＣＯ3／ｇ以上というものである。高硬度水でのクレ
ー分散能は５５％以上であることが好ましく、６０％以
上であることがより好ましい。高硬度水でのクレー分散
能は高いほど好ましいが、９０％を越える共重合体を得
るには生産効率が低下したり高コストになるおそれがあ
る。カルシウムイオン捕捉能は３００ｍｇＣａＣＯ3／
ｇ以上であることが好ましい。カルシウムイオン捕捉能
は高いほど好ましいが、４５０ｍｇＣａＣＯ3／ｇを越
える共重合体を得るには生産効率が低下したり高コスト
になるおそれがある。なお、本発明でいう「高硬度水で
のクレー分散能」および「カルシウムイオン捕捉能」
は、実施例に記載された測定方法により測定されるもの
である。BEST MODE FOR CARRYING OUT THE INVENTION The copolymer of the present invention will be described below in detail along with a production method. The acrylic acid-maleic acid copolymer of the present invention has a clay dispersibility of 50 in high hardness water.
% Or more, and the calcium ion trapping ability is 270 mgC
aCO 3 / g or more. The clay dispersibility in high hardness water is preferably 55% or more, more preferably 60% or more. The higher the clay dispersing ability in high-hardness water, the better, but there is a possibility that the production efficiency may decrease or the cost may increase to obtain a copolymer exceeding 90%. Calcium ion scavenging capacity is 300mgCaCO 3 /
g or more. The higher the calcium ion-capturing ability, the better, but there is a possibility that the production efficiency may decrease or the cost may increase in order to obtain a copolymer exceeding 450 mg CaCO 3 / g. In the present invention, "clay dispersing ability in high hardness water" and "calcium ion trapping ability"
Is measured by the measuring method described in the examples.
【００１１】高硬度水でのクレー分散能とカルシウムイ
オン捕捉能の両方に優れた共重合体は従来には存在しな
かった新規かつ優れたものである。特に「高硬度水での
クレー分散能」は本発明者らの検討の結果見出された新
たな指標であり、従来知られた指標である「低硬度水
（炭酸カルシウム換算で２０〜５０ｐｐｍ程度）でのク
レー分散能」からその数値の予測はできないものであ
る。「低硬度水でのクレー分散能」が同程度の共重合体
同士であっても、より厳しい条件である「高硬度水での
クレー分散能」で比較すると顕著な違いが見られる場合
も多く存在する。しかも、本発明の共重合体は「高硬度
水でのクレー分散能」が優れるだけではなく、「カルシ
ウムイオン捕捉能」についても十分高い値を示し、全体
としてバランスよく優れた洗浄能力を発揮するものであ
る。A copolymer excellent in both the clay dispersing ability in high hardness water and the calcium ion capturing ability is a novel and excellent one which has not existed conventionally. In particular, the "clay dispersing ability in high hardness water" is a new index found as a result of the study of the present inventors, and a conventionally known index "low hardness water (about 20 to 50 ppm in terms of calcium carbonate). The numerical value cannot be predicted from the “clay dispersing ability”). Even if the copolymers have similar clay dispersing ability in low hardness water, there are many cases where remarkable differences can be seen when compared under more severe conditions of clay dispersing ability in high hardness water. Exists. Moreover, the copolymer of the present invention not only has excellent "clay dispersing ability in high-hardness water", but also has a sufficiently high value for "calcium ion trapping ability", and exhibits excellent washing ability with a good balance as a whole. Things.
【００１２】本発明の共重合体は、主に高硬度水でのク
レー分散能の点からは、共重合体におけるマレイン酸
（塩）単位の割合（ＭＡ（モル％））と、該共重合体の
重量平均分子量（Ｍｗ）との積（ＭＡ×Ｍｗ）が１５
０，０００以下であり、かつＭｗが２０，０００以下で
あることが好ましい。これは、マレイン酸（塩）単位の
割合が多くなるにつれ、また分子量が大きくなるにつ
れ、カルシウムイオン捕捉能は上昇するが、クレー分散
能は低下する傾向があるためであり、マレイン酸（塩）
単位の割合が高くなると、重量平均分子量の上限の制約
がより厳しくなる。いくつか例示するならば、ＭＡが
７．５モル％以下ではＭｗは２０，０００以下が好まし
く、ＭＡが１０モル％ではＭｗは１５，０００以下が好
ましく、ＭＡが１５モル％では１０，０００以下が好ま
しい。The copolymer of the present invention is characterized mainly by the ratio of maleic acid (salt) units (MA (mol%)) to the copolymer in terms of clay dispersibility in high hardness water. The product (MA × Mw) of the union with the weight average molecular weight (Mw) is 15
It is preferable that the molecular weight is not more than 0000 and the Mw is not more than 20,000. This is because as the proportion of maleic acid (salt) unit increases and as the molecular weight increases, the calcium ion trapping ability increases but the clay dispersing ability tends to decrease.
As the unit ratio increases, the restriction on the upper limit of the weight average molecular weight becomes more severe. For example, when MA is 7.5 mol% or less, Mw is preferably 20,000 or less, when MA is 10 mol%, Mw is preferably 15,000 or less, and when MA is 15 mol%, 10,000 or less. Is preferred.
【００１３】また、高硬度水でのクレー分散能とカルシ
ウムイオン捕捉能とを両立するためには、本発明の共重
合体におけるアクリル酸（塩）単位とマレイン酸（塩）
単位のモル比は９５〜８０／５〜２０であることが好ま
しく、９０〜８５／１０〜１５がさらに好ましい。マレ
イン酸（塩）単位が前記範囲を下回ると、カルシウムイ
オン捕捉能が低下し、アクリル酸（塩）単位が前記範囲
を下回ると、高硬度水でのクレー分散能が低下する。In order to achieve both clay dispersing ability in high hardness water and calcium ion capturing ability, acrylic acid (salt) units and maleic acid (salt) in the copolymer of the present invention are required.
The molar ratio of the unit is preferably from 95 to 80/5 to 20, more preferably from 90 to 85/10 to 15. When the maleic acid (salt) unit falls below the above range, the calcium ion trapping ability decreases, and when the acrylic acid (salt) unit falls below the above range, the clay dispersing ability in high hardness water decreases.
【００１４】なお、上記した共重合体におけるマレイン
酸（塩）単位の割合（ＭＡ）、および、アクリル酸
（塩）単位とマレイン酸（塩）単位のモル比は、仕込み
比率によって制御される。したがって、本発明の共重合
体を得るためには、マレイン酸（塩）を低い割合で含む
（言い換えれば、アクリル酸（塩）を高い割合で含む）
単量体成分を用いて、かつ重量平均分子量があまり大き
くならないような方法で重合を行うことが好ましい。ま
た、高硬度水でのクレー分散能の点からは重合体の分子
量分布は狭い方が好ましいので、この点にも留意するこ
とが好ましい。従来、低硬度水でのクレー分散能とカル
シウムイオン捕捉能との両立を目指していたときは、主
にカルシウムイオン捕捉能に主眼がおかれていたため、
マレイン酸（塩）を多く含む単量体成分が用いられてい
た。マレイン酸（塩）は反応性が低いため、一般的に高
い重合濃度（重合終了後の重合体の理論固形分濃度）で
重合が行われることが多く、その結果分子量が比較的低
い重合体が得られる。しかしながら、同じ方法をそのま
まアクリル酸（塩）を多く含む単量体成分に適用して
も、アクリル酸（塩）はマレイン酸（塩）とは異なり非
常に反応性が高いために、高濃度で重合を行うと非常に
分子量が高い重合体が得られてしまう。逆に低濃度で重
合を行うと、低分子量の重合体が得られるものの分子量
分布が広いものとなるため、高硬度水でのクレー分散能
が劣ったものとなってしまう。The ratio (MA) of maleic acid (salt) units and the molar ratio of acrylic acid (salt) units to maleic acid (salt) units in the above copolymer are controlled by the charge ratio. Therefore, in order to obtain the copolymer of the present invention, maleic acid (salt) is contained in a low proportion (in other words, acrylic acid (salt) is contained in a high proportion).
The polymerization is preferably carried out using a monomer component and in such a manner that the weight average molecular weight does not become too large. From the viewpoint of clay dispersing ability in high hardness water, it is preferable that the molecular weight distribution of the polymer is narrow. Therefore, it is preferable to pay attention to this point. Conventionally, when aiming to achieve both clay dispersing ability and calcium ion capturing ability in low hardness water, the main focus was on calcium ion capturing ability,
A monomer component containing a large amount of maleic acid (salt) has been used. Since maleic acid (salt) has low reactivity, polymerization is generally performed at a high polymerization concentration (theoretical solid content concentration of the polymer after completion of polymerization), and as a result, a polymer having a relatively low molecular weight is produced. can get. However, even if the same method is directly applied to a monomer component containing a large amount of acrylic acid (salt), acrylic acid (salt) is very reactive unlike maleic acid (salt), so that it has a high concentration. When polymerization is performed, a polymer having a very high molecular weight is obtained. Conversely, when the polymerization is carried out at a low concentration, a polymer having a low molecular weight can be obtained, but the molecular weight distribution becomes broad, so that the clay dispersing ability in high-hardness water is inferior.
【００１５】すなわち、本発明の共重合体を得るために
は重合条件を厳密に特定することが必要であり、本発明
者らの鋭意検討の結果、以下に示すとおりの本発明の製
造方法に到達したものである。以下に本発明の製造方法
について説明する。本発明の製造方法では、単量体成分
として、アクリル酸（塩）およびマレイン酸（塩）を主
成分として含むものを用いる。主成分として含むとは、
単量体成分中でアクリル酸（塩）およびマレイン酸
（塩）の合計量が占める割合が８５モル％以上であるこ
とをいい、好ましくは９０モル％以上、より好ましくは
９５モル％以上である。That is, in order to obtain the copolymer of the present invention, it is necessary to strictly specify the polymerization conditions, and as a result of intensive studies by the present inventors, the production method of the present invention as shown below is shown. It has been reached. Hereinafter, the production method of the present invention will be described. In the production method of the present invention, a monomer component containing acrylic acid (salt) and maleic acid (salt) as main components is used. Containing as the main component means
The ratio of the total amount of acrylic acid (salt) and maleic acid (salt) in the monomer component is 85 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more. .
【００１６】アクリル酸（塩）としては、アクリル酸、
アクリル酸塩のいずれでもよく、これらの混合物であっ
てもよいが、アクリル酸を用いることが好ましい。アク
リル酸塩としては、アクリル酸ナトリウム、アクリル酸
カリウム等のアクリル酸アルカリ金属塩、アクリル酸ア
ンモニウム、あるいはアクリル酸の有機アミン類の塩等
を挙げることができる。アクリル酸（塩）は、好ましく
は７０重量％以上、より好ましくは９０重量％以上、さ
らに好ましくは全量を滴下により反応器に供給すること
が好ましい。後述のように重合開始剤として過硫酸塩と
重亜硫酸塩とを併用する場合は、滴下終了時の中和度が
アクリル酸、マレイン酸の合計量の１５モル％以下であ
ることが好ましく、１０モル％以下であることがより好
ましい。重合開始剤として過酸化水素と多価金属イオン
とを併用する場合は、滴下終了時の中和度はアクリル
酸、マレイン酸の合計量の３０モル％以下であることが
好ましく、２０モル％以下であることがより好ましい。
中和は反応器に供給する前に予め行われていてもよい
し、酸と塩基とを別々に反応器に供給して反応器内で中
和を行ってもよい。As acrylic acid (salt), acrylic acid,
Any of acrylic acid salts may be used, and a mixture thereof may be used, but it is preferable to use acrylic acid. Examples of the acrylate include alkali metal acrylates such as sodium acrylate and potassium acrylate, ammonium acrylate, and salts of organic amines of acrylic acid. The acrylic acid (salt) is preferably supplied to the reactor by dropping preferably 70% by weight or more, more preferably 90% by weight or more, and even more preferably the whole amount. When a persulfate and a bisulfite are used in combination as a polymerization initiator as described below, the degree of neutralization at the end of the dropwise addition is preferably 15 mol% or less of the total amount of acrylic acid and maleic acid. More preferably, it is at most mol%. When hydrogen peroxide and a polyvalent metal ion are used in combination as the polymerization initiator, the degree of neutralization at the end of the dropwise addition is preferably 30 mol% or less, more preferably 20 mol% or less, of the total amount of acrylic acid and maleic acid. Is more preferable.
Neutralization may be performed in advance before supplying to the reactor, or neutralization may be performed in the reactor by separately supplying the acid and the base to the reactor.
【００１７】マレイン酸（塩）としては、無水マレイン
酸、マレイン酸、マレイン酸塩のいずれであってもよ
く、これらの２種以上の混合物を用いてもよい。マレイ
ン酸塩としては、水酸化ナトリウム、水酸化カリウム等
のアルカリ金属の水酸化物、アンモニア、モノエタノー
ルアミン等の有機アミン類等の塩を挙げることができ
る。マレイン酸（塩）は、好ましくは５０重量％以上、
より好ましくは８０重量％以上、さらに好ましくは全量
を初期に反応器に仕込むことが好ましい。後述のように
重合開始剤として過硫酸塩と重亜硫酸塩とを併用する場
合は、マレイン酸の中和度は５〜３０モル％が好まし
く、１０〜２５モル％がより好ましい。重合開始剤とし
て過酸化水素と多価金属イオンとを併用する場合は、マ
レイン酸の中和度は任意であるが、１０〜５０モル％が
好ましい。中和は反応器に供給する前に予め行われてい
てもよいし、酸と塩基とを別々に反応器に供給して反応
器内で中和を行ってもよい。The maleic acid (salt) may be any of maleic anhydride, maleic acid and maleate, or a mixture of two or more of these. Examples of the maleate include salts of hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, and salts of organic amines such as ammonia and monoethanolamine. Maleic acid (salt) is preferably at least 50% by weight,
More preferably, 80% by weight or more, and even more preferably, the whole amount is initially charged in the reactor. When a persulfate and a bisulfite are used in combination as a polymerization initiator as described below, the degree of neutralization of maleic acid is preferably 5 to 30 mol%, more preferably 10 to 25 mol%. When hydrogen peroxide and a polyvalent metal ion are used in combination as a polymerization initiator, the degree of neutralization of maleic acid is arbitrary, but is preferably 10 to 50 mol%. Neutralization may be performed in advance before supplying to the reactor, or neutralization may be performed in the reactor by separately supplying the acid and the base to the reactor.
【００１８】アクリル酸（塩）とマレイン酸（塩）の使
用量としては、アクリル酸（塩）とマレイン酸（塩）の
モル比が９５〜８０／５〜２０であることが必要であ
り、９０〜８５／１０〜１５がより好ましい。マレイン
酸（塩）の使用量が前記範囲よりも下回るとカルシウム
イオン捕捉能が低下し、アクリル酸（塩）の使用量が前
記範囲よりも下回ると高硬度水でのクレー分散能が低下
する。The amount of the acrylic acid (salt) and the maleic acid (salt) to be used must be such that the molar ratio of the acrylic acid (salt) and the maleic acid (salt) is 95-80 / 5-20. 90-85 / 10-15 are more preferable. When the amount of maleic acid (salt) used is lower than the above range, the calcium ion trapping ability decreases, and when the amount of acrylic acid (salt) used is lower than the above range, the clay dispersing ability in high hardness water decreases.
【００１９】本発明では単量体成分として、本発明の効
果を損なわない範囲でアクリル酸（塩）、マレイン酸
（塩）以外の単量体を含むことができる。このような単
量体は、アクリル酸（塩）、マレイン酸（塩）と共重合
可能なものであればよく、例えば、メタクリル酸、クロ
トン酸等の不飽和モノカルボン酸系単量体；上記不飽和
モノカルボン酸系単量体を、１価金属、２価金属、アン
モニア、有機アミン等で部分中和または完全中和してな
る中和物；フマル酸、イタコン酸、シトラコン酸等の不
飽和ジカルボン酸系単量体；上記不飽和ジカルボン酸系
単量体を、１価金属、２価金属、アンモニア、有機アミ
ン等で部分中和または完全中和してなる中和物；（メ
タ）アクリルアミド、ｔ−ブチル（メタ）アクリルアミ
ド等のアミド系単量体；（メタ）アクリル酸エステル、
スチレン、２−メチルスチレン、酢酸ビニル等の疎水性
単量体；ビニルスルホン酸、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、２−アクリルアミ
ド−２−メチルプロパンスルホン酸、３−アリロキシ−
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、スルホプロピル（メタ）アクリレー
ト、２−ヒドロキシスルホプロピル（メタ）アクリレー
ト、スルホエチルマレイミド等の不飽和スルホン酸系単
量体；上記不飽和スルホン酸系単量体を、１価金属、２
価金属、アンモニア、有機アミン等で部分中和または完
全中和してなる中和物；３−メチル−２−ブテン−１−
オール（プレノール）、３−メチル−３−ブテン−１−
オール（イソプレノール）、２−メチル−３−ブテン−
２−オール（イソプレンアルコール）、２−ヒドロキシ
エチル（メタ）アクリレート、ポリエチレングリコール
モノ（メタ）アクリレート、ポリプロピレングリコール
モノ（メタ）アクリレート、ポリエチレングリコールモ
ノイソプレノールエーテル、ポリプロピレングリコール
モノイソプレノールエーテル、ポリエチレングリコール
モノアリルエーテル、ポリプロピレングリコールモノア
リルエーテル、グリセロールモノアリルエーテル、α−
ヒドロキシアクリル酸、Ｎ−メチロール（メタ）アクリ
ルアミド、グリセロールモノ（メタ）アクリレート、ビ
ニルアルコール等の水酸基含有不飽和単量体；ジメチル
アミノエチル（メタ）アクリレート、ジメチルアミノプ
ロピル（メタ）アクリルアミド等のカチオン性単量体；
（メタ）アクリロニトリル等のニトリル系単量体；（メ
タ）アクリルアミドメタンホスホン酸、（メタ）アクリ
ルアミドメタンホスホン酸メチルエステル、２−（メ
タ）アクリルアミド−２−メチルプロパンホスホン酸等
の含リン単量体；等が挙げられるが、特に限定されるも
のではない。これらの単量体は１種のみを用いてもよ
く、また２種以上を併用してもよい。In the present invention, monomers other than acrylic acid (salt) and maleic acid (salt) can be contained as monomer components as long as the effects of the present invention are not impaired. Such a monomer may be any as long as it can be copolymerized with acrylic acid (salt) and maleic acid (salt). For example, unsaturated monocarboxylic acid monomers such as methacrylic acid and crotonic acid; A neutralized product obtained by partially or completely neutralizing an unsaturated monocarboxylic acid monomer with a monovalent metal, a divalent metal, ammonia, an organic amine, or the like; an unsaturated monomer such as fumaric acid, itaconic acid, or citraconic acid; Saturated dicarboxylic acid monomer; neutralized product obtained by partially or completely neutralizing the above unsaturated dicarboxylic acid monomer with a monovalent metal, a divalent metal, ammonia, an organic amine, or the like; Amide monomers such as acrylamide and t-butyl (meth) acrylamide; (meth) acrylates;
Hydrophobic monomers such as styrene, 2-methylstyrene and vinyl acetate; vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and 3-allyloxy-
Unsaturated sulfonic acid monomers such as 2-hydroxypropanesulfonic acid, sulfoethyl (meth) acrylate, sulfopropyl (meth) acrylate, 2-hydroxysulfopropyl (meth) acrylate, and sulfoethylmaleimide; Monomers are monovalent metals, 2
Neutralized product obtained by partial or complete neutralization with a valent metal, ammonia, an organic amine or the like; 3-methyl-2-butene-1-
All (prenol), 3-methyl-3-butene-1-
All (isoprenol), 2-methyl-3-butene-
2-ol (isoprene alcohol), 2-hydroxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol monoisoprenol ether, polypropylene glycol monoisoprenol ether, polyethylene glycol mono Allyl ether, polypropylene glycol monoallyl ether, glycerol monoallyl ether, α-
Hydroxyl-containing unsaturated monomers such as hydroxyacrylic acid, N-methylol (meth) acrylamide, glycerol mono (meth) acrylate and vinyl alcohol; cationic such as dimethylaminoethyl (meth) acrylate and dimethylaminopropyl (meth) acrylamide Monomer;
Nitrile monomers such as (meth) acrylonitrile; phosphorus-containing monomers such as (meth) acrylamide methanephosphonic acid, methyl (meth) acrylamide methanephosphonate, 2- (meth) acrylamide-2-methylpropanephosphonic acid And the like, but are not particularly limited. One of these monomers may be used alone, or two or more thereof may be used in combination.
【００２０】本発明の製造方法では、重合開始剤とし
て、(1)過硫酸塩と重亜硫酸塩とを併用するか、および
／または、(2)過酸化水素と多価金属イオンとを併用す
ることが必要である。過硫酸塩、重亜硫酸塩、過酸化水
素、多価金属イオンのいずれも、これら以外の重合開始
剤（アゾ系化合物、有機過酸化物など）とともに重合開
始剤として既に知られたものではあるが、本発明者らの
知見によると、過硫酸塩と重亜硫酸塩とを併用するか、
および／または、過酸化水素と多価金属イオンとを併用
した場合にのみ、本発明の目的とする高硬度水でのクレ
ー分散能が５０％以上であり、カルシウムイオン捕捉能
が２７０ｍｇＣａＣＯ3／ｇ以上である共重合体を得る
ことができる。過硫酸塩、重亜硫酸塩、過酸化水素、多
価金属イオンをそれぞれ単独で用いた場合や、他の化合
物と組み合わせて用いた場合（空気と重亜硫酸塩との併
用など）や、上記化合物を上記以外の組み合わせで用い
た場合（過硫酸塩と過酸化水素の併用など）は、本発明
の共重合体を得ることはできない。ただし、本発明の効
果を損なわない範囲で、過硫酸塩と重亜硫酸塩に加えて
さらに他の重合開始剤を併用することや、同様に過酸化
水素と多価金属イオンに加えてさらに他の重合開始剤を
併用することは可能である。In the production method of the present invention, (1) a combination of a persulfate and a bisulfite and / or (2) a combination of hydrogen peroxide and a polyvalent metal ion is used as a polymerization initiator. It is necessary. Persulfate, bisulfite, hydrogen peroxide, and polyvalent metal ions are all known as polymerization initiators together with other polymerization initiators (azo compounds, organic peroxides, etc.). According to the findings of the present inventors, a combination of persulfate and bisulfite,
And / or only when hydrogen peroxide and a polyvalent metal ion are used in combination, the clay dispersibility in high-hardness water is 50% or more, and the calcium ion-capturing ability is 270 mgCaCO 3 / g. The above copolymer can be obtained. When persulfate, bisulfite, hydrogen peroxide, and polyvalent metal ions are used alone or in combination with other compounds (such as a combination of air and bisulfite), When used in a combination other than the above (for example, a combination of persulfate and hydrogen peroxide), the copolymer of the present invention cannot be obtained. However, as long as the effects of the present invention are not impaired, another polymerization initiator may be used in addition to the persulfate and the bisulfite, and further, in addition to the hydrogen peroxide and the polyvalent metal ion, another It is possible to use a polymerization initiator in combination.
【００２１】重合開始剤として過硫酸塩と重亜硫酸塩と
を併用する場合について説明する。過硫酸塩としては、
過硫酸ナトリウム、過硫酸カリウム、過硫酸アンモニウ
ム等が好ましく、これらの１種または２種以上を使用で
きる。重亜硫酸塩としては、重亜硫酸ナトリウム、重亜
硫酸カリウム、重亜硫酸アンモニウム等が好ましく、こ
れらの１種または２種以上を使用できる。The case where a persulfate and a bisulfite are used together as a polymerization initiator will be described. As persulfate,
Sodium persulfate, potassium persulfate, ammonium persulfate and the like are preferred, and one or more of these can be used. As the bisulfite, sodium bisulfite, potassium bisulfite, ammonium bisulfite and the like are preferable, and one or more of these can be used.
【００２２】過硫酸塩の使用量と重亜硫酸塩の使用量は
重量比で１／０．５〜１／５の範囲であることが好まし
く、１／１〜１／２の範囲であることがより好ましい。
過硫酸塩の使用量が前記範囲より少ない場合には、分子
量が増大する傾向にあり、重亜硫酸塩の使用量が前記範
囲より少ない場合には、分子量分布が広がる傾向にあ
る。The amount of persulfate used and the amount of bisulfite used are preferably in the range of 1 / 0.5 to 1/5 and more preferably in the range of 1/1 to 1/2 by weight. More preferred.
When the amount of persulfate used is less than the above range, the molecular weight tends to increase, and when the amount of bisulfite used is less than the above range, the molecular weight distribution tends to widen.
【００２３】過硫酸塩と重亜硫酸塩の合計の使用量は、
単量体成分１モルに対し５〜１５ｇであることが好まし
く、より好ましくは１０〜１５ｇである。合計の使用量
が前記範囲より少ない場合には、分子量が増大し、分子
量分布も広がる傾向にあり、合計の使用量を前記範囲よ
り多くしても、もはや添加効果が現れない傾向にある。The total amount of persulfate and bisulfite used is:
The amount is preferably 5 to 15 g, more preferably 10 to 15 g, per 1 mol of the monomer component. If the total amount used is less than the above range, the molecular weight tends to increase and the molecular weight distribution tends to widen. Even if the total amount exceeds the above range, the addition effect tends to no longer appear.
【００２４】過硫酸塩、重亜硫酸塩ともに８０重量％以
上、より好ましくは全量を滴下により反応器に供給する
ことが好ましい。滴下により供給する過硫酸塩、重亜硫
酸塩の量が８０重量％未満の場合、即ち２０重量％以上
初期仕込みの場合は有効に利用されなくなり、初期の段
階で分解が起きやすい。また、過硫酸塩および重亜硫酸
塩の滴下時間は単量体成分の滴下時間の前後２０分以内
であることが好ましく、１０分以内がより好ましい。It is preferable that both the persulfate and the bisulfite are supplied to the reactor by dropping 80% by weight or more, more preferably the whole amount thereof. When the amount of persulfate and bisulfite supplied by dropping is less than 80% by weight, that is, 20% by weight or more, the initial charge does not make effective use, and decomposition tends to occur at an early stage. Further, the dropping time of the persulfate and the bisulfite is preferably within 20 minutes before and after the dropping time of the monomer component, and more preferably within 10 minutes.
【００２５】重合開始剤として過酸化水素と多価金属イ
オンとを併用する場合について説明する。過酸化水素の
使用量は、単量体成分１モルに対し５〜１５ｇであるこ
とが好ましく、より好ましくは８〜１２ｇである。過酸
化水素の使用量が前記範囲より少ない場合には、分子量
が増大し、分子量分布も広がる傾向にあり、過酸化水素
の使用量を前記範囲より多くしても、もはや添加効果が
現れない傾向にある。The case where hydrogen peroxide and a polyvalent metal ion are used in combination as a polymerization initiator will be described. The amount of hydrogen peroxide to be used is preferably 5 to 15 g, more preferably 8 to 12 g, per mol of the monomer component. If the amount of hydrogen peroxide used is less than the above range, the molecular weight tends to increase and the molecular weight distribution tends to be widened, and even if the amount of hydrogen peroxide used is larger than the above range, the addition effect no longer appears. It is in.
【００２６】過酸化水素は好ましくは８０重量％以上、
より好ましくは全量を滴下により反応器に供給すること
が好ましい。滴下により供給する過酸化水素の量が８０
重量％未満の場合、即ち２０重量％以上初期仕込みの場
合は有効に利用されなくなり、初期の段階で分解が起き
やすい。また、過酸化水素の滴下時間は単量体成分の滴
下よりも２０分以上早く終了することが好ましい。The hydrogen peroxide is preferably at least 80% by weight,
More preferably, it is preferable to supply the whole amount to the reactor dropwise. The amount of hydrogen peroxide supplied by dropping is 80
When the amount is less than 20% by weight, that is, when the initial preparation is 20% by weight or more, it is not effectively used, and decomposition is likely to occur at an initial stage. Further, it is preferable that the dropping time of hydrogen peroxide is completed at least 20 minutes earlier than the dropping of the monomer component.
【００２７】多価金属イオンとしては、鉄イオン（Ｆｅ
2+，Ｆｅ3+）、バナジウムイオン（Ｖ2+，Ｖ3+，Ｖ
Ｏ2+）、銅イオン（Ｃｕ2+）の１種または２種以上を用
いることが好ましく、特に好ましくは鉄イオンである。
多価金属イオンの供給形態については特に制限はなく、
重合反応系内でイオン化する金属および／または金属化
合物を用いることができる。例えば、オキシ三塩化バナ
ジウム、三塩化バナジウム、シュウ酸バナジウム、硫酸
バナジウム、無水バナジン酸、メタバナジン酸アンモニ
ウム、硫酸アンモニウムハイポバナダス（（ＮＨ4）2Ｓ
Ｏ4・ＶＳＯ4・６Ｈ 2Ｏ）、硫酸アンモニウムバナダス
（（ＮＨ4）Ｖ（ＳＯ4）2・１２Ｈ2Ｏ）、酢酸銅（I
I）、臭化銅（II）、銅（II）アセチルアセテート、塩
化第二銅、炭酸銅、塩化銅（II）、クエン酸銅（II）、
ギ酸銅（II）、水酸化銅（II）、オレイン酸銅（II）、
マレイン酸銅、リン酸銅、硫酸銅（II）、鉄アセチルア
セトナート、クエン酸鉄アンモニウム、シュウ酸第二鉄
アンモニウム、硫酸第一鉄アンモニウム、硫酸第二鉄ア
ンモニウム、クエン酸鉄、フマル酸鉄、マレイン酸鉄、
乳酸第一鉄、硝酸第二鉄、鉄ペンタカルボニル、リン酸
第二鉄、ピロリン酸第二鉄等の水溶性金属塩；五酸化バ
ナジウム、酸化銅（II）、酸化第一鉄、酸化第二鉄等の
金属酸化物；硫化銅（II）、硫化鉄等の金属硫化物を挙
げることができる。As the polyvalent metal ions, iron ions (Fe
2+, Fe3+), Vanadium ion (V2+, V3+, V
O2+), Copper ions (Cu2+1) or 2 or more
Is preferable, and particularly preferably an iron ion.
There is no particular limitation on the supply form of the polyvalent metal ion,
Metals and / or metallisation ionizing in the polymerization reaction system
Compounds can be used. For example, oxytrichloride banana
Indium, vanadium trichloride, vanadium oxalate, sulfuric acid
Vanadium, vanadic anhydride, ammonium metavanadate
And ammonium sulfate hypovanadas ((NHFour)TwoS
OFour・ VSOFour・ 6H TwoO), ammonium sulfate vanadas
((NHFour) V (SOFour)Two・ 12HTwoO), copper acetate (I
I), copper (II) bromide, copper (II) acetyl acetate, salt
Cupric chloride, copper carbonate, copper (II) chloride, copper (II) citrate,
Copper (II) formate, copper (II) hydroxide, copper (II) oleate,
Copper maleate, copper phosphate, copper (II) sulfate, iron acetyl acetate
Sementato, ferric ammonium citrate, ferric oxalate
Ammonium, ferrous ammonium sulfate, ferric sulfate
Ammonium, iron citrate, iron fumarate, iron maleate,
Ferrous lactate, ferric nitrate, iron pentacarbonyl, phosphoric acid
Water-soluble metal salts such as ferric and ferric pyrophosphate;
Nadium, copper (II) oxide, ferrous oxide, ferric oxide, etc.
Metal oxides: Metal sulfides such as copper (II) sulfide and iron sulfide
I can do it.
【００２８】多価金属イオン（上記金属化合物および金
属）は好ましくは８０重量％以上、より好ましくは全量
を、初期に反応容器に仕込むことが好ましい。多価金属
イオンは、反応液の全量に対して５〜５００ｐｐｍとな
るように用いることが好ましく、より好ましくは１０〜
４００ｐｐｍである。多価金属イオンの使用量が前記範
囲より少ない場合には、過酸化水素の分解効率が悪くな
る傾向にあり、多価金属イオンの使用量が前記範囲より
多い場合には、着色の原因ともなり、また添加効果も現
れにくい。The polyvalent metal ions (the above metal compounds and metals) are preferably initially charged to the reaction vessel in an amount of 80% by weight or more, more preferably the entire amount. The polyvalent metal ion is preferably used in an amount of 5 to 500 ppm based on the total amount of the reaction solution, and more preferably 10 to 500 ppm.
400 ppm. When the amount of the polyvalent metal ion used is less than the above range, the decomposition efficiency of hydrogen peroxide tends to deteriorate, and when the amount of the polyvalent metal ion used is larger than the above range, it may cause coloring. Also, the effect of addition is hard to appear.
【００２９】重合溶媒としては水性溶媒を用いる。特に
水を８０重量％以上、有機溶剤を２０重量％未満の割合
で含む水性溶媒が好ましく、より好ましくは水である。
水性溶媒に用いられる有機溶剤としては、メタノール、
エタノール、イソプロピルアルコール等の低級アルコー
ル、ジエチルホルムアルデヒド等のアミド類、ジエチル
エーテル等のエーテル類等の１種または２種以上を挙げ
ることができる。An aqueous solvent is used as a polymerization solvent. In particular, an aqueous solvent containing 80% by weight or more of water and less than 20% by weight of an organic solvent is preferable, and water is more preferable.
As the organic solvent used for the aqueous solvent, methanol,
One or more of lower alcohols such as ethanol and isopropyl alcohol, amides such as diethylformaldehyde, and ethers such as diethyl ether can be used.
【００３０】本発明においては、上記した単量体成分、
重合開始剤、水性溶媒および必要に応じて用いられるそ
の他の原材料を、重合終了後の重合体の理論固形分濃度
が４０重量％以上となるような使用量で用いる必要があ
る。該理論固形分濃度が４０重量％未満では、分子量分
布が広がる傾向にある。該理論固形分濃度は、初期仕込
みおよび滴下により反応器に供給される各原材料の重量
により調節することができる。例えば、アクリル酸や
（無水）マレイン酸と水酸化ナトリウム等の塩基とを別
々に反応器に供給して反応器内で中和を行う場合には、
中和により水が生成することも考慮しなければならな
い。In the present invention, the above monomer component,
It is necessary to use the polymerization initiator, the aqueous solvent, and other raw materials used as needed in such amounts that the theoretical solid content concentration of the polymer after the polymerization is 40% by weight or more. If the theoretical solid content is less than 40% by weight, the molecular weight distribution tends to widen. The theoretical solids concentration can be adjusted by the weight of each raw material supplied to the reactor by initial charging and dropping. For example, when acrylic acid or (anhydrous) maleic acid and a base such as sodium hydroxide are separately supplied to a reactor to perform neutralization in the reactor,
It must also be taken into account that water is formed by neutralization.
【００３１】重合条件としては、温度は８０℃以上が好
ましく、重合溶媒の沸点近傍の温度であることがより好
ましい。圧力は特に限定されず、常圧（大気圧）、加
圧、減圧のいずれでもよい。また、前述のように重合開
始剤として過硫酸塩と重亜硫酸塩とを併用する場合は、
重合時のｐＨが５以下であることが好ましく、４以下で
あることがより好ましい。重合時のｐＨが５より大きい
場合には、分子量が増大しやすく好ましくない。As the polymerization conditions, the temperature is preferably 80 ° C. or higher, and more preferably a temperature near the boiling point of the polymerization solvent. The pressure is not particularly limited, and may be normal pressure (atmospheric pressure), pressurization, or pressure reduction. Further, as described above, when using a combination of persulfate and bisulfite as a polymerization initiator,
The pH during polymerization is preferably 5 or less, more preferably 4 or less. If the pH during the polymerization is higher than 5, the molecular weight tends to increase, which is not preferable.
【００３２】本発明のアクリル酸（塩）−マレイン酸
（塩）系共重合体は、高硬度水でのクレー分散能が高
く、カルシウムイオン捕捉能も高いので、該共重合体と
界面活性剤とを含む本発明の洗剤組成物は非常に優れた
洗浄能力を発揮する。洗剤組成物中、本発明の共重合体
の配合量は０．１〜２０重量％が好ましく、０．５〜１
５重量％がより好ましい。界面活性剤の配合量は５〜７
０重量％が好ましく、２０〜６０重量％がより好まし
い。The acrylic acid (salt) -maleic acid (salt) copolymer of the present invention has a high clay dispersing ability in high hardness water and a high calcium ion trapping ability. The detergent composition of the present invention comprising: exhibits excellent cleaning ability. In the detergent composition, the amount of the copolymer of the present invention is preferably 0.1 to 20% by weight, more preferably 0.5 to 1% by weight.
5% by weight is more preferred. The amount of the surfactant is 5-7.
0% by weight is preferable, and 20 to 60% by weight is more preferable.
【００３３】界面活性剤としては、アニオン界面活性
剤、ノニオン界面活性剤、両性界面活性剤、カチオン界
面活性剤のいずれも使用可能である。アニオン界面活性
剤としては、アルキルベンゼンスルホン酸塩、アルキル
またはアルケニルエーテル硫酸塩、アルキルまたはアル
ケニル硫酸塩、α−オレフィンスルホン酸塩、α−スル
ホ脂肪酸またはエステル塩、アルカンスルホン酸塩、飽
和または不飽和脂肪酸塩、アルキルまたはアルケニルエ
ーテルカルボン酸塩、アミノ酸型界面活性剤、Ｎ−アシ
ルアミノ酸型界面活性剤、アルキルまたはアルケニルリ
ン酸エステルまたはその塩を挙げることができる。ノニ
オン界面活性剤としては、ポリオキシアルキレンアルキ
ルまたはアルケニルエーテル、ポリオキシエチレンアル
キルフェニルエーテル、高級脂肪酸アルカノールアミド
またはそのアルキレンオキサイド付加物、ショ糖脂肪酸
エステル、アルキルグリコキシド、脂肪酸グリセリンモ
ノエステル、アルキルアミンオキサイドを挙げることが
できる。両性界面活性剤としては、カルボキシ型または
スルホベタイン型両性界面活性剤を挙げることができ
る。カチオン界面活性剤としては、第４級アンモニウム
塩を挙げることができる。As the surfactant, any of anionic surfactants, nonionic surfactants, amphoteric surfactants and cationic surfactants can be used. Examples of the anionic surfactant include alkyl benzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, α-olefin sulfonate, α-sulfofatty acid or ester salt, alkane sulfonate, saturated or unsaturated fatty acid. Salts, alkyl or alkenyl ether carboxylates, amino acid type surfactants, N-acyl amino acid type surfactants, alkyl or alkenyl phosphates or salts thereof can be mentioned. Examples of the nonionic surfactant include polyoxyalkylene alkyl or alkenyl ether, polyoxyethylene alkyl phenyl ether, higher fatty acid alkanolamide or an alkylene oxide adduct thereof, sucrose fatty acid ester, alkyl glycooxide, fatty acid glycerin monoester, and alkylamine oxide. Can be mentioned. Examples of the amphoteric surfactant include a carboxy type or a sulfobetaine type amphoteric surfactant. Examples of the cationic surfactant include quaternary ammonium salts.
【００３４】本発明の洗剤組成物には、必要に応じて、
酵素、アルカリビルダー、キレートビルダー、再付着防
止剤、蛍光剤、漂白剤、香料等の洗剤組成物に常用され
る成分を配合することもできる。本発明のアクリル酸
（塩）−マレイン酸（塩）系共重合体は、洗剤用途の他
にも、無機顔料分散剤、水処理剤、繊維処理剤等として
使用することもできる。In the detergent composition of the present invention, if necessary,
Components commonly used in detergent compositions such as enzymes, alkali builders, chelate builders, anti-redeposition agents, fluorescent agents, bleaching agents, and fragrances can also be blended. The acrylic acid (salt) -maleic acid (salt) copolymer of the present invention can be used as an inorganic pigment dispersant, a water treatment agent, a fiber treatment agent, and the like, in addition to detergent use.
【００３５】[0035]
【実施例】以下に実施例によりさらに詳細に本発明を説
明するが、本発明はこれに限定されるものではない。実
施例中で「部」、「％」とは特にことわりがない限り、
それぞれ「重量部」、「重量％」を表すものとする。 （重合体物性測定方法） ＜重量平均分子量（以下Ｍｗ）＞ＧＰＣ（ゲルパーミエ
ーションクロマトグラフィー）により測定 ・カラム；ＧＦ−７ＭＨＱ （昭和電工製） ・移動相；リン酸水素二ナトリウム１２水和物３４．５
ｇ及びリン酸二水素ナトリウム２水和物４６．２ｇ（何
れも試薬特級、以下測定に用いる試薬は全て特級を使
用）に純水を加えて全量を５，０００ｇとし、その後
０．４５ミクロンのメンブランフィルターで濾過した水
溶液 ・検出器；ＵＶ ２１４ｎｍ （ウォーターズ製 モデ
ル４８１型） ・ポンプ；Ｌ−７１１０（日立製） ・流量；０．５ｍｌ／ｍｉｎ ・温度；３５℃ ・検量線；ポリアクリル酸ナトリウム標準サンプル（創
和科学製） ＜カルシウムイオン捕捉能＞ まず、カルシウムイオン標準水溶液（検量線用水溶
液）を次のように調整した。即ち、塩化カルシウム・２
水和物を用いて、Ｃａ2+イオンが０．０１ｍｏｌ／ｌ、
０．００１ｍｏｌ／ｌ、０．０００１ｍｏｌ／ｌの水溶
液を各々５０ｃｃづつ調整し、４．８％の水酸化ナトリ
ウム水溶液でｐＨ９〜１１に調整した後、塩化カリウム
の４ｍｏｌ／ｌ水溶液を１ｍｌ加えた。The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. In the examples, “parts” and “%” are unless otherwise specified.
The terms “parts by weight” and “% by weight” are respectively represented. (Method for measuring polymer physical properties) <Weight average molecular weight (Mw)> Measured by GPC (gel permeation chromatography) Column: GF-7MHQ (manufactured by Showa Denko) Mobile phase: disodium hydrogen phosphate dodecahydrate 34.5
g and 46.2 g of sodium dihydrogen phosphate dihydrate (each of which is a special grade of reagent, all reagents used in the following measurement use the special grade) to make a total amount of 5,000 g, and then 0.45 μm Aqueous solution filtered by membrane filter ・ Detector; UV 214 nm (Model 481 manufactured by Waters) ・ Pump; L-7110 (manufactured by Hitachi) ・ Flow rate: 0.5 ml / min ・ Temperature: 35 ° C. ・ Calibration curve: Sodium polyacrylate Standard sample (manufactured by Soka Kagaku) <Calcium ion capturing ability> First, a calcium ion standard aqueous solution (aqueous solution for calibration curve) was prepared as follows. That is, calcium chloride-2
Using hydrate, Ca 2+ ion is 0.01 mol / l,
50 cc of each of 0.001 mol / l and 0.0001 mol / l aqueous solutions were adjusted to pH 9 to 11 with a 4.8% aqueous sodium hydroxide solution, and then 1 ml of a 4 mol / l aqueous solution of potassium chloride was added.
【００３６】次に、測定サンプルの水溶液を調整し
た。即ち、固形分換算で１０ｍｇの重合体（ｐＨ７に調
整）を１００ｃｃのビーカーに秤量し、塩化ナトリウム
・２水和物を用いて調整した０．００１ｍｏｌ／ｌのカ
ルシウムイオン水溶液を５０ｃｃ加え、スターラーで均
一に攪拌した後、４．８％の水酸化ナトリウム水溶液で
ｐＨ９〜１１に調整し、塩化カリウムの４ｍｏｌ／ｌ水
溶液を１ｍｌ加えた。Next, an aqueous solution of the measurement sample was prepared. That is, 10 mg of a polymer (adjusted to pH 7) in terms of solid content was weighed into a 100 cc beaker, and 50 cc of a 0.001 mol / l calcium ion aqueous solution adjusted using sodium chloride dihydrate was added, followed by a stirrer. After stirring uniformly, the pH was adjusted to 9 to 11 with a 4.8% aqueous sodium hydroxide solution, and 1 ml of a 4 mol / l aqueous solution of potassium chloride was added.
【００３７】測定は、オリオン社製イオンアナライザ
ーＥＡ９２０を用いて、オリオン社製カルシウムイオン
電極９３−２０により行った。 検量線及びサンプル（重合体）の測定値から、サンプ
ルが捕捉したカルシウムイオン量を求め、重合体固形分
１ｇ当りの捕捉量を炭酸カルシウム換算のｍｇ数で表わ
し、その値をカルシウムイオン捕捉能値とした。The measurement was carried out with an Orion calcium ion electrode 93-20 using an Orion ion analyzer EA920. From the calibration curve and the measured value of the sample (polymer), the amount of calcium ions captured by the sample was determined, and the captured amount per gram of polymer solid content was expressed in mg of calcium carbonate conversion, and the value was calculated as the calcium ion capturing ability value And
【００３８】＜高硬度水でのクレー分散能＞ まず、グリシン６７．５６ｇ、塩化ナトリウム５２．
６ｇ、１Ｎ−ＮａＯＨ６０ｍｌにイオン交換水を加えて
６００ｇとしたグリシン緩衝溶液を調整した。 塩化カルシウム・２水和物を０．３２６８ｇ、の調
整液６０ｇを取って、イオン交換水を加えて１０００ｇ
とし、分散液を調整した。<Clay dispersing ability in high hardness water> First, 67.56 g of glycine and 52.g of sodium chloride.
A glycine buffer solution was prepared by adding ion-exchanged water to 6 g and 60 ml of 1N-NaOH to make 600 g. Take 60 g of the prepared solution of 0.3268 g of calcium chloride dihydrate, and add ion-exchanged water to 1000 g.
To prepare a dispersion.
【００３９】次に重合体（ｐＨ７に調整）の固形分換
算で０．１％の水溶液を調整した。 試験管に、ＪＩＳ試験用粉体Ｉ，８種（関東ローム，
微粒：日本粉体工業技術協会）のクレー０．３ｇを入
れ、の調整液２７ｇ、の調整液３ｇを添加した。こ
の時、試験液のカルシウム濃度は炭酸カルシウム換算で
２００ｐｐｍとなっている。Next, an aqueous solution of 0.1% in terms of solid content of the polymer (adjusted to pH 7) was prepared. JIS test powder I, 8 kinds (Kanto Rohm,
Fine particles: 0.3 g of clay manufactured by Japan Powder Industry Technology Association) was added, and 27 g of the adjustment liquid was added, and 3 g of the adjustment liquid was added. At this time, the calcium concentration of the test solution was 200 ppm in terms of calcium carbonate.
【００４０】試験管をパラフィルムで密封した後、ク
レーが全体に分散するように軽く振った後、さらに、上
下に２０回振った。 この試験管を直射日光の当たらないところに２０時間
静置し、その後分散液の上澄みをホールピペットで５ｍ
ｌ採取した。 この液をＵＶ分光器を用いて、波長３８０ｎｍ、１ｃ
ｍのセルで透過率（Ｔ％）を測定した。１００からこの
Ｔ％の値を差し引いた値をクレー分散能（濁度）とし
た。 ＜低硬度水でのクレー分散能＞上記の高硬度水でのクレ
ー分散能の測定方法において、の塩化カルシウム・２
水和物の添加量を０．０８１７ｇ（炭酸カルシウム換算
で５０ｐｐｍとなる）とした他は、高硬度水でのクレー
分散能と全く同様にして、低硬度水でのクレー分散能を
求めた。 （実施例１）還流冷却器、攪拌機を備えた容量５リット
ルのＳＵＳ製セパラブルフラスコにイオン交換水１５０
ｇ、無水マレイン酸９８ｇを仕込み、さらに４８％の水
酸化ナトリウム水溶液８３．３ｇを添加した。その後攪
拌下、沸点まで昇温せしめ、８０％のアクリル酸水溶液
を８１０ｇ、１５％の過硫酸ナトリウム水溶液を２６
６．７ｇ、３５％の重亜硫酸ナトリウム水溶液を２２
８．６ｇ、及びイオン交換水を４６．８ｇそれぞれ別々
の滴下ノズルより、８０％アクリル酸は１８０分間、そ
の他は１９０分間に渡って滴下した。After sealing the test tube with parafilm, the clay was gently shaken so as to be dispersed throughout, and further shaken up and down 20 times. The test tube was allowed to stand for 20 hours in a place where it was not exposed to direct sunlight, and then the supernatant of the dispersion was measured for 5 m with a whole pipette.
1 was collected. Using a UV spectrometer, this liquid was used for wavelength 380 nm, 1c
The transmittance (T%) was measured in the cell of m. The value obtained by subtracting the value of T% from 100 was defined as the clay dispersing ability (turbidity). <Clay dispersing ability in low hardness water> In the method for measuring clay dispersing ability in high hardness water, calcium chloride
The clay dispersing ability in low hardness water was determined in exactly the same manner as the clay dispersing ability in high hardness water except that the amount of hydrate added was 0.0817 g (50 ppm in terms of calcium carbonate). (Example 1) Ion-exchanged water 150 was placed in a 5-liter SUS separable flask equipped with a reflux condenser and a stirrer.
g and 98 g of maleic anhydride, and 83.3 g of a 48% aqueous sodium hydroxide solution were further added. Thereafter, the temperature was raised to the boiling point under stirring, and 810 g of an 80% aqueous solution of acrylic acid and 26% of a 15% aqueous solution of sodium persulfate were added.
6.7 g of a 35% aqueous sodium bisulfite solution in 22
8.6 g and 46.8 g of ion-exchanged water were dropped from separate dropping nozzles over 80 minutes for 80% acrylic acid and 190 minutes for the others.
【００４１】滴下終了後、さらに２０分間に渡って反応
溶液を沸点還流状態に保持して重合を完結せしめた。重
合完結後、反応溶液を放冷し、４８％の水酸化ナトリウ
ム水溶液７５０ｇを徐々に添加し中和した。このように
して、固形分濃度４８％、最終中和度９１％のアクリル
酸−マレイン酸共重合体を得た。得られた重合体の各物
性測定を行ない結果は表４にまとめた。 （実施例２〜８）実施例１において、表１に示した通り
の初期仕込量、滴下量、後中和量にした以外は同様の方
法で行なった。得られた重合体の物性測定結果は表４に
まとめた。 （実施例９）実施例１と同様に、還流冷却器、攪拌機を
備えた容量５リットルのＳＵＳ製セパラブルフラスコを
用い、純水４９５ｇ、無水マレイン酸９８ｇ、硫酸第一
鉄アンモニウムを０．５ｇを仕込み、さらに４８％の水
酸化ナトリウム水溶液４１．７ｇを添加した。その後攪
拌下、沸点まで昇温せしめ、８０％のアクリル酸水溶液
を８１０ｇ、及び３５％の過酸化水素水溶液を２８５．
７ｇを別々の滴下ノズルより、８０％アクリル酸は１８
０分間、３５％過酸化水素は１２０分間に渡って滴下し
た。After the completion of the dropwise addition, the reaction solution was kept at the boiling point reflux state for further 20 minutes to complete the polymerization. After the polymerization was completed, the reaction solution was allowed to cool, and 750 g of a 48% aqueous sodium hydroxide solution was gradually added to neutralize the solution. Thus, an acrylic acid-maleic acid copolymer having a solid content of 48% and a final degree of neutralization of 91% was obtained. The physical properties of the obtained polymer were measured, and the results are shown in Table 4. (Examples 2 to 8) The same procedures as in Example 1 were carried out except that the initial charge, the dropping amount and the post-neutralization amount were as shown in Table 1. Table 4 summarizes the measurement results of the physical properties of the obtained polymer. Example 9 In the same manner as in Example 1, a SUS separable flask having a capacity of 5 liters equipped with a reflux condenser and a stirrer was used, and 495 g of pure water, 98 g of maleic anhydride, and 0.5 g of ammonium ferrous sulfate were used. , And 41.7 g of a 48% aqueous sodium hydroxide solution were further added. Thereafter, the temperature was raised to the boiling point under stirring, and 810 g of an 80% aqueous solution of acrylic acid and 285 g of an aqueous solution of 35% hydrogen peroxide.
7 g from a separate dripping nozzle, 80% acrylic acid is 18
During 0 minutes, 35% hydrogen peroxide was added dropwise over 120 minutes.
【００４２】滴下終了後、さらに２０分間に渡って反応
溶液を沸点還流状態に保持して重合を完結せしめた。こ
のようにして固形分濃度４２％、最終中和度５％のアク
リル酸−マレイン酸共重合体を得た。得られた重合体を
ｐＨ７に調整した後、各物性測定を行ない、結果を表４
にまとめた。 （実施例１０〜１６）実施例９において、表２に示した
通りの初期仕込量、滴下量、滴下時間にした以外は同様
の方法で行なった。得られた重合体の物性測定結果は表
４にまとめた。 （比較例１）実施例１と同様に、還流冷却器、攪拌機を
備えた容量５リットルのＳＵＳ製セパラブルフラスコを
用い、イオン交換水６３０ｇを仕込み、攪拌下、温度を
２５℃一定に保持した。亜硫酸ナトリウム１モルに対し
て標準状態に換算して５１リットルの空気を反応液中に
吹き込みながら、３５％のアクリル酸ナトリウム水溶液
を１４３０ｇ、及び２０％亜硫酸水素ナトリウム水溶液
を２７６．５ｇを別々の滴下ノズルより、それぞれ２４
０分間に渡って滴下した。重合反応中、温度を２２〜２
７℃に保持し、滴下終了後３０分間に渡って、温度を保
持しながら空気の投入を続け重合を完結せしめ、固形分
濃度２５％、完全中和型ポリアクリル酸重合体を得た。
各物性測定を行ない、結果を表４にまとめた。 （比較例２）実施例１と同様に、還流冷却器、攪拌機を
備えた容量５リットルのＳＵＳ製セパラブルフラスコを
用い、純水７００ｇを仕込み、攪拌下、沸点まで昇温せ
しめた。その後、３７％のアクリル酸ナトリウム水溶液
を２０３２ｇ、１５％過硫酸ナトリウム水溶液を１０
６．７ｇ及びイオン交換水１０００ｇを別々の滴下ノズ
ルより、３７％のアクリル酸ナトリウム水溶液は１８０
分、その他は１９０分間に渡って滴下した。After completion of the dropwise addition, the reaction solution was kept at the boiling point reflux state for further 20 minutes to complete the polymerization. Thus, an acrylic acid-maleic acid copolymer having a solid content of 42% and a final degree of neutralization of 5% was obtained. After adjusting the pH of the obtained polymer to 7, each physical property was measured.
Summarized in (Examples 10 to 16) The procedure of Example 9 was repeated, except that the initial charge, the amount of dropping, and the dropping time were as shown in Table 2. Table 4 summarizes the measurement results of the physical properties of the obtained polymer. (Comparative Example 1) As in Example 1, 630 g of ion-exchanged water was charged using a 5-liter SUS separable flask equipped with a reflux condenser and a stirrer, and the temperature was kept constant at 25 ° C under stirring. . While blowing 51 liters of air into the reaction solution in terms of the standard state with respect to 1 mol of sodium sulfite, 1430 g of a 35% aqueous sodium acrylate solution and 276.5 g of a 20% aqueous sodium bisulfite solution were separately dropped. 24 nozzles each
It was added dropwise over 0 minutes. During the polymerization reaction, the temperature is 22 to 2
The temperature was kept at 7 ° C., and for 30 minutes after the completion of the dropwise addition, the introduction of air was continued while maintaining the temperature to complete the polymerization, whereby a solid content concentration of 25% and a completely neutralized polyacrylic acid polymer were obtained.
Each physical property was measured, and the results are shown in Table 4. Comparative Example 2 In the same manner as in Example 1, a 5-liter SUS separable flask equipped with a reflux condenser and a stirrer was charged with 700 g of pure water, and the temperature was raised to the boiling point under stirring. Thereafter, 2032 g of a 37% aqueous sodium acrylate solution and 10% of a 15% aqueous sodium persulfate solution were added.
6.7 g and 1000 g of ion-exchanged water were separately dropped from a 37% aqueous solution of sodium acrylate by 180%.
Minutes and others were dropped over 190 minutes.
【００４３】滴下終了後、さらに２０分間に渡って反応
溶液を沸点還流状態に保持して重合を完結せしめた。重
合完結後、反応溶液を放冷し、４８％の水酸化ナトリウ
ム水溶液６５８．３ｇを徐々に添加し中和し、固形分濃
度３５％、最終中和度９０％のアクリル酸−マレイン酸
共重合体を得た。物性測定結果を表４にまとめた。 （比較例３〜６）比較例２において、表３に示した通り
の、仕込量、滴下量、滴下時間以外は、同様に行ない、
それぞれ重合体を得た。結果を表４にまとめた。 （比較例７〜１４）特許第２５７４１４４号公報の実施
例１−１、１−４、１−６、１−１２、１−１３、１−
１６、１−２０、１−２２に準じて共重合体を得た。物
性測定評価結果を表４にまとめた。After completion of the dropwise addition, the reaction solution was kept at the boiling point reflux state for another 20 minutes to complete the polymerization. After the completion of the polymerization, the reaction solution was allowed to cool, and 658.3 g of a 48% aqueous sodium hydroxide solution was gradually added to neutralize the mixture. Acrylic acid-maleic acid copolymer having a solid content of 35% and a final neutralization degree of 90% A coalescence was obtained. Table 4 summarizes the measurement results of physical properties. (Comparative Examples 3 to 6) In Comparative Example 2, the same procedure was performed except for the charging amount, the dropping amount, and the dropping time as shown in Table 3,
Polymers were obtained respectively. The results are summarized in Table 4. (Comparative Examples 7-14) Examples 1-1, 1-4, 1-6, 1-12, 1-13, 1- of Japanese Patent No. 2574144.
Copolymers were obtained according to 16, 1-20 and 1-22. Table 4 summarizes the evaluation results of the physical properties.
【００４４】[0044]
【表１】 [Table 1]
【００４５】[0045]
【表２】 [Table 2]
【００４６】[0046]
【表３】 [Table 3]
【００４７】[0047]
【表４】 [Table 4]
【００４８】表１〜４に示されるように、本発明の製造
方法により得られた実施例の共重合体はいずれも、高硬
度水でのクレー分散能が５０％以上であり、カルシウム
イオン捕捉能が２７０ｍｇＣａＣＯ3／ｇ以上と非常に
優れたものである。実施例１〜８は重合開始剤として過
硫酸ナトリウムと重亜硫酸ナトリウムを併用したもので
あり、実施例９〜１６は重合開始剤として過酸化水素と
鉄イオン（Ｆｅ2+）を併用したものである。As shown in Tables 1 to 4, all of the copolymers of the examples obtained by the production method of the present invention have a clay dispersing ability of 50% or more in high hardness water and have a calcium ion trapping property. The performance is as excellent as 270 mg CaCO 3 / g or more. Examples 1 to 8 use sodium persulfate and sodium bisulfite as polymerization initiators, and Examples 9 to 16 use hydrogen peroxide and iron ions (Fe 2+ ) as polymerization initiators. is there.
【００４９】比較例１、２では、マレイン酸（塩）を共
重合せず、また重合開始剤として特定の化合物を組み合
わせて用いていないため、高硬度水でのクレー分散能は
高いが、カルシウムイオン捕捉能が非常に低い。比較例
３〜６では、重合開始剤として特定の化合物を組み合わ
せて用いていないため、積（ＭＡ×Ｍｗ）が１５万を越
えており、カルシウムイオン捕捉能は高いが、高硬度水
でのクレー分散能に劣るものである。比較例３、４、
５、６の順に重合濃度が高くなっており、それにつれて
積（ＭＡ×Ｍｗ）も大きくなり、同時に高硬度水でのク
レー分散能が低下している。In Comparative Examples 1 and 2, maleic acid (salt) was not copolymerized, and a specific compound was not used in combination as a polymerization initiator. Very low ion trapping ability. In Comparative Examples 3 to 6, since a specific compound was not used in combination as a polymerization initiator, the product (MA × Mw) exceeded 150,000, and the calcium ion trapping ability was high, but the clay in high-hardness water was used. It has poor dispersing ability. Comparative Examples 3, 4,
The polymerization concentration increases in the order of Nos. 5 and 6, and accordingly, the product (MA × Mw) increases, and at the same time, the clay dispersing ability in high hardness water decreases.
【００５０】比較例７〜１４は、マレイン酸（塩）の割
合が高く、また重合開始剤として特定の化合物を組み合
わせて用いていないため、カルシウムイオン捕捉能は高
いが、高硬度水でのクレー分散能が低い。また、実施例
と比較例の重合体を低硬度水でのクレー分散能で比較す
ると違いは見られないが、高硬度水でのクレー分散能で
は顕著な違いが見られる。Comparative Examples 7 to 14 have a high ratio of maleic acid (salt) and do not use a specific compound in combination as a polymerization initiator. Low dispersibility. Further, when the polymers of the examples and the comparative examples are compared in terms of clay dispersibility in low-hardness water, no difference is observed, but a remarkable difference is observed in clay dispersibility in high-hardness water.
【００５１】[0051]
【発明の効果】本発明によると、高硬度水でのクレー分
散能が高く、しかもカルシウムイオン捕捉能も高いアク
リル酸（塩）−マレイン酸（塩）系共重合体を提供する
ことができる。したがって、これを用いた洗剤組成物
は、米国や中国などの非常に高硬度の水の地域において
も、優れた洗浄能力を発揮する。According to the present invention, an acrylic acid (salt) -maleic acid (salt) copolymer having high clay dispersing ability in high hardness water and high calcium ion trapping ability can be provided. Therefore, the detergent composition using the same exhibits excellent cleaning ability even in very hard water areas such as the United States and China.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 山口 繁 大阪府吹田市西御旅町５番８号 株式会社 日本触媒内 Ｆターム(参考） 4H003 EB32 FA07 4J015 BA02 4J100 AJ02P AJ09Q AK01P AK03P AK08P AK18Q AK32Q CA04 DA01 DA28 FA03 FA30 FA37 JA15 JA57 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Shigeru Yamaguchi 5-8, Nishiobari-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd. F-term (reference) 4H003 EB32 FA07 4J015 BA02 4J100 AJ02P AJ09Q AK01P AK03P AK08P AK18Q AK32Q CA04 DA01 DA28 FA03 FA30 FA37 JA15 JA57
Claims (6)
であり、カルシウムイオン捕捉能が２７０ｍｇＣａＣＯ
3／ｇ以上である、アクリル酸（塩）−マレイン酸
（塩）系共重合体。1. A clay dispersing ability in high hardness water of 50% or more, and a calcium ion trapping ability of 270 mg CaCO
An acrylic acid (salt) -maleic acid (salt) copolymer having a content of 3 / g or more.
位とマレイン酸（塩）単位の比率がモル比で９５〜８０
／５〜２０の範囲であり、該共重合体におけるマレイン
酸（塩）単位の割合（ＭＡ（モル％））と、該共重合体
の重量平均分子量（Ｍｗ）との積（ＭＡ×Ｍｗ）が１５
０，０００以下であり、かつＭｗが２０，０００以下で
ある、請求項１記載のアクリル酸（塩）−マレイン酸
（塩）系共重合体。2. The copolymer has a molar ratio of acrylic acid (salt) unit to maleic acid (salt) unit of from 95 to 80 in molar ratio.
/ 5 to 20 and the product (MA × Mw) of the ratio of maleic acid (salt) units in the copolymer (MA (mol%)) and the weight average molecular weight (Mw) of the copolymer Is 15
The acrylic acid (salt) -maleic acid (salt) copolymer according to claim 1, which has a molecular weight of 20,000 or less and Mw of 20,000 or less.
存在下に、アクリル酸（塩）およびマレイン酸（塩）を
主成分として含む単量体成分を重合してアクリル酸
（塩）−マレイン酸（塩）系共重合体を製造する方法で
あって、 単量体成分、重合開始剤、水性溶媒および必要に応じて
用いられるその他の原材料は、重合終了後の重合体の理
論固形分濃度が４０重量％以上となるような使用量で用
いられ、 アクリル酸（塩）の使用量とマレイン酸（塩）の使用量
がモル比で９５〜８０／５〜２０の範囲であり、 重合開始剤として、(1) 過硫酸塩と重亜硫酸塩とを併用
するか、および／または、(2) 過酸化水素と多価金属イ
オンとを併用する、ことを特徴とするアクリル酸（塩）
−マレイン酸（塩）系共重合体の製造方法。3. A monomer component containing acrylic acid (salt) and maleic acid (salt) as main components in an aqueous solvent at least in the presence of a polymerization initiator to form acrylic acid (salt) -maleic. A method for producing an acid (salt) -based copolymer, in which a monomer component, a polymerization initiator, an aqueous solvent, and other raw materials used as needed are a theoretical solid concentration of the polymer after completion of the polymerization. Is used in an amount of 40% by weight or more. The amount of acrylic acid (salt) and the amount of maleic acid (salt) are in the range of 95 to 80/5 to 20 in molar ratio, and Acrylic acid (salt) characterized in that (1) a combination of persulfate and bisulfite and / or (2) a combination of hydrogen peroxide and a polyvalent metal ion as an agent.
-A method for producing a maleic acid (salt) copolymer.
とを併用し、過硫酸塩の使用量と重亜硫酸塩の使用量が
重量比で１／０．５〜１／５の範囲である、請求項３記
載のアクリル酸（塩）−マレイン酸（塩）系共重合体の
製造方法。4. A combination of persulfate and bisulfite as a polymerization initiator, wherein the amount of persulfate used and the amount of bisulfite used are in the range of 1 / 0.5 to 1/5 by weight. The method for producing an acrylic acid (salt) -maleic acid (salt) copolymer according to claim 3.
イオンとを併用し、過酸化水素の使用量が単量体成分１
モルに対し５〜１５ｇの範囲であり、多価金属イオンの
使用量が用いられる原材料の全量に対して５〜５００ｐ
ｐｍの範囲である、請求項３記載のアクリル酸（塩）−
マレイン酸（塩）系共重合体の製造方法。5. A method in which hydrogen peroxide and a polyvalent metal ion are used in combination as a polymerization initiator, and the amount of hydrogen peroxide used is
It is in the range of 5 to 15 g per mol, and the amount of the polyvalent metal ion used is 5 to 500 p with respect to the total amount of the raw materials used.
The acrylic acid (salt) according to claim 3, which is in the range of pm.
A method for producing a maleic acid (salt) -based copolymer.
（塩）−マレイン酸（塩）系共重合体と界面活性剤とを
含む洗剤組成物。6. A detergent composition comprising the acrylic acid (salt) -maleic acid (salt) copolymer according to claim 1 or 2 and a surfactant.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22600698A JP3398837B2 (en) | 1998-08-10 | 1998-08-10 | Acrylic acid (salt) -maleic acid (salt) copolymer, method for producing the same, and detergent composition |
| US09/262,011 US6310156B1 (en) | 1998-03-06 | 1999-03-04 | (Meth) acrylic acid polymer and manufacturing method thereof |
| EP99301647A EP0942015B1 (en) | 1998-03-06 | 1999-03-04 | (Meth)acrylic acid polymer and manufacturing method thereof |
| DE69917106T DE69917106T2 (en) | 1998-03-06 | 1999-03-04 | (Meth) acrylic acid polymer and process for its preparation |
| IDP990185D ID22160A (en) | 1998-03-06 | 1999-03-05 | ACRYLIC POLYMER (MET) ACRYLIC AND THE METHOD OF MAKING IT |
| CNB991034880A CN1161410C (en) | 1998-03-06 | 1999-03-06 | (meth) acrylic acid polymer and method for producing same |
| CNB031588581A CN1222573C (en) | 1998-03-06 | 1999-03-06 | (Meth) acrylic acid (salt) polymer and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22600698A JP3398837B2 (en) | 1998-08-10 | 1998-08-10 | Acrylic acid (salt) -maleic acid (salt) copolymer, method for producing the same, and detergent composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000053729A true JP2000053729A (en) | 2000-02-22 |
| JP3398837B2 JP3398837B2 (en) | 2003-04-21 |
Family
ID=16838320
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22600698A Expired - Fee Related JP3398837B2 (en) | 1998-03-06 | 1998-08-10 | Acrylic acid (salt) -maleic acid (salt) copolymer, method for producing the same, and detergent composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3398837B2 (en) |
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