JP6014372B2 - Polycarboxylic acid polymer and process for producing the same - Google Patents
Polycarboxylic acid polymer and process for producing the same Download PDFInfo
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- JP6014372B2 JP6014372B2 JP2012125564A JP2012125564A JP6014372B2 JP 6014372 B2 JP6014372 B2 JP 6014372B2 JP 2012125564 A JP2012125564 A JP 2012125564A JP 2012125564 A JP2012125564 A JP 2012125564A JP 6014372 B2 JP6014372 B2 JP 6014372B2
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- Prior art keywords
- mol
- polymerization
- polycarboxylic acid
- monomer
- acid polymer
- Prior art date
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- 229920000642 polymer Polymers 0.000 title claims description 144
- 239000002253 acid Substances 0.000 title claims description 113
- 238000000034 method Methods 0.000 title description 23
- 239000000178 monomer Substances 0.000 claims description 132
- 238000006116 polymerization reaction Methods 0.000 claims description 98
- 150000003839 salts Chemical group 0.000 claims description 77
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 38
- 150000001412 amines Chemical class 0.000 claims description 28
- 239000003505 polymerization initiator Substances 0.000 claims description 28
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 26
- 238000004519 manufacturing process Methods 0.000 claims description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 20
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 19
- 239000012986 chain transfer agent Substances 0.000 claims description 18
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 8
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 description 85
- 238000006243 chemical reaction Methods 0.000 description 83
- 239000000203 mixture Substances 0.000 description 81
- 239000000243 solution Substances 0.000 description 74
- 239000003599 detergent Substances 0.000 description 47
- 238000003756 stirring Methods 0.000 description 43
- 238000006386 neutralization reaction Methods 0.000 description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 33
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 22
- -1 amine salt Chemical class 0.000 description 21
- 238000010992 reflux Methods 0.000 description 21
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 18
- 229910001385 heavy metal Inorganic materials 0.000 description 18
- 239000001023 inorganic pigment Substances 0.000 description 16
- 239000007787 solid Substances 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 15
- 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 14
- 239000002270 dispersing agent Substances 0.000 description 14
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 13
- 150000002500 ions Chemical class 0.000 description 13
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- 238000009835 boiling Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000004094 surface-active agent Substances 0.000 description 9
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 239000002280 amphoteric surfactant Substances 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- 230000005070 ripening Effects 0.000 description 4
- 125000000542 sulfonic acid group Chemical group 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical class CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical class C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-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
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical class NCCN PIICEJLVQHRZGT-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
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 239000002455 scale inhibitor Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- STGNLGBPLOVYMA-TZKOHIRVSA-N (z)-but-2-enedioic acid Chemical compound OC(=O)\C=C/C(O)=O.OC(=O)\C=C/C(O)=O STGNLGBPLOVYMA-TZKOHIRVSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-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
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 description 1
- AAMTXHVZOHPPQR-UHFFFAOYSA-N 2-(hydroxymethyl)prop-2-enoic acid Chemical compound OCC(=C)C(O)=O AAMTXHVZOHPPQR-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- QMYCJCOPYOPWTI-UHFFFAOYSA-N 2-[(1-amino-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidamide;hydron;chloride Chemical compound Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N QMYCJCOPYOPWTI-UHFFFAOYSA-N 0.000 description 1
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 1
- DNYWXJPIRSNXIP-UHFFFAOYSA-N 2-bromo-1,1,1-trichloroethane Chemical compound ClC(Cl)(Cl)CBr DNYWXJPIRSNXIP-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
- CWNNYYIZGGDCHS-UHFFFAOYSA-N 2-methylideneglutaric acid Chemical compound OC(=O)CCC(=C)C(O)=O CWNNYYIZGGDCHS-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
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- XHULUQRDNLRXPF-UHFFFAOYSA-N 3-ethenyl-1,3-oxazolidin-2-id-4-one Chemical compound C(=C)N1[CH-]OCC1=O XHULUQRDNLRXPF-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 1
- 229910016876 Fe(NH4)2(SO4)2 Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 229950005228 bromoform Drugs 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000002761 deinking Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000005332 diethylamines Chemical class 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 229940043276 diisopropanolamine Drugs 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- RMGVZKRVHHSUIM-UHFFFAOYSA-N dithionic acid Chemical compound OS(=O)(=O)S(O)(=O)=O RMGVZKRVHHSUIM-UHFFFAOYSA-N 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical compound CC(=C)CCO CPJRRXSHAYUTGL-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 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
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 1
- PZUGJLOCXUNFLM-UHFFFAOYSA-N n-ethenylaniline Chemical compound C=CNC1=CC=CC=C1 PZUGJLOCXUNFLM-UHFFFAOYSA-N 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 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
- HEZHYQDYRPUXNJ-UHFFFAOYSA-L potassium dithionite Chemical compound [K+].[K+].[O-]S(=O)S([O-])=O HEZHYQDYRPUXNJ-UHFFFAOYSA-L 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- 229910001380 potassium hypophosphite Inorganic materials 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
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 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
- 238000000746 purification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003573 thiols Chemical group 0.000 description 1
- 229940034610 toothpaste Drugs 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 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
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、ポリカルボン酸系重合体、及びその製造方法に関するものである。 The present invention relates to a polycarboxylic acid polymer and a method for producing the same.
従来から、（メタ）アクリル酸系重合体等のポリカルボン酸系重合体のうち、低分子量のものは、その優れたキレート能や分散能を利用して、洗剤ビルダーや、無機顔料や金属イオン等の分散剤やスケール防止剤等に好適に用いられている。 Conventionally, among polycarboxylic acid-based polymers such as (meth) acrylic acid-based polymers, low molecular weight ones use detergent builder, inorganic pigments and metal ions by utilizing their excellent chelating ability and dispersing ability. It is suitably used for dispersants such as the above and scale inhibitors.
例えば引用文献１には、５０〜１００ｍｏｌ％の（メタ）アクリル酸、および０〜５０ｍｏｌ％の、（メタ）アクリル酸に共重合可能な水溶性モノエチレン性不飽和単量体を水溶液中で重合してなる重合体であって、末端にスルホン酸基を有するとともに、次式、Ｑ＝ゲル化度×１０５／重量平均分子量で定義される耐ゲル能Ｑ値が２．０未満であることを特徴とする（メタ）アクリル酸系重合体が開示されている。上記重合体は、高いキレート能および分散能に加え、良好な耐ゲル性を示すことが開示されている。 For example, in Cited Document 1, 50 to 100 mol% (meth) acrylic acid and 0 to 50 mol% of a water-soluble monoethylenically unsaturated monomer copolymerizable with (meth) acrylic acid are polymerized in an aqueous solution. And having a sulfonic acid group at the terminal, and having a gel resistance Q value defined by the following formula: Q = degree of gelation × 10 5 / weight average molecular weight is less than 2.0 A (meth) acrylic acid polymer characterized by the following is disclosed. It is disclosed that the polymer exhibits good gel resistance in addition to high chelating ability and dispersibility.
例えば特許文献２には、Ｓ＝（ポリマーに含まれるＳ量）／（全Ｓ量）×１００で定義される硫黄元素導入量Ｓ値が３５以上であることを特徴とする（メタ）アクリル酸系重合体が開示されている。上記重合体は、高いキレート能および分散能に加え、良好な耐ゲル性を示すことが開示されている。 For example, Patent Document 2 discloses (meth) acrylic acid characterized in that the sulfur element introduction amount S value defined by S = (S amount contained in polymer) / (total S amount) × 100 is 35 or more. System polymers are disclosed. It is disclosed that the polymer exhibits good gel resistance in addition to high chelating ability and dispersibility.
上述したように、従来、様々なポリカルボン酸系重合体（組成物）が報告されているものの、例えば洗剤組成物等に多量に添加しても洗剤組成物の色調を損ねないように、ポリカルボン酸系重合体（組成物）の色調（着色が少ない）を改良する余地があった。
そこで、本発明は、従来のポリカルボン酸系重合体（組成物）よりも色調が良好となる（着色が少ない）ことにより、洗剤組成物への添加剤等（例えば洗剤ビルダー）に好ましく使用できるポリカルボン酸系重合体（組成物）を提供することを目的とする。
As described above, various polycarboxylic acid polymers (compositions) have been reported so far, but for example, a polycondensate so as not to impair the color of the detergent composition even if added in a large amount to the detergent composition, for example. There was room for improving the color tone (low coloration) of the carboxylic acid polymer (composition).
Therefore, the present invention can be preferably used as an additive to a detergent composition (for example, a detergent builder) because the color tone is better (less colored) than a conventional polycarboxylic acid polymer (composition). An object is to provide a polycarboxylic acid polymer (composition).
本発明者らは、上記目的を達成するために様々な重合体について鋭意検討を行なった結果、特定の構造を有するポリカルボン酸系重合体が優れた色調（着色が少ない）を示すことを知得し、該知見に基づいて本発明を完成した。
すなわち、本発明は、主鎖末端にスルホン酸（塩）基を有し、カルボキシル基の一部が有機アミン塩である、ポリカルボン酸系重合体である。
As a result of intensive studies on various polymers in order to achieve the above object, the present inventors have found that a polycarboxylic acid polymer having a specific structure exhibits excellent color tone (low coloration). And the present invention was completed based on the findings.
That is, the present invention is a polycarboxylic acid polymer having a sulfonic acid (salt) group at the main chain terminal and a part of the carboxyl group being an organic amine salt.
本発明のポリカルボン酸系重合体は、優れた色調（着色が少ない）を有する。従って、例えば洗剤組成物への添加剤等として有用に使用することができる。 The polycarboxylic acid polymer of the present invention has an excellent color tone (low coloration). Therefore, it can be usefully used, for example, as an additive to a detergent composition.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
〔本発明のポリカルボン酸系重合体〕
＜カルボキシル基含有単量体（Ａ）由来の構造単位（ａ）＞
本発明のポリカルボン酸系重合体は、カルボキシル基含有単量体（Ａ）由来の構造単位（ａ）を有する。本発明において、カルボキシル基含有単量体（Ａ）とは、１）炭素炭素不飽和二重結合と、２）カルボキシル基および／またはその塩とを必須として含有する単量体である。具体的には、アクリル酸、メタクリル酸、クロトン酸、αーヒドロキシアクリル酸、α−ヒドロキシメチルアクリル酸及びその誘導体等の、不飽和モノカルボン酸及びこれらの塩等；イタコン酸、フマル酸、マレイン酸、２−メチレングルタル酸等の不飽和ジカルボン酸及びこれらの塩等が挙げられる。
[Polycarboxylic acid polymer of the present invention]
<Structural unit (a) derived from carboxyl group-containing monomer (A)>
The polycarboxylic acid polymer of the present invention has a structural unit (a) derived from the carboxyl group-containing monomer (A). In the present invention, the carboxyl group-containing monomer (A) is a monomer that essentially contains 1) a carbon-carbon unsaturated double bond, and 2) a carboxyl group and / or a salt thereof. Specifically, unsaturated monocarboxylic acids and their salts such as acrylic acid, methacrylic acid, crotonic acid, α-hydroxyacrylic acid, α-hydroxymethylacrylic acid and derivatives thereof; itaconic acid, fumaric acid, malee Examples thereof include unsaturated dicarboxylic acids such as acid and 2-methyleneglutaric acid, and salts thereof.
上記塩とは、金属塩、アンモニウム塩、有機アミン塩である。金属塩としては、ナトリウム塩、リチウム塩、カリウム塩等のアルカリ金属の塩；マグネシウム塩、カルシウム塩、等のアルカリ土類金属の塩；アルミニウム、鉄等の塩等が挙げられる。また、有機アミン塩としては、モノエタノールアミン塩、ジエタノールアミン塩、トリエタノールアミン塩等のアルカノールアミン塩；モノエチルアミン塩、ジエチルアミン塩、トリエチルアミン塩等のアルキルアミン塩；エチレンジアミン塩、トリエチレンジアミン塩等のポリアミン等の有機アミンの塩が挙げられる。 The salt is a metal salt, an ammonium salt, or an organic amine salt. Examples of the metal salt include alkali metal salts such as sodium salt, lithium salt and potassium salt; alkaline earth metal salts such as magnesium salt and calcium salt; salts such as aluminum and iron. Organic amine salts include monoethanolamine salts, diethanolamine salts, triethanolamine salts and other alkanolamine salts; monoethylamine salts, diethylamine salts, triethylamine salts and other alkylamine salts; ethylenediamine salts, triethylenediamine salts and other polyamines And salts of organic amines such as
本発明のポリカルボン酸系重合体（組成物）の色調が良好となる（着色が少なくなる）ことから、本発明のポリカルボン酸系重合体の有するカルボキシル基の一部が有機アミンで中和されていることを必須としている。すなわち、カルボキシル基含有単量体（Ａ）由来の構造単位（ａ）の一部は、カルボキシル基（構造単位（ａ）が２以上のカルボキシル基を有する場合には少なくとも１つのカルボキシル基）が有機アミン（塩）である構造単位である（以下、構造単位（ａ１）ということもある）。
上記有機アミン塩の中でも、２級アミンの塩が好ましく、ジエタノールアミンがより好ましい。
Since the color tone of the polycarboxylic acid polymer (composition) of the present invention is good (coloring is reduced), some of the carboxyl groups of the polycarboxylic acid polymer of the present invention are neutralized with an organic amine. It is essential to be. That is, a part of the structural unit (a) derived from the carboxyl group-containing monomer (A) is organic in a carboxyl group (at least one carboxyl group when the structural unit (a) has two or more carboxyl groups). It is a structural unit that is an amine (salt) (hereinafter sometimes referred to as structural unit (a1)).
Among the organic amine salts, secondary amine salts are preferable, and diethanolamine is more preferable.
カルボキシル基含有単量体（Ａ）の中でも、洗剤ビルダーとしての性能（よごれ粒子の分散性能等）が高くなる傾向にあることから、アクリル酸、アクリル酸塩、メタクリル酸、メタクリル酸塩、マレイン酸、マレイン酸塩が好ましく、アクリル酸、アクリル酸塩、メタクリル酸、メタクリル酸塩（これらを「（メタ）アクリル酸（塩）」とも言う。）を必須とすることがより好ましい。
本発明のポリカルボン酸系重合体は、構造単位（ａ）を１種のみで含んでいても良いが、２種類以上含んでいても良い。
上記構造単位（ａ）は、単量体（Ａ）の炭素炭素二重結合（例えば、ＣＨ２＝Ｃ（Ｒ１）−）が単結合（例えば、−ＣＨ２−Ｃ（Ｒ１）−）になった構造である。
Among the carboxyl group-containing monomers (A), the performance as a detergent builder (dispersion performance of dirt particles, etc.) tends to be high, so acrylic acid, acrylate, methacrylic acid, methacrylate, maleic acid Maleate is preferable, and it is more preferable to use acrylic acid, acrylic acid salt, methacrylic acid, and methacrylic acid salt (these are also referred to as “(meth) acrylic acid (salt)”).
The polycarboxylic acid polymer of the present invention may contain only one type of structural unit (a), but may contain two or more types.
In the structural unit (a), the carbon-carbon double bond (for example, CH 2 ═C (R 1 ) —) of the monomer (A) is a single bond (for example, —CH 2 —C (R 1 ) —). This is the structure.
本発明のポリカルボン酸系重合体は、カルボキシル基含有単量体（Ａ）由来の構造単位（ａ）を全単量体に由来する構造単位の合計１００モル％（すなわち、カルボキシル基含有単量体に由来する構造単位と、その他の単量体に由来する構造単位との合計１００モル％）に対して、５０モル％以上、１００モル％以下の割合で有することが好ましい。構造単位（ａ）が上記範囲内であることにより、洗剤ビルダーとしての性能（よごれ粒子の分散性能等）が向上する傾向にある。全単量体に由来する構造単位の合計１００モル％に対する構造単位（ａ）の割合は、８０モル％以上、１００モル％以下であることがより好ましく、９０モル％以上、１００モル％以下であることがさらに好ましく、１００モル％であることが特に好ましい。 In the polycarboxylic acid polymer of the present invention, the structural unit (a) derived from the carboxyl group-containing monomer (A) is 100 mol% in total of the structural units derived from all monomers (that is, the carboxyl group-containing single monomer). It is preferable to have a proportion of 50 mol% or more and 100 mol% or less with respect to 100 mol% in total of the structural units derived from the body and the structural units derived from other monomers. When the structural unit (a) is within the above range, the performance as a detergent builder (such as the dispersion performance of dirt particles) tends to be improved. The ratio of the structural unit (a) to the total of 100 mol% of the structural units derived from all monomers is more preferably 80 mol% or more and 100 mol% or less, and 90 mol% or more and 100 mol% or less. More preferably, it is particularly preferably 100 mol%.
本発明のポリカルボン酸系重合体は、上記の通りカルボキシル基含有単量体に由来する構造単位として、好ましくは（メタ）アクリル酸（塩）に由来する構造単位を含むが、その場合、全単量体に由来する構造単位の合計１００モル％に対して、（メタ）アクリル酸（塩）に由来する構造単位が５０モル％以上、１００モル％以下であることが好ましく、８０モル％以上、１００モル％以下であることがより好ましく、９０モル％以上、１００モル％以下であることがさらに好ましく、１００モル％であることが特に好ましい。 The polycarboxylic acid polymer of the present invention preferably contains structural units derived from (meth) acrylic acid (salt) as structural units derived from the carboxyl group-containing monomer as described above. It is preferable that the structural unit derived from (meth) acrylic acid (salt) is 50 mol% or more and 100 mol% or less with respect to a total of 100 mol% of the structural units derived from the monomer, and 80 mol% or more. 100 mol% or less is more preferable, 90 mol% or more and 100 mol% or less is more preferable, and 100 mol% is particularly preferable.
上記の通り、本発明のポリカルボン酸系重合体は、カルボキシル基の一部が有機アミンで中和されていることを特徴としている。本発明のポリカルボン酸系重合体の有するカルボキシル基１００モル％に対して、有機アミンで中和されているカルボキシル基が、１〜７０モル％であることが好ましく、５〜６０モル％であることがより好ましく、１０〜５０モル％であることが特に好ましい。 As described above, the polycarboxylic acid polymer of the present invention is characterized in that a part of the carboxyl group is neutralized with an organic amine. The carboxyl group neutralized with an organic amine is preferably 1 to 70 mol%, preferably 5 to 60 mol%, based on 100 mol% of the carboxyl group of the polycarboxylic acid polymer of the present invention. Is more preferable, and it is especially preferable that it is 10-50 mol%.
本発明のポリカルボン酸系重合体は、上記構造単位（ａ１）を、全単量体に由来する構造単位の合計１００モル％に対して、１〜７０モル％の割合で有することが好ましく、５〜６０モル％の割合で有することがより好ましく、１０〜５０モル％の割合で有することが特に好ましい。 The polycarboxylic acid polymer of the present invention preferably has the structural unit (a1) in a proportion of 1 to 70 mol% with respect to 100 mol% in total of the structural units derived from all monomers, It is more preferable to have it in the ratio of 5-60 mol%, and it is especially preferable to have it in the ratio of 10-50 mol%.
本発明のポリカルボン酸系重合体は、（メタ）アクリル酸（塩）に由来する構造単位のカルボキシル基が有機アミン塩である構造単位（以下、構造単位（ａ２）ともいう）を全単量体に由来する構造単位の合計１００モル％に対して、１〜７０モル％の割合で有することが好ましく、５〜６０モル％の割合で有することがより好ましく、１０〜５０モル％の割合で有することが特に好ましい。なお、構造単位（ａ２）は、−ＣＨ２−ＣＲ（ＣＯＯＭ）−で表わされる（Ｒは水素原子、メチル基を表し、Ｍは有機アンモニウム基を表す。）。 The polycarboxylic acid polymer of the present invention is a single unit of a structural unit (hereinafter also referred to as structural unit (a2)) in which the carboxyl group of the structural unit derived from (meth) acrylic acid (salt) is an organic amine salt. It is preferable to have a proportion of 1 to 70 mol%, more preferably 5 to 60 mol%, and more preferably 10 to 50 mol%, based on 100 mol% of the structural units derived from the body. It is particularly preferable to have it. The structural unit (a2) is represented by —CH 2 —CR (COOM) — (R represents a hydrogen atom or a methyl group, and M represents an organic ammonium group).
ポリカルボン酸系重合体に含まれるカルボキシル基含有単量体（Ａ）由来の構造単位（ａ）の内、カルボキシル基が金属塩である構造単位（以下、構造単位（ａ３）ともいう）の存在量が高くなると、ポリカルボン酸系重合体の界面活性剤との相溶性が低下する傾向にある為、液体洗剤に配合しにくくなる場合がある。その為、本発明のポリカルボン酸系重合体は、上記構造単位（ａ３）を、全単量体に由来する構造単位の合計１００モル％に対して、０〜９０モル％の割合にすることが好ましく、０〜３０モル％の割合にすることがより好ましい。 Of the structural unit (a) derived from the carboxyl group-containing monomer (A) contained in the polycarboxylic acid polymer, the presence of a structural unit (hereinafter also referred to as structural unit (a3)) in which the carboxyl group is a metal salt. When the amount is high, the compatibility of the polycarboxylic acid polymer with the surfactant tends to be reduced, so that it may be difficult to blend in the liquid detergent. Therefore, in the polycarboxylic acid polymer of the present invention, the structural unit (a3) is in a proportion of 0 to 90 mol% with respect to 100 mol% in total of the structural units derived from all monomers. Is more preferable, and a ratio of 0 to 30 mol% is more preferable.
ポリカルボン酸系重合体に含まれるカルボキシル基含有単量体（Ａ）由来の構造単位（ａ）の内、カルボキシル基が未中和（酸型）である構造単位（以下、構造単位（ａ４）ともいう）の存在量が高くなると、洗剤に配合した場合に皮膚への刺激等が高くなる傾向にある。その為、本発明のポリカルボン酸系重合体は、上記構造単位（ａ４）を、全単量体に由来する構造単位の合計１００モル％に対して、０〜９９モル％の割合にすることが好ましく、０〜９０モル％の割合にすることがより好ましい。 Of the structural unit (a) derived from the carboxyl group-containing monomer (A) contained in the polycarboxylic acid polymer, a structural unit in which the carboxyl group is unneutralized (acid type) (hereinafter, structural unit (a4)) When the abundance of (also referred to as) is increased, the skin irritation and the like tend to increase when blended with a detergent. Therefore, in the polycarboxylic acid polymer of the present invention, the structural unit (a4) is in a proportion of 0 to 99 mol% with respect to 100 mol% of the total structural units derived from all monomers. Is preferable, and a ratio of 0 to 90 mol% is more preferable.
＜その他の単量体（Ｅ）由来の構造単位（ｅ）＞
本発明のポリカルボン酸系重合体は、その他の単量体（Ｅ）由来の構造単位（ｅ）を有していても構わない。
本発明のポリカルボン酸系重合体が他の単量体（Ｅ）を含む際の他の単量体（Ｅ）としては、上記単量体（Ａ）と共重合可能なものであれば特に限定されるものではなく、所望の効果によって適宜選択される。具体的には、３−アリルオキシ−２−ヒドロキシプロパンスルホン酸、（メタ）アリルスルホン酸、イソプレンスルホン酸、ビニルスルホン酸、スチレンスルホン酸及びこれらの塩等のスルホン酸基含有単量体；（メタ）アリルアルコール、イソプレノール等の不飽和アルコールにアルキレンオキサイドを付加した単量体、（メタ）アクリル酸のポリアルキレングリコールエステル、等のポリアルキレングリコール系単量体；Ｎ−ビニルピロリドン、Ｎ−ビニルホルムアミド、Ｎ−ビニルアセトアミド、Ｎ−ビニルオキサゾリドン等のＮ−ビニル単量体；（メタ）アクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ−イソプロピルアクリルアミド等のアクリルアミド系単量体；ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ドデシル（メタ）アクリレート等の（メタ）アクリル酸アルキルエステル系単量体；２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、３−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、ヒドロキシペンチル（メタ）アクリレート等の（メタ）アクリル酸ヒドロキシアルキル系単量体；ビニルピリジン、ビニルイミダゾール等の複素環式芳香族炭化水素基と重合性基を有するビニル芳香族系アミノ基含有単量体およびこれらの４級化物や塩；ジアリルアミン、ジアリルジメチルアミン等のアリルアミン類およびこれらの４級化物や塩；（ｉ）（メタ）アリルグリシジルエーテル、イソプレニルグリシジルエーテル、ビニルグリシジルエーテルのエポキシ環に、（ｉｉ）ジメチルアミン、ジエチルアミン、ジイソプロピルアミン、ジｎ−ブチルアミン等のアルキルアミン、ジエタノールアミン、ジイソプロパノールアミン等のアルカノールアミン、モルホリン、ピロール等の環状アミン類等のアミンを反応させることにより得られる単量体およびこれらの４級化物や塩等；スチレン、インデン、ビニルアニリン等のビニルアリール単量体、イソブチレン、酢酸ビニル；等が挙げられる。
また、上記他の単量体（Ｅ）は、１種を単独で使用してもあるいは２種以上の混合物の形態で使用されてもよい。
<Structural unit (e) derived from other monomer (E)>
The polycarboxylic acid polymer of the present invention may have a structural unit (e) derived from other monomer (E).
As the other monomer (E) when the polycarboxylic acid-based polymer of the present invention contains another monomer (E), it is particularly preferable that it can be copolymerized with the monomer (A). It is not limited and is appropriately selected depending on the desired effect. Specifically, sulfonic acid group-containing monomers such as 3-allyloxy-2-hydroxypropanesulfonic acid, (meth) allylsulfonic acid, isoprenesulfonic acid, vinylsulfonic acid, styrenesulfonic acid, and salts thereof; ) Monomers obtained by adding alkylene oxide to unsaturated alcohols such as allyl alcohol and isoprenol, polyalkylene glycol monomers such as polyalkylene glycol esters of (meth) acrylic acid; N-vinylpyrrolidone, N-vinylformamide N-vinyl monomers such as N-vinylacetamide and N-vinyloxazolidone; acrylamide monomers such as (meth) acrylamide, N, N-dimethylacrylamide and N-isopropylacrylamide; butyl (meth) acrylate, 2 -Ethylhexyl (meth) (Meth) acrylic acid alkyl ester monomers such as acrylate and dodecyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2- Hydroxyalkyl (meth) acrylate monomers such as hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and hydroxypentyl (meth) acrylate; heterocyclic aromatic hydrocarbons such as vinylpyridine and vinylimidazole Vinyl aromatic amino group-containing monomers having a group and a polymerizable group, and quaternized products and salts thereof; allylamines such as diallylamine and diallyldimethylamine, and quaternized products and salts thereof; (i) (meth) Allyl glycidyl ether, isoprene (Ii) alkylamines such as dimethylamine, diethylamine, diisopropylamine and di-n-butylamine, alkanolamines such as diethanolamine and diisopropanolamine, cyclic amines such as morpholine and pyrrole, etc. on the epoxy ring of glycidyl ether and vinyl glycidyl ether Monomers obtained by reacting these amines, and quaternized products and salts thereof; vinyl aryl monomers such as styrene, indene and vinylaniline; isobutylene and vinyl acetate; and the like.
Moreover, the said other monomer (E) may be used individually by 1 type, or may be used with the form of a 2 or more types of mixture.
本発明のポリカルボン酸系重合体は、任意であるが、上記構造単位（ｅ）を全単量体に由来する構造単位の合計１００モル％に対して、０モル％以上、５０モル％以下の割合で有していても良く。０モル％以上、２０モル％以下であることがより好ましく、０モル％以上、１０モル％以下であることがさらに好ましく、０モル％であることが特に好ましい。 The polycarboxylic acid polymer of the present invention is optional, but the above structural unit (e) is 0 mol% or more and 50 mol% or less with respect to 100 mol% of the total structural units derived from all monomers. You may have in ratio. It is more preferably 0 mol% or more and 20 mol% or less, further preferably 0 mol% or more and 10 mol% or less, and particularly preferably 0 mol%.
本発明のポリカルボン酸系重合体の重量平均分子量は、適宜設定できるものであり、特に限定されないが、洗剤ビルダーとしての性能（よごれ粒子の分散性能等）が向上する傾向になることから、具体的には、２，０００〜２００，０００であることが好ましく、より好ましくは３，０００〜６０，０００、最も好ましくは４，０００〜４０，０００である。なお、本明細書において、重量平均分子量は、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）による測定値であり、実施例に記載される方法に従って測定されたものである。 The weight average molecular weight of the polycarboxylic acid-based polymer of the present invention can be set as appropriate and is not particularly limited. However, since the performance as a detergent builder (such as the ability to disperse dirty particles) tends to be improved, it is specific. Specifically, it is preferably 2,000 to 200,000, more preferably 3,000 to 60,000, and most preferably 4,000 to 40,000. In addition, in this specification, a weight average molecular weight is a measured value by GPC (gel permeation chromatography), and was measured according to the method described in an Example.
＜主鎖末端のスルホン酸（塩）基＞
本発明のポリカルボン酸系重合体は、重合体分子の少なくとも一つの主鎖末端にスルホン酸（塩）基を有することを特徴としている。少なくとも一つの主鎖末端にスルホン酸（塩）基を有するとは、１または２以上の主鎖末端にスルホン酸（塩）基を有することをいい、例えば直鎖状の重合体分子であれば２の主鎖末端にスルホン酸（塩）基を有していてもよく、分岐状の重合体分子であれば、３以上の主鎖末端にスルホン酸（塩）基を有していても良い。少なくとも一つの主鎖末端にスルホン酸（塩）基を有することにより洗剤ビルダーとしての性能（よごれ粒子の分散性能等）が向上する傾向にあることから好ましい。１または２の主鎖末端にスルホン酸（塩）基を有することが好ましい。
<Sulphonic acid (salt) group at the end of the main chain>
The polycarboxylic acid polymer of the present invention is characterized by having a sulfonic acid (salt) group at the end of at least one main chain of the polymer molecule. Having a sulfonic acid (salt) group at at least one main chain terminal means having one or two or more main chain terminals having a sulfonic acid (salt) group, for example, a linear polymer molecule. 2 may have a sulfonic acid (salt) group at the terminal end of the main chain, and may have a sulfonic acid (salt) group at three or more main chain terminals as long as it is a branched polymer molecule. . Having a sulfonic acid (salt) group at at least one main chain terminal is preferable because the performance as a detergent builder (such as the dispersibility of dirt particles) tends to be improved. It is preferable to have a sulfonic acid (salt) group at one or two main chain terminals.
共重合体の分子末端にスルホン酸（塩）基を含む構造単位を形成する方法としては、単量体（Ａ）を必須に含む単量体を、重亜硫酸（塩）類（亜硫酸、重亜硫酸、亜二チオン酸、メタ重亜硫酸、及びそれらの塩等をいう）の存在下で重合する方法が好ましく用いられる。上記の場合、重亜硫酸（塩）類が連鎖移動剤等として作用することにより、スルホン酸（塩）基が重合体分子内に取り込まれることとなる。
共重合体の分子末端のスルホン酸（塩）基は例えば１ＨＮＭＲ等により測定することができる。
なお、スルホン酸（塩）基における塩とは、金属塩、アンモニウム塩、有機アミン塩である。
As a method for forming a structural unit containing a sulfonic acid (salt) group at the molecular end of the copolymer, a monomer containing the monomer (A) as an essential component is converted to a bisulfite (salt) class (sulfurous acid, bisulfite). , Dithionic acid, metabisulfite, and salts thereof) are preferably used. In the above case, the bisulfite (salt) acts as a chain transfer agent or the like, whereby the sulfonic acid (salt) group is incorporated into the polymer molecule.
The sulfonic acid (salt) group at the molecular end of the copolymer can be measured, for example, by 1 HNMR.
The salt in the sulfonic acid (salt) group is a metal salt, an ammonium salt, or an organic amine salt.
＜ポリカルボン酸系重合体組成物＞
本発明のポリカルボン酸系重合体組成物は、本発明のポリカルボン酸系重合体を必須として含有する。本発明のポリカルボン酸系重合体組成物は、本発明のポリカルボン酸系重合体以外に任意の成分を含有することが可能であるが、通常はその他に、原料の残渣、重合時の副生成物、水分から選ばれる１以上を含有する。
本発明のポリカルボン酸系重合体組成物の好ましい形態は、本発明のポリカルボン酸系重合体を２０〜８０質量％含有し、水を２０〜８０質量％含有する形態である。
本発明のポリカルボン酸系重合体組成物は、残存単量体の含有量が固形分換算で、０〜１５０００ｐｐｍであることが好ましく、０〜１００００ｐｐｍであることがより好ましい。
<Polycarboxylic acid polymer composition>
The polycarboxylic acid polymer composition of the present invention contains the polycarboxylic acid polymer of the present invention as an essential component. The polycarboxylic acid polymer composition of the present invention can contain optional components in addition to the polycarboxylic acid polymer of the present invention. Contains one or more selected from products and moisture.
A preferable form of the polycarboxylic acid polymer composition of the present invention is a form containing 20 to 80% by mass of the polycarboxylic acid polymer of the present invention and 20 to 80% by mass of water.
In the polycarboxylic acid-based polymer composition of the present invention, the content of the residual monomer is preferably 0 to 15000 ppm, more preferably 0 to 10,000 ppm in terms of solid content.
〔本発明のポリカルボン酸系重合体（組成物）の製造方法〕
本発明のポリカルボン酸系重合体（組成物）の製造方法は、特に断りの無い限りは、公知の重合方法と同様にしてあるいは修飾した方法が使用できる。本発明のポリカルボン酸系重合体（組成物）を製造する方法としては、カルボキシル基含有単量体を必須として含む単量体（単量体成分）を重合する工程（重合工程）を必須に含むことにより製造することができる。また、単量体成分を重合する際には、必要に応じ、上記その他の単量体（Ｅ）を更に共重合させてもよい。
[Production Method of Polycarboxylic Acid Polymer (Composition) of the Present Invention]
The production method of the polycarboxylic acid-based polymer (composition) of the present invention can be the same as a known polymerization method or a modified method unless otherwise specified. As a method for producing the polycarboxylic acid polymer (composition) of the present invention, a step of polymerizing a monomer (monomer component) containing a carboxyl group-containing monomer as an essential component (polymerization step) is essential. It can manufacture by including. Further, when the monomer component is polymerized, the other monomer (E) may be further copolymerized as necessary.
このような製造方法においては、重合開始剤を用いて単量体成分を重合すればよい。なお、ポリカルボン酸系重合体を構成する構成単位が上述したようになるように、単量体成分に含まれる単量体の種類や使用量を適宜設定することになる。
本発明のポリカルボン酸系重合体（組成物）の製造に用いられるカルボキシル基含有単量体の組成比は、全単量体（すなわち、カルボキシル基含有単量体と、その他の単量体の合計）１００モル％に対して、カルボキシル基含有単量体が５０モル％以上、１００モル％以下であることが好ましく、８０モル％以上、１００モル％以下であることがより好ましく、９０モル％以上、１００モル％以下であることがさらに好ましく、１００モル％であることが特に好ましい。本発明のポリカルボン酸系重合体（組成物）の製造に用いられるその他の単量体の組成比は、全単量体１００モル％に対して、その他の単量体が０モル％以上、５０モル％以下であることが好ましく、０モル％以上、２０モル％以下であることがより好ましく、０モル％以上、１０モル％以下であることがさらに好ましく、０モル％であることが特に好ましい。
In such a production method, the monomer component may be polymerized using a polymerization initiator. In addition, the kind and usage-amount of the monomer contained in a monomer component are set suitably so that the structural unit which comprises a polycarboxylic acid-type polymer may become as above-mentioned.
The composition ratio of the carboxyl group-containing monomer used in the production of the polycarboxylic acid polymer (composition) of the present invention is the total monomer (that is, the carboxyl group-containing monomer and other monomers). The total carboxyl group-containing monomer is preferably 50 mol% or more and 100 mol% or less, more preferably 80 mol% or more and 100 mol% or less, and 90 mol% relative to 100 mol%. As mentioned above, it is more preferable that it is 100 mol% or less, and it is especially preferable that it is 100 mol%. The composition ratio of other monomers used in the production of the polycarboxylic acid polymer (composition) of the present invention is such that the other monomers are 0 mol% or more with respect to 100 mol% of all monomers, It is preferably 50 mol% or less, more preferably 0 mol% or more and 20 mol% or less, further preferably 0 mol% or more and 10 mol% or less, and particularly preferably 0 mol%. preferable.
本発明のポリカルボン酸系重合体（組成物）の洗剤ビルダーとしての性能（よごれ粒子の分散性能等）が向上する傾向にあることから、上記カルボキシル基含有単量体は（メタ）アクリル酸（塩）を含むことが好ましい。本発明のポリカルボン酸系重合体（組成物）の製造に用いられる（メタ）アクリル酸（塩）の組成比は、全単量体１００モル％に対して、（メタ）アクリル酸（塩）が５０モル％以上、１００モル％以下であることが好ましく、８０モル％以上、１００モル％以下であることがより好ましく、９０モル％以上、１００モル％以下であることがさらに好ましく、１００モル％であることが特に好ましい。 Since the performance as a detergent builder of the polycarboxylic acid polymer (composition) of the present invention (such as the dispersion performance of dirt particles) tends to improve, the carboxyl group-containing monomer is (meth) acrylic acid ( Salt). The composition ratio of (meth) acrylic acid (salt) used in the production of the polycarboxylic acid polymer (composition) of the present invention is (meth) acrylic acid (salt) with respect to 100 mol% of all monomers. Is preferably 50 mol% or more and 100 mol% or less, more preferably 80 mol% or more and 100 mol% or less, still more preferably 90 mol% or more and 100 mol% or less, and even more preferably 100 mol% % Is particularly preferred.
本発明のポリカルボン酸系重合体（組成物）の製造方法において、使用する重合溶媒としては、水を含むことが好ましく、使用する全溶剤量に対して水を５０質量％以上、１００質量％使用することが好ましく、使用する溶媒の全量を水とすることが好ましい。
単独で、または水と共に使用でき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類；アセトン、メチルエチルケトン、ジエチルケトン等の低級ケトン類；ジメチルエーテル、ジオキサン等のエーテル類；ジメチルホルムアルデヒド等のアミド類が挙げられる。有機溶剤は１種または２種以上で使用することができる。
In the method for producing a polycarboxylic acid polymer (composition) of the present invention, the polymerization solvent to be used preferably contains water, and water is contained in an amount of 50% by mass or more and 100% by mass with respect to the total amount of the solvent used. It is preferable to use it, and it is preferable that the total amount of the solvent used is water.
Organic solvents that can be used alone or in combination with water include lower alcohols such as methanol, ethanol and isopropyl alcohol; lower ketones such as acetone, methyl ethyl ketone and diethyl ketone; ethers such as dimethyl ether and dioxane; amides such as dimethylformaldehyde Kind. One or more organic solvents can be used.
上記溶媒の使用量としては、全単量体の合計１００質量％に対して４０〜２００質量％が好ましい。より好ましくは、４５質量％以上であり、更に好ましくは、５０質量％以上である。また、より好ましくは、１８０質量％以下であり、更に好ましくは、１５０質量％以下である。溶媒の使用量が４０質量％以下であると、得られる重合体の分子量が高くなるおそれがあり、２００質量％を超えると、得られる重合体の濃度が低くなり、溶媒除去が必要となるおそれがある。 As the usage-amount of the said solvent, 40-200 mass% is preferable with respect to a total of 100 mass% of all the monomers. More preferably, it is 45 mass% or more, More preferably, it is 50 mass% or more. Moreover, More preferably, it is 180 mass% or less, More preferably, it is 150 mass% or less. If the amount of the solvent used is 40% by mass or less, the molecular weight of the obtained polymer may be increased, and if it exceeds 200% by mass, the concentration of the obtained polymer may be decreased and the solvent may be required to be removed. There is.
本発明のポリカルボン酸系重合体（組成物）の製造方法においては、過硫酸塩と共に、公知の重合開始剤を使用することができ、公知の重合開始剤としては、例えば、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の過硫酸塩；過酸化水素；２，２’−アゾビス（２−アミジノプロパン）塩酸塩、４，４’−アゾビス−４−シアノパレリン酸、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）等のアゾ系化合物；過酸化ベンゾイル、過酸化ラウロイル、過酢酸、ジ−ｔ−ブチルパーオキサイド、クメンヒドロパーオキサイド等の有機過酸化物等が例示される。これらの重合開始剤は、単独または２種以上を併用して使用しても良い。 In the method for producing the polycarboxylic acid polymer (composition) of the present invention, a known polymerization initiator can be used together with the persulfate, and examples of the known polymerization initiator include sodium persulfate, Persulfates such as potassium persulfate and ammonium persulfate; hydrogen peroxide; 2,2′-azobis (2-amidinopropane) hydrochloride, 4,4′-azobis-4-cyanoparerenic acid, azobisisobutyronitrile, Azo compounds such as 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, peracetic acid, di-t-butyl peroxide, cumene hydroperoxide, etc. An organic peroxide etc. are illustrated. These polymerization initiators may be used alone or in combination of two or more.
本発明のポリカルボン酸系重合体（組成物）の製造方法において、得られるポリカルボン酸系重合体（組成物）の色調や、加熱時の色調を良好にする（着色が少ない）ことができることから、重合開始剤の使用量を少なくすることが好ましい。後述するように、有機アミン存在下で重合反応を行うことにより、重合開始剤の使用量を少なくすることができる傾向にあり、また、ポリカルボン酸系重合体（組成物）の色調が顕著に向上する傾向にある。 In the method for producing a polycarboxylic acid polymer (composition) of the present invention, the color tone of the resulting polycarboxylic acid polymer (composition) and the color tone upon heating can be improved (coloring is small). Therefore, it is preferable to reduce the amount of the polymerization initiator used. As will be described later, by performing the polymerization reaction in the presence of an organic amine, the amount of the polymerization initiator tends to be reduced, and the color tone of the polycarboxylic acid polymer (composition) is remarkable. It tends to improve.
本発明のポリカルボン酸系重合体（組成物）の製造方法において、重合開始剤の使用量を、全単量体（カルボキシル基含有単量体とその他の単量体の合計）１モルに対して０．１ｇ以上、４．０ｇ以下の割合で使用することが好ましく、０．２ｇ以上、３．５ｇ以下使用することがより好ましく、０．３ｇ以上、３．０ｇ以下使用することが特に好ましい。上記範囲にすることにより、得られる重合体（組成物）の洗剤ビルダーとしての性能（よごれ粒子の分散性能等）が良好なものとなると共に、重合体（組成物）の色調が良くなる傾向にある。 In the method for producing a polycarboxylic acid polymer (composition) of the present invention, the amount of polymerization initiator used is 1 mol of all monomers (total of carboxyl group-containing monomers and other monomers). 0.1 g or more and 4.0 g or less, preferably 0.2 g or more and 3.5 g or less, more preferably 0.3 g or more and 3.0 g or less. . By making it in the above range, the performance of the resulting polymer (composition) as a detergent builder (such as the dispersibility of dirt particles) becomes good, and the color tone of the polymer (composition) tends to improve. is there.
本発明のポリカルボン酸系重合体（組成物）は、連鎖移動剤の存在下で重合を行っても良い。使用可能な連鎖移動剤としては、具体的には、メルカプトエタノール、２−メルカプトプロピオン酸、３−メルカプトプロピオン酸、ｎ−ドデシルメルカプタン等のチオール系連鎖移動剤；四塩化炭素、塩化メチレン、ブロモホルム、ブロモトリクロロエタン等の、ハロゲン化物；イソプロパノール、グリセリン等の、第２級アルコール；亜リン酸、次亜リン酸、及びその塩（次亜リン酸ナトリウム、次亜リン酸カリウム等）等；亜硫酸、重亜硫酸塩、亜ジチオン酸塩、メタ重亜硫酸塩、亜硫酸塩、チオ硫酸塩（具体的には、亜硫酸水素ナトリウム、亜硫酸水素カリウム、亜二チオン酸ナトリウム、亜二チオン酸カリウム、メタ重亜硫酸ナトリウム、メタ重亜硫酸カリウム等）等（「重亜硫酸（塩）類」ともいう）；等が挙げられる。上記連鎖移動剤は、単独でまたは２種以上併用して使用しても良い。ただし、本発明のポリカルボン酸系重合体（組成物）を洗剤用途に使用する場合、リンの混入が厳しく制限される場合があるので、洗剤用途に使用する場合にはリンを含む連鎖移動剤の使用を避けることが好ましい。 The polycarboxylic acid polymer (composition) of the present invention may be polymerized in the presence of a chain transfer agent. Specific examples of the chain transfer agent that can be used include thiol chain transfer agents such as mercaptoethanol, 2-mercaptopropionic acid, 3-mercaptopropionic acid, and n-dodecyl mercaptan; carbon tetrachloride, methylene chloride, bromoform, Halogens such as bromotrichloroethane; secondary alcohols such as isopropanol and glycerin; phosphorous acid, hypophosphorous acid, and salts thereof (sodium hypophosphite, potassium hypophosphite, etc.); sulfurous acid, heavy Sulfite, dithionite, metabisulfite, sulfite, thiosulfate (specifically, sodium bisulfite, potassium bisulfite, sodium dithionite, potassium dithionite, sodium metabisulfite, Etc. (also referred to as “bisulfite (salts)”); and the like. The chain transfer agents may be used alone or in combination of two or more. However, when the polycarboxylic acid polymer (composition) of the present invention is used for detergent applications, the incorporation of phosphorus may be severely restricted. Therefore, when used for detergent applications, a chain transfer agent containing phosphorus. Is preferably avoided.
本発明のポリカルボン酸系重合体（組成物）の製造方法において、重合体の主鎖末端にスルホン酸（塩）基を導入できることから、連鎖移動剤として重亜硫酸（塩）類を使用することが好ましい。 In the method for producing a polycarboxylic acid polymer (composition) of the present invention, a sulfonic acid (salt) group can be introduced at the end of the main chain of the polymer, and therefore bisulfurous acid (salt) is used as a chain transfer agent. Is preferred.
本発明のポリカルボン酸系重合体（組成物）の製造方法において、得られるポリカルボン酸系重合体（組成物）の色調や、加熱時の色調を良好にする（着色が少ない）ことができることから、重合開始剤の使用量を少なくすることが好ましい。後述するように、有機アミン存在下で重合反応を行うことにより、重合開始剤の使用量を少なくすることができる傾向にある。
上記連鎖移動剤の使用量は、好ましくは全単量体（カルボキシル基含有単量体とその他の単量体の合計）１モルに対して、連鎖移動剤と上記重合開始剤の合計の使用量が、１５．０ｇ以下であることが好ましく、１０．０ｇ以下であることがより好ましく、５．０ｇ以下であることがさらに好ましく、３．０ｇ以下であることが特に好ましい。一方、連鎖移動剤と上記重合開始剤の合計の使用量の下限としては、全単量体１モルに対して、２．０ｇ以上であることが特に好ましい。上記範囲にすることにより、得られる重合体（組成物）の洗剤ビルダーとしての性能（よごれ粒子の分散性能等）が良好なものとなると共に、重合体（組成物）の色調が良くなる傾向にある。
In the method for producing a polycarboxylic acid polymer (composition) of the present invention, the color tone of the resulting polycarboxylic acid polymer (composition) and the color tone upon heating can be improved (coloring is small). Therefore, it is preferable to reduce the amount of the polymerization initiator used. As will be described later, by using the polymerization reaction in the presence of an organic amine, the amount of the polymerization initiator used tends to be reduced.
The amount of the chain transfer agent used is preferably the total amount of the chain transfer agent and the polymerization initiator used relative to 1 mol of all monomers (the total of carboxyl group-containing monomers and other monomers). Is preferably 15.0 g or less, more preferably 10.0 g or less, even more preferably 5.0 g or less, and particularly preferably 3.0 g or less. On the other hand, the lower limit of the total amount of the chain transfer agent and the polymerization initiator used is particularly preferably 2.0 g or more per 1 mol of all monomers. By making it in the above range, the performance of the resulting polymer (composition) as a detergent builder (such as the dispersibility of dirt particles) becomes good, and the color tone of the polymer (composition) tends to improve. is there.
本発明のポリカルボン酸系重合体（組成物）の製造方法において、反応促進剤として重金属イオンを使用しても良い。本発明において重金属とは、比重が４ｇ／ｃｍ３以上の金属を意味する。上記金属イオンとしては、例えば、鉄、コバルト、マンガン、クロム、モリブデン、タングステン、銅、銀、金、鉛、白金、イリジウム、オスミウム、パラジウム、ロジウム、ルテニウム等が好ましい。これらの重金属は１種又は２種以上を用いることができる。これらの中でも、鉄がより好ましい。上記重金属イオンのイオン価は特に限定されるものではなく、例えば、重金属として鉄が用いられる場合、開始剤における鉄イオンとしては、Ｆｅ２＋であっても、Ｆｅ３＋であってよく、これらが組み合わされていてもよい。
上記重金属イオンは、イオンの形態として含まれるものであれば特に限定されないが、重金属化合物を溶解してなる溶液を用いる方法を用いると、取り扱い性に優れるため好適である。
上記重金属イオンとして鉄を用いる場合、モール塩（Ｆｅ（ＮＨ４）２（ＳＯ４）２・６Ｈ２Ｏ）、硫酸第一鉄・７水和物、塩化第一鉄、塩化第二鉄等の重金属化合物等を用いることが好ましい。また、重金属イオンとしてマンガンを用いる場合、塩化マンガン等を好適に用いることができる。これらの重金属化合物を用いる場合においては、いずれも水溶性の化合物であるため、水溶液の形態として用いることができ、取り扱い性に優れることになる。なお、上記重金属化合物を溶解してなる溶液の溶媒としては、水に限定されるものではない。
In the method for producing a polycarboxylic acid polymer (composition) of the present invention, heavy metal ions may be used as a reaction accelerator. In the present invention, the heavy metal means a metal having a specific gravity of 4 g / cm 3 or more. As said metal ion, iron, cobalt, manganese, chromium, molybdenum, tungsten, copper, silver, gold, lead, platinum, iridium, osmium, palladium, rhodium, ruthenium etc. are preferable, for example. These heavy metals can be used alone or in combination of two or more. Among these, iron is more preferable. The ionic valence of the heavy metal ions is not particularly limited. For example, when iron is used as the heavy metal, the iron ions in the initiator may be Fe 2+ or Fe 3+ , and these may be combined. May be.
The heavy metal ions are not particularly limited as long as they are included in the form of ions. However, it is preferable to use a method using a solution in which a heavy metal compound is dissolved because the handleability is excellent.
When iron is used as the heavy metal ion, the mole salt (Fe (NH 4 ) 2 (SO 4 ) 2 · 6H 2 O), ferrous sulfate · 7 hydrate, ferrous chloride, ferric chloride, etc. It is preferable to use a heavy metal compound or the like. Moreover, when using manganese as a heavy metal ion, manganese chloride etc. can be used suitably. In the case of using these heavy metal compounds, since they are water-soluble compounds, they can be used in the form of an aqueous solution and have excellent handleability. The solvent of the solution obtained by dissolving the heavy metal compound is not limited to water.
上記重金属イオンを使用する場合その使用量は、重合反応完結時における重合反応液の全質量に対して０〜１０ｐｐｍであることが好ましい。重金属イオンの含有量が１０ｐｐｍを超えると、得られる重合体の色調の悪化を来たすおそれがある。
なお、上記重合反応完結時とは、重合反応液中において重合反応が実質的に完了し、所望する重合体が得られた時点を意味する。例えば、重合反応液中において重合された重合体がアルカリ成分で中和される場合には、中和した後の重合反応液の全質量を基準に、重金属イオンの含有量を算出する。２種以上の重金属イオンが含まれる場合には、重金属イオンの総量が上述の範囲であればよい。
When using the said heavy metal ion, it is preferable that the usage-amount is 0-10 ppm with respect to the total mass of the polymerization reaction liquid at the time of polymerization reaction completion. If the content of heavy metal ions exceeds 10 ppm, the color tone of the resulting polymer may be deteriorated.
The time when the polymerization reaction is completed means the time when the polymerization reaction is substantially completed in the polymerization reaction solution and a desired polymer is obtained. For example, when the polymer polymerized in the polymerization reaction solution is neutralized with an alkali component, the content of heavy metal ions is calculated based on the total mass of the polymerization reaction solution after neutralization. When two or more kinds of heavy metal ions are included, the total amount of heavy metal ions may be in the above range.
上記連鎖移動剤、重合開始剤及び反応促進剤の好ましい組み合わせとして、過硫酸塩と重亜硫酸（塩）類、過硫酸塩と重亜硫酸（塩）類と重金属イオン、が例示される。
なお、本発明において、重亜硫酸塩等の無機酸塩における塩とは、金属塩、アンモニウム塩、有機アミン塩を表わし、金属塩としてはナトリウム塩、カリウム塩が好ましい。
Examples of preferable combinations of the chain transfer agent, the polymerization initiator, and the reaction accelerator include persulfates and bisulfites (salts), persulfates, bisulfites (salts), and heavy metal ions.
In the present invention, a salt in an inorganic acid salt such as bisulfite represents a metal salt, an ammonium salt, or an organic amine salt, and a sodium salt or potassium salt is preferable as the metal salt.
本発明のポリカルボン酸系重合体（組成物）の製造方法において、単量体の重合時に有機アミンを存在させておくことが好ましい。有機アミンを存在させておくことにより、重合開始剤や連鎖移動剤の使用量を低減することが可能である。また、有機アミンの存在下で重合反応を行うことにより、得られる重合体（組成物）の色調が顕著に向上する傾向にある。有機アミンとしては、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等のアルカノールアミン；モノエチルアミン、ジエチルアミン、トリエチルアミン等のアルキルアミン；エチレンジアミン、トリエチレンジアミン等のポリアミン等が例示される。有機アミンの中でも、重合体（組成物）の色調が向上することから２級アミン、トリエタノールアミンが特に好ましい。
重合中に存在させる有機アミンは、本発明のポリカルボン酸系重合体（組成物）の製造に使用する有機アミンの一部であっても、全部であっても構わない。例えば重合開始前、又は重合中に、有機アミンの一部を添加して、重合終了後、例えば中和工程で残りの有機アミンを添加するなどしても良い。
本発明のポリカルボン酸系重合体（組成物）の製造方法の重合工程において、単量体を反応容器への添加が終了した時点において、添加したカルボキシル含有単量体１００モル％に対して、有機アミンが３％モル％以上、８モル％以下であることが好ましい。
In the method for producing a polycarboxylic acid polymer (composition) of the present invention, it is preferable that an organic amine is present during the polymerization of the monomer. By using the organic amine, it is possible to reduce the amount of the polymerization initiator and the chain transfer agent used. Moreover, it exists in the tendency for the color tone of the polymer (composition) obtained to improve notably by performing a polymerization reaction in presence of organic amine. Examples of the organic amine include alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; alkylamines such as monoethylamine, diethylamine and triethylamine; polyamines such as ethylenediamine and triethylenediamine. Among organic amines, secondary amines and triethanolamine are particularly preferable because the color tone of the polymer (composition) is improved.
The organic amine present during the polymerization may be a part or all of the organic amine used in the production of the polycarboxylic acid polymer (composition) of the present invention. For example, a part of the organic amine may be added before the polymerization starts or during the polymerization, and the remaining organic amine may be added in the neutralization step after the polymerization is completed.
In the polymerization step of the production method of the polycarboxylic acid polymer (composition) of the present invention, at the time when the addition of the monomer to the reaction vessel is completed, with respect to 100 mol% of the added carboxyl-containing monomer, The organic amine is preferably 3% by mol or more and 8% by mol or less.
上記重合工程において、単量体を反応容器へ添加する方法としては、重合開始前に単量体の一部又は全部を予め反応溶液に添加しておく方法、単量体の全量を重合開始以降に反応容器に添加する方法等が可能であるが、単量体の一部または全部を重合開始以後に反応容器に逐次的（好ましくは連続的）に添加することが好ましい。なお、後述する重合開始時点より前を重合開始前、重合開始時点より後を重合開始後という。
単量体は、予め溶媒に溶解して反応容器に添加しても良い。
In the above polymerization step, as a method of adding the monomer to the reaction vessel, a method in which a part or all of the monomer is previously added to the reaction solution before the start of polymerization, and the entire amount of the monomer is added after the start of polymerization. However, it is preferable to add some or all of the monomers to the reaction vessel sequentially (preferably continuously) after the start of polymerization. In addition, before the polymerization start time mentioned later is called before polymerization start, and after the polymerization start time is called after polymerization start.
The monomer may be previously dissolved in a solvent and added to the reaction vessel.
上記重合工程において、重合開始剤を反応容器へ添加する方法としては、重合開始前に重合開始剤の一部又は全部を予め反応溶液に添加しておく方法、重合開始剤の全量を重合開始以降に反応容器に添加する方法等が可能であるが、重合開始剤の一部または全部を重合開始以後に反応容器に逐次的（好ましくは連続的）に添加することが好ましい。
重合開始剤は、予め溶媒に溶解して反応容器に添加してもよい。重合開始剤として過硫酸塩を使用する場合には、水溶液として添加することが好ましい。
過硫酸塩の添加終了時点が、単量体の添加終了時点以降になることが好ましく、単量体の添加終了時から６０分以内であることがより好ましく、単量体の添加終了時から３０分以内であることが特に好ましい。
In the above polymerization step, as a method of adding a polymerization initiator to the reaction vessel, a method in which a part or all of the polymerization initiator is previously added to the reaction solution before the start of polymerization, and the entire amount of the polymerization initiator after the start of polymerization. However, it is preferable to add part or all of the polymerization initiator to the reaction vessel sequentially (preferably continuously) after the start of polymerization.
The polymerization initiator may be dissolved in a solvent in advance and added to the reaction vessel. When using a persulfate as a polymerization initiator, it is preferably added as an aqueous solution.
The end point of the addition of the persulfate is preferably after the end point of the addition of the monomer, more preferably within 60 minutes from the end of the addition of the monomer, and 30 from the end of the addition of the monomer. Particularly preferred is within minutes.
上記重合工程において、連鎖移動剤を使用する場合、連鎖移動剤を反応容器へ添加する方法としては、重合開始前に連鎖移動剤の一部又は全部を予め反応溶液に添加しておく方法、連鎖移動剤の全量を重合開始以降に反応容器に添加する方法等が可能であるが、連鎖移動剤の一部または全部を重合開始以後に反応容器に逐次的（好ましくは連続的）に添加することが好ましい。
連鎖移動剤は、予め溶媒に溶解して反応容器に添加してもよい。重合開始剤として重亜硫酸（塩）類を使用する場合には、水溶液として添加することが好ましい。
また、重亜硫酸（塩）類を使用する場合、重合初期の分子量は最終分子量に大きく影響する。このため、初期分子量を低下させるために、重合開始より６０分以内、好ましくは３０分以内、より好ましくは１０分以内に重亜硫酸（塩）類ないしその溶液を使用量の５〜２０質量％添加（滴下）するのが望ましい。
単量体、重合開始剤、連鎖移動剤等を逐次的に添加する場合、その添加速度は一定であっても良いが、添加速度を途中で変えても良い。
In the polymerization step, when a chain transfer agent is used, as a method of adding the chain transfer agent to the reaction vessel, a method in which a part or all of the chain transfer agent is added to the reaction solution in advance before the polymerization is started. Although it is possible to add the entire amount of transfer agent to the reaction vessel after the start of polymerization, it is possible to add part or all of the chain transfer agent to the reaction vessel sequentially (preferably continuously) after the start of polymerization. Is preferred.
The chain transfer agent may be previously dissolved in a solvent and added to the reaction vessel. When bisulfite (salt) is used as the polymerization initiator, it is preferably added as an aqueous solution.
When bisulfite (salt) is used, the molecular weight at the initial stage of polymerization greatly affects the final molecular weight. For this reason, in order to reduce the initial molecular weight, the bisulfite (salt) or a solution thereof is added within 5 to 20% by mass of the used amount within 60 minutes, preferably within 30 minutes, more preferably within 10 minutes from the start of polymerization. (Drip) is desirable.
When the monomer, polymerization initiator, chain transfer agent, etc. are added sequentially, the addition rate may be constant, but the addition rate may be changed during the process.
上記重合工程において、有機アミンを使用する場合、有機アミンを反応容器へ添加する方法としては、重合開始前に有機アミンの一部又は全部を予め反応溶液に添加しておく方法、有機アミンの全量を重合開始以降に反応容器に添加する方法等が可能である。有機アミンは反応容器に、有機アミンのみで添加しても良いし、カルボキシル基含有単量体と予め反応（中和反応）させてから添加しても良いし、溶剤に溶解して添加しても良い。 When using an organic amine in the polymerization step, as a method of adding the organic amine to the reaction vessel, a method in which a part or all of the organic amine is previously added to the reaction solution before the start of polymerization, the total amount of the organic amine Or the like can be added to the reaction vessel after the start of polymerization. The organic amine may be added to the reaction vessel only with the organic amine, may be added after reacting with the carboxyl group-containing monomer in advance (neutralization reaction), or dissolved in a solvent and added. Also good.
上記重合工程における重合方法としては、例えば、溶液重合やバルク重合、懸濁重合、乳化重合等の通常用いられる方法で行うことができ、特に限定されるものではないが、溶液重合が好ましい。溶剤を使用する場合には、溶媒は、通常重合開始前に一部又は全量を反応容器内に仕込んでおくことが好ましいが、溶媒の一部を重合開始以後に反応系内に添加（滴下）してもよいし、単量体成分や開始剤等を予め溶媒に溶解させた形で、これらの成分と共に重合反応中に反応系内に添加（滴下）してもよい。 As a polymerization method in the polymerization step, for example, it can be carried out by a commonly used method such as solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization and the like, and is not particularly limited, but solution polymerization is preferable. When a solvent is used, it is preferable that a part or all of the solvent is usually charged in the reaction vessel before the start of polymerization, but a part of the solvent is added to the reaction system after the start of polymerization (dropping). Alternatively, a monomer component, an initiator, or the like may be added (dropped) into the reaction system during the polymerization reaction together with these components in a form in which the monomer component or initiator is dissolved in advance.
上記重合工程において、重合温度としては、通常、０℃以上であることが好ましく、また、１５０℃以下であることが好ましい。より好ましくは、４０℃以上であり、更に好ましくは、６０℃以上であり、特に好ましくは、８０℃以上である。また、より好ましくは、１２０℃以下であり、更に好ましくは、１１０℃以下である。特に、重亜硫酸（塩）類を用いる場合には、共重合温度は、通常、６０℃〜９５℃、好ましくは７０℃〜９５℃、さらに好ましくは、８０℃〜９５℃である。この際、６０℃以下では、重亜硫酸（塩）類由来の不純物が多量に生成するおそれがある。逆に、９５℃を越えると、有毒な亜硫酸ガスが放出されるおそれがある。
上記重合工程において、重合温度は常にほぼ一定に保持する必要はなく、例えば、室温から重合を開始し、適当な昇温時間又は昇温速度で設定温度まで昇温し、その後、設定温度を保持するようにしてもよいし、単量体成分や開始剤等の滴下方法に応じて、重合反応中に経時的に温度変動（昇温又は降温）させてもよい。
In the polymerization step, the polymerization temperature is usually preferably 0 ° C. or higher and preferably 150 ° C. or lower. More preferably, it is 40 degreeC or more, More preferably, it is 60 degreeC or more, Most preferably, it is 80 degreeC or more. Moreover, More preferably, it is 120 degrees C or less, More preferably, it is 110 degrees C or less. In particular, when bisulfurous acid (salt) is used, the copolymerization temperature is usually 60 ° C to 95 ° C, preferably 70 ° C to 95 ° C, and more preferably 80 ° C to 95 ° C. At this time, at 60 ° C. or less, there is a possibility that a large amount of impurities derived from bisulfurous acid (salts) is generated. On the contrary, when it exceeds 95 ° C., toxic sulfurous acid gas may be released.
In the above polymerization step, the polymerization temperature does not always need to be kept almost constant. For example, polymerization is started from room temperature, the temperature is increased to a set temperature at an appropriate temperature increase time or rate, and then the set temperature is maintained. Depending on the dropping method of the monomer component, the initiator, etc., the temperature may be changed over time (temperature increase or decrease) during the polymerization reaction.
本発明のポリカルボン酸系重合体の製造方法において、重合時間としては、３０〜３６０分であることが好ましい。より好ましくは、６０〜２４０分であり、更に好ましくは、１２０〜１８０分である。
なお、本発明において「重合時間」とは、回文式（バッチ式）重合方法において、単量体の一部または全部を反応器（反応釜）に添加しながら重合する場合には、最初に重合開始剤の一部または全部と、単量体の一部または全部が反応器に添加された時点（重合開始時点という）から、単量体の全量が反応器に添加された時点（重合終了時点という）までをいう。また、回文式（バッチ式）重合方法において、単量体の全量を予め反応器に添加して（初期仕込みという）、重合開始剤の一部または全部を反応器（反応釜）に添加しながら重合する場合には、最初に重合開始剤の一部または全部と、単量体の全部が反応器に添加された時点から、重合開始剤の全量が反応器に添加された時点までである。また、回文式（バッチ式）重合方法において、単量体の全量と、重合開始剤の全量とを予め反応器に添加して、加熱等の手段により重合を行なう場合には、発熱（重合熱の発生）が見られる時間をいう。また、連続式で重合する場合には、反応器に滞留している時間をいう。
In the method for producing a polycarboxylic acid polymer of the present invention, the polymerization time is preferably 30 to 360 minutes. More preferably, it is 60-240 minutes, More preferably, it is 120-180 minutes.
In the present invention, the “polymerization time” refers to the first time when polymerization is carried out while adding a part or all of the monomer to the reactor (reaction kettle) in the palindromic (batch type) polymerization method. From the time when a part or all of the polymerization initiator and a part or all of the monomer are added to the reactor (referred to as polymerization start time) to the time when the whole amount of monomer is added to the reactor (polymerization completed) Until the time). In addition, in the palindromic (batch type) polymerization method, the entire amount of monomer is added to the reactor in advance (referred to as initial charge), and a part or all of the polymerization initiator is added to the reactor (reaction kettle). In the case of polymerization, it is from the time when all or part of the polymerization initiator and all the monomers are first added to the reactor to the time when the entire amount of the polymerization initiator is added to the reactor. . In addition, in the palindromic (batch type) polymerization method, when the total amount of the monomer and the total amount of the polymerization initiator are added to the reactor in advance and the polymerization is performed by means such as heating, an exothermic (polymerization) This is the time when heat generation is observed. Moreover, when superposing | polymerizing by a continuous type, the time which has stayed in the reactor is said.
上記重合工程における反応系内の圧力としては、常圧（大気圧）下、減圧下、加圧下の何れであってもよいが、得られる共重合体の分子量の点で、常圧下、又は、反応系内を密閉し、加圧下で行うのが好ましい。また、加圧装置や減圧装置、耐圧性の反応容器や配管等の設備の点で、常圧（大気圧）下で行うのが好ましい。反応系内の雰囲気としては、空気雰囲気でもよいが、不活性雰囲気とするのが好ましく、例えば、重合開始前に系内を窒素等の不活性ガスで置換することが好ましい。 The pressure in the reaction system in the polymerization step may be any of normal pressure (atmospheric pressure), reduced pressure, and increased pressure, but in terms of the molecular weight of the resulting copolymer, The reaction system is preferably sealed and the reaction is carried out under pressure. Moreover, it is preferable to carry out under a normal pressure (atmospheric pressure) at the point of equipment, such as a pressurization apparatus, a pressure reduction apparatus, a pressure-resistant reaction container, and piping. The atmosphere in the reaction system may be an air atmosphere, but is preferably an inert atmosphere. For example, the inside of the system is preferably replaced with an inert gas such as nitrogen before the start of polymerization.
上記重合工程における重合中のｐＨは、酸性が好ましい。酸性条件下で行うことによって、重合反応系の水溶液の粘度の上昇を抑制し、重合体を良好に製造することができる。また、高濃度の条件下で重合反応を進行させることができるので、製造効率を大幅に上昇することができ、最終固形分濃度が４０％以上の高濃度重合とすることができる。上記酸性条件としては、重合中の反応溶液の２５℃でのｐＨが１〜６であることが好ましく、より好ましくは５以下であり、更に好ましくは３以下である。 The pH during the polymerization in the polymerization step is preferably acidic. By carrying out the reaction under acidic conditions, an increase in the viscosity of the aqueous solution in the polymerization reaction system can be suppressed, and the polymer can be produced favorably. Further, since the polymerization reaction can proceed under high concentration conditions, the production efficiency can be greatly increased, and high concentration polymerization with a final solid content concentration of 40% or more can be achieved. As said acidic conditions, it is preferable that pH at 25 degreeC of the reaction solution in superposition | polymerization is 1-6, More preferably, it is 5 or less, More preferably, it is 3 or less.
上記重合工程において、重合を行う際の単量体の中和率は、重合開始剤等によって適宜変更できる。例えば、過硫酸塩と重亜硫酸（塩）類とを併用する場合は、単量体の中和率を３〜６０モル％として単量体成分の共重合を行うことが好ましい。上記単量体の中和率は、反応液に含まれる単量体と単量体に由来する構造単位のカルボキシル基の全モル数を１００モル％としたときに、塩を形成している単量体と塩を形成している単量体に由来する構造単位のカルボキシル基の割合（モル％）で表される。単量体の中和率を上記範囲にすることにより、重合率が向上したり、重合体の分子量を好ましい範囲に制御することが容易になる傾向にある。より好ましくは、５０モル％以下であり、更に好ましくは、４０モル％以下、特に好ましくは、３０モル％以下であり、より特に好ましくは、２０モル％以下であり、最も好ましくは、１０モル％以下である。 In the polymerization step, the neutralization rate of the monomer during the polymerization can be appropriately changed depending on the polymerization initiator or the like. For example, when a persulfate and a bisulfite (salt) are used in combination, it is preferable to carry out the copolymerization of the monomer components with the monomer neutralization rate of 3 to 60 mol%. The neutralization rate of the monomer is defined as a unit that forms a salt when the total number of moles of the monomer contained in the reaction solution and the carboxyl group of the structural unit derived from the monomer is 100 mol%. It is represented by the ratio (mol%) of the carboxyl group of the structural unit derived from the monomer that forms a salt with the monomer. By setting the neutralization rate of the monomer within the above range, the polymerization rate tends to be improved, and the molecular weight of the polymer tends to be easily controlled within a preferable range. More preferably, it is 50 mol% or less, more preferably 40 mol% or less, particularly preferably 30 mol% or less, more particularly preferably 20 mol% or less, and most preferably 10 mol%. It is as follows.
本発明の製造方法は、上記重合工程を必須として含むことになる。その他、熟成工程、中和工程、精製工程等を含んでいても良い。
例えば、連鎖移動剤として重亜硫酸塩を使用する場合に、過酸化水素などの過酸化物を添加して残存する重亜硫酸塩を分解する工程を含んでいても良い。該工程を含むことにより、本発明のポリカルボン酸系重合体（組成物）を酸性条件下においたり、加熱したりした場合に亜硫酸ガスが発生することを抑制することが可能となる。
中和工程を含む場合、中和工程においては、中和剤として有機アミンを使用しても良い。有機アミンで中和する場合の中和温度としては、０〜１００℃であることが好ましい。
［本発明のポリカルボン酸系重合体（組成物）の用途］
上記ポリカルボン酸系重合体（または重合体組成物）は、洗剤組成物への添加剤（洗剤ビルダー等）、スケール防止剤等の水処理剤、繊維処理剤、分散剤、脱墨剤、金属イオン封止剤、増粘剤、有機繊維・無機繊維のバインダー、粉体のバインダー、乳化剤、スキンケア剤、ヘアケア剤等として用いることができる。
The production method of the present invention includes the above polymerization step as an essential step. In addition, an aging step, a neutralization step, a purification step, and the like may be included.
For example, when bisulfite is used as the chain transfer agent, a step of adding a peroxide such as hydrogen peroxide to decompose the remaining bisulfite may be included. By including this step, it is possible to suppress the generation of sulfurous acid gas when the polycarboxylic acid polymer (composition) of the present invention is placed under acidic conditions or heated.
When a neutralization step is included, an organic amine may be used as a neutralizing agent in the neutralization step. When neutralizing with an organic amine, the neutralization temperature is preferably 0 to 100 ° C.
[Use of polycarboxylic acid polymer (composition) of the present invention]
The polycarboxylic acid polymer (or polymer composition) includes additives for detergent compositions (detergent builders, etc.), water treatment agents such as scale inhibitors, fiber treatment agents, dispersants, deinking agents, metals It can be used as an ion sealing agent, thickener, organic fiber / inorganic fiber binder, powder binder, emulsifier, skin care agent, hair care agent and the like.
＜洗剤ビルダー＞
本発明のポリカルボン酸系重合体（または重合体組成物）は、洗剤ビルダーとして用いられうる。洗剤ビルダーとしては、衣料用、食器用、住居用、毛髪用、身体用、歯磨き用、及び自動車用など、様々な用途の洗剤に添加されて使用されうる。
すなわち、本発明のポリカルボン酸系重合体（または重合体組成物）は、洗剤組成物にも添加しうる。上記洗剤組成物の概念には、家庭用洗剤組成物、繊維工業その他の工業用洗剤組成物、硬質表面洗浄剤組成物等が含まれ、さらに例えば漂白洗剤組成物等の洗剤組成物に含まれる特定の成分の働きを高めた洗剤組成物も含まれる。
洗剤組成物における本発明のポリカルボン酸系重合体の含有量は特に制限されない。ただし、優れたビルダー性能を発揮しうるという観点からは、本発明のポリカルボン酸系重合体の含有量は、洗剤組成物の全量に対して、好ましくは０．１〜１５質量％であり、より好ましくは０．３〜１０質量％であり、さらに好ましくは０．５〜５質量％である。
<Detergent Builder>
The polycarboxylic acid polymer (or polymer composition) of the present invention can be used as a detergent builder. As a detergent builder, it can be used by adding to detergents for various uses such as clothing, tableware, residential, hair, body, toothpaste, and automobile.
That is, the polycarboxylic acid polymer (or polymer composition) of the present invention can be added to a detergent composition. The concept of the detergent composition includes household detergent compositions, textile industry and other industrial detergent compositions, hard surface cleaner compositions, and the like, and further included in detergent compositions such as bleach detergent compositions. Also included are detergent compositions that enhance the function of certain ingredients.
The content of the polycarboxylic acid polymer of the present invention in the detergent composition is not particularly limited. However, from the viewpoint of exhibiting excellent builder performance, the content of the polycarboxylic acid polymer of the present invention is preferably 0.1 to 15% by mass relative to the total amount of the detergent composition, More preferably, it is 0.3-10 mass%, More preferably, it is 0.5-5 mass%.
洗剤用途で用いられる洗剤組成物には、通常、洗剤に用いられる界面活性剤や添加剤が含まれる。これらの界面活性剤や添加剤の具体的な形態は特に制限されず、洗剤分野において従来公知の知見が適宜参照されうる。また、上記洗剤組成物は、粉末洗剤組成物の場合に特に好ましいが、液体洗剤組成物である場合にも使用することができる。 Detergent compositions used in detergent applications usually include surfactants and additives used in detergents. Specific forms of these surfactants and additives are not particularly limited, and conventionally known knowledge can be appropriately referred to in the detergent field. The detergent composition is particularly preferred in the case of a powder detergent composition, but can also be used in the case of a liquid detergent composition.
界面活性剤は、アニオン性界面活性剤、ノニオン性界面活性剤、カチオン性界面活性剤および両性界面活性剤からなる群から選択される１種または２種以上である。２種以上が併用される場合、アニオン性界面活性剤とノニオン性界面活性剤との合計量は、界面活性剤の全量に対して５０質量％以上であることが好ましく、より好ましくは６０質量％以上であり、さらに好ましくは７０質量％以上であり、特に好ましくは８０質量％以上である。
界面活性剤の配合割合は、洗剤組成物の全量に対して１０〜７０質量％であることが好ましく、より好ましくは１５〜６０質量％である。界面活性剤の配合割合が少なすぎると、十分な洗浄力を発揮できなくなる虞がある。
上記界面活性剤として具体的には、アニオン性界面活性剤としては、アルキルベンゼンスルホン酸塩、アルキル硫酸塩等；ノニオン性界面活性剤としては、ポリオキシアルキレンアルキルエーテル、ポリオキエチレンアルキルフェニルエーテル等；カチオン性界面活性剤としては、第４級アンモニウム塩等；両性界面活性剤としては、カルボキシル型両性界面活性剤、スルホベタイン型両性界面活性剤等；が例示される。
The surfactant is one or more selected from the group consisting of an anionic surfactant, a nonionic surfactant, a cationic surfactant and an amphoteric surfactant. When two or more kinds are used in combination, the total amount of the anionic surfactant and the nonionic surfactant is preferably 50% by mass or more, more preferably 60% by mass with respect to the total amount of the surfactant. It is above, More preferably, it is 70 mass% or more, Most preferably, it is 80 mass% or more.
It is preferable that the compounding ratio of surfactant is 10-70 mass% with respect to the whole quantity of a detergent composition, More preferably, it is 15-60 mass%. When the blending ratio of the surfactant is too small, there is a possibility that sufficient detergency cannot be exhibited.
Specific examples of the surfactant include alkylbenzene sulfonates and alkyl sulfates as anionic surfactants; polyoxyalkylene alkyl ethers, polyoxyethylene alkylphenyl ethers and the like as nonionic surfactants; Examples of cationic surfactants include quaternary ammonium salts; examples of amphoteric surfactants include carboxyl-type amphoteric surfactants and sulfobetaine-type amphoteric surfactants.
本発明の洗剤組成物は、本発明のポリカルボン酸系重合体、界面活性剤以外の添加剤（その他の添加剤）として、炭酸塩、炭酸水素塩、珪酸（塩）等のアルカリビルダー；トリポリリン酸（塩）、クエン酸（塩）、アクリル酸−マレイン酸共重合体（塩）、エチレンジアミンテトラ酢酸（塩）、ボウ硝、ゼオライト等のキレートビルダー；カルボキシメチルセルロース（塩）等の汚染物質の再沈着を防止するための再付着防止剤；ベンゾトリアゾールやエチレン−チオ尿素等の汚れ抑制剤；ソイルリリース剤；ポリビニルピロリドン等の色移り防止剤；柔軟剤；ｐＨ調節のためのアルカリ性物質；香料；可溶化剤；蛍光剤；着色剤；起泡剤；泡安定剤；つや出し剤；殺菌剤；漂白剤；漂白助剤；酵素；染料；溶媒等を添加しても良い。上記その他の添加剤における塩としては、金属塩、アンモニウム塩、有機アミン塩が例示される。
上記その他の添加剤の合計の配合割合は、洗浄剤組成物１００質量％に対して１５〜８９．９質量％が好ましく、３０〜８４．７質量％がより好ましい。
本発明の洗剤組成物が粉末洗剤組成物の場合には、ゼオライトを配合することが好ましい。
本発明の洗剤組成物が液体洗剤組成物の場合には、水を液体洗剤組成物の全量に対して０．１〜７５質量％含むことが好ましく、１．５〜５０質量％含むことがより好ましい。
The detergent composition of the present invention comprises an alkali builder such as carbonate, hydrogen carbonate, silicic acid (salt) as an additive (other additives) other than the polycarboxylic acid polymer and surfactant of the present invention; Chelate builders such as acid (salt), citric acid (salt), acrylic acid-maleic acid copolymer (salt), ethylenediaminetetraacetic acid (salt), bow glass, zeolite, etc .; Anti-redeposition agent for preventing deposition; Stain inhibitor such as benzotriazole and ethylene-thiourea; Soil release agent; Color transfer inhibitor such as polyvinylpyrrolidone; Softener; Alkaline substance for pH adjustment; Solubilizer; fluorescent agent; coloring agent; foaming agent; foam stabilizer; glossing agent; bactericidal agent; bleaching agent; bleaching aid; enzyme; dye; Examples of the salt in the other additives include metal salts, ammonium salts, and organic amine salts.
15-89.9 mass% is preferable with respect to 100 mass% of cleaning composition, and, as for the total mixture ratio of the said other additive, 30-84.7 mass% is more preferable.
When the detergent composition of the present invention is a powder detergent composition, it is preferable to blend zeolite.
When the detergent composition of the present invention is a liquid detergent composition, water is preferably contained in an amount of 0.1 to 75% by mass, more preferably 1.5 to 50% by mass, based on the total amount of the liquid detergent composition. preferable.
＜無機顔料分散剤＞
本発明のポリカルボン酸系重合体（または重合体組成物）は、無機顔料分散剤に用いることができる。該無機顔料分散剤には、必要に応じて、他の配合剤として、縮合リン酸およびその塩、ホスホン酸およびその塩、ポリビニルアルコールを用いても良い。
上記無機顔料分散剤中における、本発明のポリカルボン酸系重合体の含有量は、無機顔料分散剤全体に対して、好ましくは５〜１００重量％である。また性能、効果に影響しない範囲で、任意の適切な水溶性重合体を含んでいてもよい。
上記無機顔料分散剤は、紙コーティングに用いられる重質ないしは軽質炭酸カルシウム、クレイの無機顔料の分散剤として良好な性能を発揮し得る。例えば、無機顔料分散剤を無機顔料に少量添加して水中に分散することにより、低粘度でしかも高流動性を有し、かつ、それらの性能の経日安定性が良好な、高濃度炭酸カルシウムスラリーのような高濃度無機顔料スラリーを製造することができる。
上記無機顔料分散剤を無機顔料の分散剤として用いる場合、該無機顔料分散剤の使用量は、無機顔料１００重量部に対して、０．０５〜２．０重量部が好ましい。該無機顔料分散剤の使用量が上記範囲内にあることによって、十分な分散効果を得ることが可能となり、添加量に見合った効果を得ることが可能となり、経済的にも有利となり得る。
<Inorganic pigment dispersant>
The polycarboxylic acid polymer (or polymer composition) of the present invention can be used as an inorganic pigment dispersant. If necessary, the inorganic pigment dispersant may contain condensed phosphoric acid and its salt, phosphonic acid and its salt, and polyvinyl alcohol as other compounding agents.
The content of the polycarboxylic acid polymer of the present invention in the inorganic pigment dispersant is preferably 5 to 100% by weight with respect to the whole inorganic pigment dispersant. Further, any appropriate water-soluble polymer may be included as long as it does not affect the performance and effect.
The inorganic pigment dispersant can exhibit good performance as a dispersant for heavy or light calcium carbonate or clay inorganic pigment used in paper coating. For example, by adding a small amount of an inorganic pigment dispersant to an inorganic pigment and dispersing it in water, high concentration calcium carbonate having low viscosity and high fluidity and good aging stability of their performance. High concentration inorganic pigment slurries such as slurries can be produced.
When the inorganic pigment dispersant is used as a dispersant for an inorganic pigment, the amount of the inorganic pigment dispersant used is preferably 0.05 to 2.0 parts by weight with respect to 100 parts by weight of the inorganic pigment. When the amount of the inorganic pigment dispersant used is within the above range, a sufficient dispersion effect can be obtained, and an effect commensurate with the addition amount can be obtained, which can be economically advantageous.
以下に実施例を掲げて本発明を更に詳細に説明するが、本発明はこれらの実施例のみに限定されるものではない。なお、特に断りのない限り、「部」は「質量部」を、「％」は「質量％」を意味するものとする。
また、本発明のポリカルボン酸系重合体の重量平均分子量、吸湿率等は、下記方法に従って測定した。
The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by mass” and “%” means “% by mass”.
Moreover, the weight average molecular weight, moisture absorption rate, etc. of the polycarboxylic acid polymer of the present invention were measured according to the following methods.
＜重量平均分子量の測定条件＞
装置：日立社製Ｌ−７０００シリーズ
検出器：ＲＩ
カラム：昭和電工社製 ＳＨＯＤＥＸ Ａｓａｈｉｐａｋ ＧＦ−３１０−ＨＱ， ＧＦ−７１０−ＨＱ， ＧＦ−１Ｇ ７Ｂ
カラム温度：４０℃
流速：０．５ｍｌ／ｍｉｎ．
検量線：創和科学株式会社製 ＰＯＬＹＡＣＲＹＬＩＣ ＡＣＩＤ ＳＴＡＮＤＡＲＤ
溶離液：０．１Ｎ酢酸ナトリウム／アセトニトリル＝３／１（質量比）．
＜重合体組成物の固形分測定方法＞
窒素雰囲気下、１３０℃に加熱したオーブンで重合体組成物（重合体組成物１．０ｇ＋水３．０ｇ）を１時間放置して乾燥処理した。乾燥前後の重量変化から、固形分（％）と、揮発成分（％）を算出した。
<Measurement conditions of weight average molecular weight>
Device: Hitachi L-7000 Series Detector: RI
Column: SHODEX Asahipak GF-310-HQ, GF-710-HQ, GF-1G 7B manufactured by Showa Denko KK
Column temperature: 40 ° C
Flow rate: 0.5 ml / min.
Calibration curve: POLYACRYLIC ACID STANDARD made by Soka Science Co., Ltd.
Eluent: 0.1N sodium acetate / acetonitrile = 3/1 (mass ratio).
<Method for measuring solid content of polymer composition>
In a nitrogen atmosphere, the polymer composition (polymer composition 1.0 g + water 3.0 g) was left to dry for 1 hour in an oven heated to 130 ° C. From the weight change before and after drying, the solid content (%) and the volatile component (%) were calculated.
＜末端スルホン酸基の測定＞
ｐＨを１に調整した重合体（水溶液）を室温で減圧乾燥して水を留去した後、重水を溶媒に用いて１ＨＮＭＲ測定を行い、ポリマー主鎖末端にスルホン酸基が導入されたことに由来する２．７ｐｐｍのピークの有無により確認した。
<Measurement of terminal sulfonic acid group>
After the polymer (aqueous solution) adjusted to pH 1 was dried under reduced pressure at room temperature and water was distilled off, 1 HNMR measurement was performed using heavy water as a solvent, and a sulfonic acid group was introduced at the end of the polymer main chain. This was confirmed by the presence or absence of a peak at 2.7 ppm derived from the above.
＜重合体の色調の分析＞
実施例および比較例で製造したポリカルボン酸系重合体水溶液の固形分濃度を４０％に調整し、日本電色工業社製の測色色差計ＳＥ２０００型を用いて、ｂ値を透過率にて測定した。ｂ値が低いほど、色調が良好であることを表わす。
<Analysis of polymer color tone>
The solid content concentration of the polycarboxylic acid polymer aqueous solution produced in the examples and comparative examples was adjusted to 40%, and the b value was determined by the transmittance using a colorimetric color difference meter SE2000 manufactured by Nippon Denshoku Industries Co., Ltd. It was measured. The lower the b value, the better the color tone.
＜実施例１＞
還流冷却器、撹拌機（パドル翼）、温度計を備えた容量５リットルのＳＵＳ製セパラブルフラスコに、純水３５２．８ｇを仕込み（初期仕込）、撹拌下、８５℃まで昇温した。次いで撹拌下、約８５℃一定状態の重合反応系中に８０質量％アクリル酸水溶液（以下「８０％ＡＡ」と称する）９００ｇ（すなわち１０ｍｏｌ）、１５質量％過硫酸ナトリウム水溶液（以下「１５％ＮａＰＳ」と称する）１２０ｇ（対単量体投入量に換算すると１．８ｇ／ｍｏｌ）、３５質量％重亜硫酸ナトリウム水溶液（以下、「３５％ＳＢＳ」とも称する）１４８．６ｇ（対単量体投入量に換算すると５．２ｇ／ｍｏｌ）、をそれぞれ別個の滴下ノズルより滴下した。それぞれの滴下時間は、８０％ＡＡを１８０分間、１５％ＮａＰＳを１９０分間、３５％ＳＢＳを１７５分間とした。また、それぞれの滴下時間の間、各成分の滴下速度は一定とし、連続的に滴下した。滴下終了後、さらに３０分間に渡って反応溶液を８５℃に保持（熟成）した。その後、反応溶液を放冷しながら８０質量％ジエタノールアミン水溶液（以下「８０％ＤＥＡ」と称する）３５０．８ｇ（ＡＡ中和率２６．７％分）を撹拌下、反応溶液に徐々に滴下して中和を行い、さらに純水２７０gを加え十分に攪拌を行った。以上のようにして、本発明のポリカルボン酸系重合体（１）の水溶液を得た。該水溶液の個形分値は５０．０％であった。ポリカルボン酸系重合体（１）の重量平均分子量（Ｍｗ）は７９００であった。
<Example 1>
352.8 g of pure water was charged into an SUS separable flask having a capacity of 5 liters equipped with a reflux condenser, a stirrer (paddle blade), and a thermometer (initial charge), and the temperature was raised to 85 ° C. with stirring. Next, 900 g (namely, 10 mol) of an 80% by weight acrylic acid aqueous solution (hereinafter referred to as “80% AA”), 15% by weight aqueous sodium persulfate (hereinafter referred to as “15% NaPS”) in a polymerization reaction system at a constant temperature of about 85 ° C. with stirring. ) 120 g (1.8 g / mol in terms of monomer input), 358.6% by weight sodium bisulfite aqueous solution (hereinafter also referred to as “35% SBS”) 148.6 g (monomer input) Converted to 5.2 g / mol) was dropped from separate dropping nozzles. The dropping time was 80% AA for 180 minutes, 15% NaPS for 190 minutes, and 35% SBS for 175 minutes. Further, during each dropping time, the dropping rate of each component was kept constant, and dropping was continuously performed. After completion of the dropwise addition, the reaction solution was kept at 85 ° C. (aged) for another 30 minutes. Thereafter, 350.8 g of an 80% by mass diethanolamine aqueous solution (hereinafter referred to as “80% DEA”) (AA neutralization rate of 26.7%) was gradually added dropwise to the reaction solution with stirring while the reaction solution was allowed to cool. Neutralization was performed, and 270 g of pure water was further added and stirred sufficiently. As described above, an aqueous solution of the polycarboxylic acid polymer (1) of the present invention was obtained. The individual fraction value of the aqueous solution was 50.0%. The weight average molecular weight (Mw) of the polycarboxylic acid polymer (1) was 7900.
＜実施例２＞
還流冷却器、撹拌機（パドル翼）、温度計を備えた容量５リットルのＳＵＳ製セパラブルフラスコに、純水３９８．８ｇを仕込み（初期仕込）、撹拌下、８５℃まで昇温した。次いで撹拌下、約８５℃一定状態の重合反応系中に８０質量％アクリル酸水溶液９００ｇ（すなわち１０ｍｏｌ）、１５質量％過硫酸ナトリウム水溶液１２０ｇ（対単量体投入量に換算すると１．８ｇ／ｍｏｌ）、３５質量％重亜硫酸ナトリウム水溶液７１．４ｇ（対単量体投入量に換算すると２．５ｇ／ｍｏｌ）、をそれぞれ別個の滴下ノズルより滴下した。それぞれの滴下時間は、８０％ＡＡを１８０分間、１５％ＮａＰＳを１９０分間、３５％ＳＢＳを１７５分間とした。また、それぞれの滴下時間の間、各成分の滴下速度は一定とし、連続的に滴下した。滴下終了後、さらに３０分間に渡って反応溶液を８５℃に保持（熟成）した。その後、反応溶液を放冷しながら８０質量％ジエタノールアミン水溶液３５０．８ｇ（ＡＡ中和率２６．７％分）を撹拌下、反応溶液に徐々に滴下して中和を行い、さらに純水２４５gを加え十分に攪拌を行った。以上のようにして、本発明のポリカルボン酸系重合体（２）の水溶液を得た。該水溶液の個形分値は５０．０％であった。ポリカルボン酸系重合体（２）の重量平均分子量（Ｍｗ）は２３０００であった。
<Example 2>
A SUS separable flask having a capacity of 5 liters equipped with a reflux condenser, a stirrer (paddle blade), and a thermometer was charged with 398.8 g of pure water (initial charge), and heated to 85 ° C. with stirring. Next, under stirring, in an polymerization reaction system at a constant state of about 85 ° C., 900 g of an 80% by mass acrylic acid aqueous solution (that is, 10 mol) and 120 g of 15% by mass aqueous sodium persulfate aqueous solution (1.8 g / mol in terms of monomer input). ), 71.4 g of a 35 mass% sodium bisulfite aqueous solution (2.5 g / mol when converted to the amount of monomer added) was dropped from separate dropping nozzles. The dropping time was 80% AA for 180 minutes, 15% NaPS for 190 minutes, and 35% SBS for 175 minutes. Further, during each dropping time, the dropping rate of each component was kept constant, and dropping was continuously performed. After completion of the dropwise addition, the reaction solution was kept at 85 ° C. (aged) for another 30 minutes. Thereafter, while the reaction solution was allowed to cool, 350.8 g of an 80% by mass diethanolamine aqueous solution (AA neutralization rate of 26.7%) was stirred and gradually dropped into the reaction solution to neutralize, and 245 g of pure water was further added. In addition, sufficient stirring was performed. As described above, an aqueous solution of the polycarboxylic acid polymer (2) of the present invention was obtained. The individual fraction value of the aqueous solution was 50.0%. The weight average molecular weight (Mw) of the polycarboxylic acid polymer (2) was 23000.
＜実施例３＞
還流冷却器、撹拌機（パドル翼）、温度計を備えた容量５リットルのＳＵＳ製セパラブルフラスコに、純水１０４７．３ｇを仕込み（初期仕込）、撹拌下、８５℃まで昇温した。次いで撹拌下、約８５℃一定状態の重合反応系中に８０質量％アクリル酸水溶液９００ｇ（すなわち１０ｍｏｌ）、１５質量％過硫酸ナトリウム水溶液３３．４ｇ（対単量体投入量に換算すると０．５ｇ／ｍｏｌ）、３５質量％重亜硫酸ナトリウム水溶液５７．１ｇ（対単量体投入量に換算すると２．０ｇ／ｍｏｌ）、をそれぞれ別個の滴下ノズルより滴下した。それぞれの滴下時間は、８０％ＡＡを１８０分間、１５％ＮａＰＳを１９０分間、３５％ＳＢＳを１７５分間とした。また、それぞれの滴下時間の間、各成分の滴下速度は一定とし、連続的に滴下した。滴下終了後、さらに３０分間に渡って反応溶液を８５℃に保持（熟成）した。その後、反応溶液を放冷しながら８０質量％ジエタノールアミン水溶液３５０．８ｇ（ＡＡ中和率２６．７％分）を撹拌下、反応溶液に徐々に滴下して中和を行い、さらに純水１７５．３gを加え十分に攪拌を行った。以上のようにして、本発明のポリカルボン酸系重合体（３）の水溶液を得た。該水溶液の個形分値は４０．０％であった。ポリカルボン酸系重合体（３）の重量平均分子量（Ｍｗ）は３６０００であった。
<Example 3>
A SUS separable flask having a capacity of 5 liters equipped with a reflux condenser, a stirrer (paddle blade), and a thermometer was charged with 1047.3 g of pure water (initial charge) and heated to 85 ° C. with stirring. Next, under stirring, in a polymerization reaction system at a constant temperature of about 85 ° C., an 80% by weight acrylic acid aqueous solution 900 g (that is, 10 mol) and a 15% by weight sodium persulfate aqueous solution 33.4 g (0.5 g in terms of monomer charge). / Mol), and 57.1 g of a 35 mass% sodium bisulfite aqueous solution (2.0 g / mol when converted to the amount of monomer charged) were dropped from separate dropping nozzles. The dropping time was 80% AA for 180 minutes, 15% NaPS for 190 minutes, and 35% SBS for 175 minutes. Further, during each dropping time, the dropping rate of each component was kept constant, and dropping was continuously performed. After completion of the dropwise addition, the reaction solution was kept at 85 ° C. (aged) for another 30 minutes. Thereafter, while the reaction solution was allowed to cool, 350.8 g of an 80% by mass diethanolamine aqueous solution (AA neutralization rate: 26.7% min) was gradually added dropwise to the reaction solution with stirring, followed by neutralization. 3 g was added and sufficiently stirred. As described above, an aqueous solution of the polycarboxylic acid polymer (3) of the present invention was obtained. The solid fraction value of the aqueous solution was 40.0%. The weight average molecular weight (Mw) of the polycarboxylic acid polymer (3) was 36000.
＜実施例４＞
還流冷却器、撹拌機（パドル翼）、温度計を備えた容量５リットルのＳＵＳ製セパラブルフラスコに、純水４２６．９ｇとモール塩０．０１６４ｇを仕込み（初期仕込）、撹拌下、８５℃まで昇温した。次いで撹拌下、約８５℃一定状態の重合反応系中に８０質量％アクリル酸水溶液９００ｇ（すなわち１０ｍｏｌ）、１５質量％過硫酸アンモニウム水溶液（以下「１５％ＡＰＳ」と称する）３３．３ｇ（対単量体投入量に換算すると０．５ｇ／ｍｏｌ）、３５質量％重亜硫酸ナトリウム水溶液５４．３ｇ（対単量体投入量に換算すると１．９ｇ／ｍｏｌ）、をそれぞれ別個の滴下ノズルより滴下した。それぞれの滴下時間は、８０％ＡＡを１８０分間、１５％ＮａＰＳを１９０分間、３５％ＳＢＳを１７５分間とした。また、それぞれの滴下時間の間、各成分の滴下速度は一定とし、連続的に滴下した。滴下終了後、さらに３０分間に渡って反応溶液を８５℃に保持（熟成）した。その後、反応溶液を放冷しながら８０質量％ジエタノールアミン水溶液３５０．５ｇ（ＡＡ中和率２６．７％分）を撹拌下、反応溶液に徐々に滴下して中和を行い、さらに純水２７２．６gを加え十分に攪拌を行った。以上のようにして、本発明のポリカルボン酸系重合体（４）の水溶液を得た。該水溶液の個形分値は５０．３％であった。ポリカルボン酸系重合体（４）の重量平均分子量（Ｍｗ）は３７０００であった。
<Example 4>
A SUS separable flask having a capacity of 5 liters equipped with a reflux condenser, a stirrer (paddle blade), and a thermometer was charged with 426.9 g of pure water and 0.0164 g of Mole salt (initial charge), and stirred at 85 ° C. The temperature was raised to. Next, under stirring, in a polymerization reaction system at a constant temperature of about 85 ° C., 80 g of an acrylic acid aqueous solution 900 g (that is, 10 mol), 15 mass% ammonium persulfate aqueous solution (hereinafter referred to as “15% APS”) 33.3 g 0.5 g / mol in terms of body input) and 54.3 g of 35% by mass aqueous sodium bisulfite solution (1.9 g / mol in terms of monomer input) were dropped from separate dropping nozzles. The dropping time was 80% AA for 180 minutes, 15% NaPS for 190 minutes, and 35% SBS for 175 minutes. Further, during each dropping time, the dropping rate of each component was kept constant, and dropping was continuously performed. After completion of the dropwise addition, the reaction solution was kept at 85 ° C. (aged) for another 30 minutes. Thereafter, while the reaction solution was allowed to cool, 350.5 g of an 80% by mass diethanolamine aqueous solution (AA neutralization rate: 26.7% min) was gradually added dropwise to the reaction solution with stirring, followed by neutralization. 6 g was added and sufficiently stirred. As described above, an aqueous solution of the polycarboxylic acid polymer (4) of the present invention was obtained. The individual fraction value of the aqueous solution was 50.3%. The weight average molecular weight (Mw) of the polycarboxylic acid polymer (4) was 37000.
＜実施例５＞
還流冷却器、撹拌機（パドル翼）、温度計を備えた容量５リットルのＳＵＳ製セパラブルフラスコに、純水１０４７．３ｇとモール塩０．０２０５ｇを仕込み（初期仕込）、撹拌下、８５℃まで昇温した。次いで撹拌下、約８５℃一定状態の重合反応系中に８０質量％アクリル酸水溶液９００ｇ（すなわち１０ｍｏｌ）、１５質量％過硫酸ナトリウム水溶液３３．４ｇ（対単量体投入量に換算すると０．５ｇ／ｍｏｌ）、３５質量％重亜硫酸ナトリウム水溶液５７．１ｇ（対単量体投入量に換算すると２．０ｇ／ｍｏｌ）、をそれぞれ別個の滴下ノズルより滴下した。それぞれの滴下時間は、８０％ＡＡを１２０分間、１５％ＮａＰＳを１３０分間、３５％ＳＢＳを１１５分間とした。また、それぞれの滴下時間の間、各成分の滴下速度は一定とし、連続的に滴下した。滴下終了後、さらに３０分間に渡って反応溶液を８５℃に保持（熟成）した。その後、反応溶液を放冷しながら８０質量％ジエタノールアミン水溶液３５０．５ｇ（ＡＡ中和率２６．７％分）を撹拌下、反応溶液に徐々に滴下して中和を行い、さらに純水１７５．３gを加え十分に攪拌を行った。
以上のようにして、本発明のポリカルボン酸系重合体（５）の水溶液を得た。該水溶液の個形分値は４０．０％であった。ポリカルボン酸系重合体（５）の重量平均分子量（Ｍｗ）は３００００であった。
<Example 5>
A SUS separable flask having a capacity of 5 liters equipped with a reflux condenser, a stirrer (paddle blade), and a thermometer was charged with 1047.3 g of pure water and 0.0205 g of Mole salt (initial charge), and stirred at 85 ° C. The temperature was raised to. Next, under stirring, in a polymerization reaction system at a constant temperature of about 85 ° C., an 80% by weight acrylic acid aqueous solution 900 g (that is, 10 mol) and a 15% by weight sodium persulfate aqueous solution 33.4 g (0.5 g in terms of monomer charge). / Mol), and 57.1 g of a 35 mass% sodium bisulfite aqueous solution (2.0 g / mol when converted to the amount of monomer charged) were dropped from separate dropping nozzles. The dropping time was 80% AA for 120 minutes, 15% NaPS for 130 minutes, and 35% SBS for 115 minutes. Further, during each dropping time, the dropping rate of each component was kept constant, and dropping was continuously performed. After completion of the dropwise addition, the reaction solution was kept at 85 ° C. (aged) for another 30 minutes. Thereafter, while the reaction solution was allowed to cool, 350.5 g of an 80% by mass diethanolamine aqueous solution (AA neutralization rate: 26.7% min) was gradually added dropwise to the reaction solution with stirring, followed by neutralization. 3 g was added and sufficiently stirred.
As described above, an aqueous solution of the polycarboxylic acid polymer (5) of the present invention was obtained. The solid fraction value of the aqueous solution was 40.0%. The weight average molecular weight (Mw) of the polycarboxylic acid polymer (5) was 30000.
＜実施例６＞
還流冷却器、撹拌機（パドル翼）、温度計を備えた容量５リットルのＳＵＳ製セパラブルフラスコに、純水１０４７．３ｇとモール塩０．０２０５ｇを仕込み（初期仕込）、撹拌下、８５℃まで昇温した。次いで撹拌下、約８５℃一定状態の重合反応系中に８０質量％アクリル酸水溶液９００ｇ（すなわち１０ｍｏｌ）、１５質量％過硫酸ナトリウム水溶液３３．４ｇ（対単量体投入量に換算すると０．５ｇ／ｍｏｌ）、３５質量％重亜硫酸ナトリウム水溶液５７．１ｇ（対単量体投入量に換算すると２．０ｇ／ｍｏｌ）、８０質量％ジエタノールアミン水溶液６５．８ｇ（ＡＡ中和率５．０％分）をそれぞれ別個の滴下ノズルより滴下した。それぞれの滴下時間は、８０％ＡＡを１２０分間、１５％ＮａＰＳを１３０分間、３５％ＳＢＳを１１５分間、８０％ＤＥＡを１２０分間とした。また、それぞれの滴下時間の間、各成分の滴下速度は一定とし、連続的に滴下した。滴下終了後、さらに３０分間に渡って反応溶液を８５℃に保持（熟成）した。その後、反応溶液を放冷しながら８０質量％ジエタノールアミン水溶液２８４．８ｇ（ＡＡ中和率２１．７％分）を撹拌下、反応溶液に徐々に滴下して中和を行い、さらに純水１７５．３gを加え十分に攪拌を行った。以上のようにして、本発明のポリカルボン酸系重合体（６）の水溶液を得た。該水溶液の個形分値は４０．０％であった。ポリカルボン酸系重合体（６）の重量平均分子量（Ｍｗ）は２４０００であった。
<Example 6>
A SUS separable flask having a capacity of 5 liters equipped with a reflux condenser, a stirrer (paddle blade), and a thermometer was charged with 1047.3 g of pure water and 0.0205 g of Mole salt (initial charge), and stirred at 85 ° C. The temperature was raised to. Next, under stirring, in a polymerization reaction system at a constant temperature of about 85 ° C., an 80% by weight acrylic acid aqueous solution 900 g (that is, 10 mol) and a 15% by weight sodium persulfate aqueous solution 33.4 g (0.5 g in terms of monomer charge). / Mol), 57.1 g of a 35% by weight aqueous sodium bisulfite solution (2.0 g / mol when converted to monomer input), 65.8 g of an 80% by weight diethanolamine aqueous solution (AA neutralization rate: 5.0%) Were dropped from separate dropping nozzles. The dropping time was 80 minutes AA for 120 minutes, 15% NaPS for 130 minutes, 35% SBS for 115 minutes, and 80% DEA for 120 minutes. Further, during each dropping time, the dropping rate of each component was kept constant, and dropping was continuously performed. After completion of the dropwise addition, the reaction solution was kept at 85 ° C. (aged) for another 30 minutes. Thereafter, while the reaction solution was allowed to cool, 284.8 g of an 80% by mass diethanolamine aqueous solution (AA neutralization rate: 21.7% min) was gradually added dropwise to the reaction solution with stirring, followed by neutralization. 3 g was added and sufficiently stirred. As described above, an aqueous solution of the polycarboxylic acid polymer (6) of the present invention was obtained. The solid fraction value of the aqueous solution was 40.0%. The weight average molecular weight (Mw) of the polycarboxylic acid polymer (6) was 24,000.
＜実施例７＞
還流冷却器、撹拌機（パドル翼）、温度計を備えた容量５リットルのＳＵＳ製セパラブルフラスコに、純水１０４７．３ｇとモール塩０．０２０５ｇを仕込み（初期仕込）、撹拌下、８５℃まで昇温した。次いで撹拌下、約８５℃一定状態の重合反応系中に８０質量％アクリル酸水溶液９００ｇ（すなわち１０ｍｏｌ）、１５質量％過硫酸ナトリウム水溶液３３．４ｇ（対単量体投入量に換算すると０．５ｇ／ｍｏｌ）、３５質量％重亜硫酸ナトリウム水溶液５７．１ｇ（対単量体投入量に換算すると２．０ｇ／ｍｏｌ）、８０質量％ジエタノールアミン水溶液１３１．４ｇ（ＡＡ中和率１０．０％分）をそれぞれ別個の滴下ノズルより滴下した。それぞれの滴下時間は、８０％ＡＡを１２０分間、１５％ＮａＰＳを１３０分間、３５％ＳＢＳを１１５分間、８０％ＤＥＡを１２０分間とした。また、それぞれの滴下時間の間、各成分の滴下速度は一定とし、連続的に滴下した。滴下終了後、さらに３０分間に渡って反応溶液を８５℃に保持（熟成）した。その後、反応溶液を放冷しながら８０質量％ジエタノールアミン水溶液２１９．０ｇ（ＡＡ中和率１６．７％分）を撹拌下、反応溶液に徐々に滴下して中和を行い、さらに純水１７５．３gを加え十分に攪拌を行った。以上のようにして、本発明のポリカルボン酸系重合体（７）の水溶液を得た。該水溶液の個形分値は４０．０％であった。ポリカルボン酸系重合体（７）の重量平均分子量（Ｍｗ）は３３０００であった。
<Example 7>
A SUS separable flask having a capacity of 5 liters equipped with a reflux condenser, a stirrer (paddle blade), and a thermometer was charged with 1047.3 g of pure water and 0.0205 g of Mole salt (initial charge), and stirred at 85 ° C. The temperature was raised to. Next, under stirring, in a polymerization reaction system at a constant temperature of about 85 ° C., an 80% by weight acrylic acid aqueous solution 900 g (that is, 10 mol) and a 15% by weight sodium persulfate aqueous solution 33.4 g (0.5 g in terms of monomer charge). / Mol), 57.1 g of 35% by weight aqueous sodium bisulfite solution (2.0 g / mol when converted to monomer input), 131.4 g of 80% by weight diethanolamine aqueous solution (AA neutralization rate of 10.0%) Were dropped from separate dropping nozzles. The dropping time was 80 minutes AA for 120 minutes, 15% NaPS for 130 minutes, 35% SBS for 115 minutes, and 80% DEA for 120 minutes. Further, during each dropping time, the dropping rate of each component was kept constant, and dropping was continuously performed. After completion of the dropwise addition, the reaction solution was kept at 85 ° C. (aged) for another 30 minutes. Thereafter, while the reaction solution was allowed to cool, 219.0 g of an 80% by mass diethanolamine aqueous solution (AA neutralization rate of 16.7% min) was gradually added dropwise to the reaction solution while stirring, and further neutralized with 175. 3 g was added and sufficiently stirred. As described above, an aqueous solution of the polycarboxylic acid polymer (7) of the present invention was obtained. The solid fraction value of the aqueous solution was 40.0%. The weight average molecular weight (Mw) of the polycarboxylic acid polymer (7) was 33000.
＜実施例８＞
還流冷却器、撹拌機（パドル翼）、温度計を備えた容量５リットルのＳＵＳ製セパラブルフラスコに、純水１０４７．３ｇとモール塩０．０２０５ｇを仕込み（初期仕込）、撹拌下、８５℃まで昇温した。次いで撹拌下、約８５℃一定状態の重合反応系中に８０質量％アクリル酸水溶液８１０ｇ（すなわち９ｍｏｌ）、８０％メタクリル酸水溶液（以下「８０％ＭＡＡ」と称する）１０７．５g（すなわち１ｍｏｌ）、１５質量％過硫酸ナトリウム水溶液３３．４ｇ（対単量体投入量に換算すると０．５ｇ／ｍｏｌ）、３５質量％重亜硫酸ナトリウム水溶液５７．１ｇ（対単量体投入量に換算すると２．０ｇ／ｍｏｌ）、８０質量％ジエタノールアミン水溶液６５．８ｇ（単量体に由来するカルボキシル基の５．０％中和分に相当）をそれぞれ別個の滴下ノズルより滴下した。それぞれの滴下時間は、８０％ＡＡを１２０分間、８０％ＭＡＡを１２０分間、１５％ＮａＰＳを１３０分間、３５％ＳＢＳを１１５分間、８０％ＤＥＡを１２０分間とした。また、それぞれの滴下時間の間、各成分の滴下速度は一定とし、連続的に滴下した。滴下終了後、さらに３０分間に渡って反応溶液を８５℃に保持（熟成）した。その後、反応溶液を放冷しながら８０質量％ジエタノールアミン水溶液２８４．８ｇ（単量体に由来するカルボキシル基の２１．７％中和分に相当）を撹拌下、反応溶液に徐々に滴下して中和を行い、さらに純水１７５．３gを加え十分に攪拌を行った。以上のようにして、本発明のポリカルボン酸系重合体（８）の水溶液を得た。該水溶液の個形分値は４０．３％であった。ポリカルボン酸系重合体（８）の重量平均分子量（Ｍｗ）は３００００であった。
<Example 8>
A SUS separable flask having a capacity of 5 liters equipped with a reflux condenser, a stirrer (paddle blade), and a thermometer was charged with 1047.3 g of pure water and 0.0205 g of Mole salt (initial charge), and stirred at 85 ° C. The temperature was raised to. Next, under stirring, in a polymerization reaction system at a constant temperature of about 85 ° C., 810 g (namely, 9 mol) of 80 mass% aqueous acrylic acid solution, 107.5 g (namely, 1 mol) of 80% aqueous methacrylic acid solution (hereinafter referred to as “80% MAA”), 33.4 g of 15% by weight aqueous sodium persulfate solution (0.5 g / mol when converted to monomer input), 57.1 g of 35% by weight aqueous sodium bisulfite solution (2.0 g converted to monomer input) / Mol), 65.8 g of 80% by mass diethanolamine aqueous solution (corresponding to 5.0% neutralization of the carboxyl group derived from the monomer) was dropped from separate dropping nozzles. The dropping time was 80% AA for 120 minutes, 80% MAA for 120 minutes, 15% NaPS for 130 minutes, 35% SBS for 115 minutes, and 80% DEA for 120 minutes. Further, during each dropping time, the dropping rate of each component was kept constant, and dropping was continuously performed. After completion of the dropwise addition, the reaction solution was kept at 85 ° C. (aged) for another 30 minutes. Thereafter, while the reaction solution was allowed to cool, 284.8 g of an 80 mass% diethanolamine aqueous solution (corresponding to 21.7% neutralization of the carboxyl group derived from the monomer) was gradually added dropwise to the reaction solution while stirring. Summing was performed, and 175.3 g of pure water was further added, followed by thorough stirring. As described above, an aqueous solution of the polycarboxylic acid polymer (8) of the present invention was obtained. The solid content of the aqueous solution was 40.3%. The weight average molecular weight (Mw) of the polycarboxylic acid polymer (8) was 30000.
＜実施例９＞
還流冷却器、撹拌機（パドル翼）、温度計を備えた容量５リットルのＳＵＳ製セパラブルフラスコに、純水６３７．４ｇとモール塩０．０１６５ｇを仕込み（初期仕込）、撹拌下、８５℃まで昇温した。次いで撹拌下、約８５℃一定状態の重合反応系中に８０質量％アクリル酸水溶液９００ｇ（すなわち１０ｍｏｌ％）、１５質量％過硫酸ナトリウム水溶液４６．２ｇ（対単量体投入量に換算すると０．７ｇ／ｍｏｌ）、３５質量％重亜硫酸ナトリウム水溶液６８．６ｇ（対単量体投入量に換算すると２．４ｇ／ｍｏｌ）、をそれぞれ別個の滴下ノズルより滴下した。それぞれの滴下時間は、８０％ＡＡを１２０分間、１５％ＮａＰＳを１５０分間、３５％ＳＢＳを１１５分間とした。また、それぞれの滴下時間の間、各成分の滴下速度は一定とし、連続的に滴下した。滴下終了後、さらに３０分間に渡って反応溶液を８５℃に保持（熟成）して重合を完結せしめた。重合の完結後、反応溶液を５０℃まで放冷し、３５質量％過酸化水素（以下、「３５％ＨＰ」と称す）５．６ｇ（対単量体投入量に換算すると０．２ｇ／ｍｏｌ）を攪拌下、反応液に滴下した。３５％ＨＰの滴下終了後８０質量％ジエタノールアミン水溶液３５０．５ｇ（ＡＡ中和率２６．７％分）を撹拌下、反応溶液に徐々に滴下して中和を行い、さらに純水５７５gを加え十分に攪拌を行った。以上のようにして、本発明のポリカルボン酸系重合体（９）の水溶液を得た。該水溶液の固形分値は４０．０％であった。ポリカルボン酸系重合体（９）の重量平均分子量（Ｍｗ）は２７０００であった。
<Example 9>
A SUS separable flask having a capacity of 5 liters equipped with a reflux condenser, a stirrer (paddle blade), and a thermometer was charged with 637.4 g of pure water and 0.0165 g of Mole salt (initial charge), and stirred at 85 ° C. The temperature was raised to. Next, under stirring, in a polymerization reaction system at a constant temperature of about 85 ° C., 900 g of an 80% by mass acrylic acid aqueous solution (that is, 10 mol%) and 46.2 g of a 15% by mass aqueous sodium persulfate aqueous solution (in terms of the amount of monomer added, the amount is 0. 7 g / mol) and 68.6 g of a 35 mass% sodium bisulfite aqueous solution (2.4 g / mol when converted to the amount of monomer charged) were dropped from separate dropping nozzles. The dropping time was 80% AA for 120 minutes, 15% NaPS for 150 minutes, and 35% SBS for 115 minutes. Further, during each dropping time, the dropping rate of each component was kept constant, and dropping was continuously performed. After completion of the dropwise addition, the reaction solution was kept at 85 ° C. (ripening) for 30 minutes to complete the polymerization. After completion of the polymerization, the reaction solution was allowed to cool to 50 ° C., and 5.6 g of 35% by mass hydrogen peroxide (hereinafter referred to as “35% HP”) (0.2 g / mol in terms of monomer input). ) Was added dropwise to the reaction mixture with stirring. After completion of the dropwise addition of 35% HP, 350.5 g of an 80% by mass diethanolamine aqueous solution (AA neutralization rate of 26.7%) was neutralized by gradually dropping into the reaction solution while stirring, and 575 g of pure water was further added. Was stirred. As described above, an aqueous solution of the polycarboxylic acid polymer (9) of the present invention was obtained. The solid content value of the aqueous solution was 40.0%. The weight average molecular weight (Mw) of the polycarboxylic acid polymer (9) was 27000.
＜実施例１０＞
還流冷却器、撹拌機（パドル翼）、温度計を備えた容量５リットルのＳＵＳ製セパラブルフラスコに、純水６３１．９ｇとモール塩０．０１６５ｇを仕込み（初期仕込）、撹拌下、８５℃まで昇温した。次いで撹拌下、約８５℃一定状態の重合反応系中に８０質量％アクリル酸水溶液９００ｇ（すなわち１０ｍｏｌ％）、１５質量％過硫酸ナトリウム水溶液４６．２ｇ（対単量体投入量に換算すると０．７ｇ／ｍｏｌ）、３５質量％重亜硫酸ナトリウム水溶液８５．７ｇ（対単量体投入量に換算すると３．０ｇ／ｍｏｌ）、をそれぞれ別個の滴下ノズルより滴下した。それぞれの滴下時間は、８０％ＡＡを１２０分間、１５％ＮａＰＳを１５０分間、３５％ＳＢＳを１１５分間とした。また、それぞれの滴下時間の間、各成分の滴下速度は一定とし、連続的に滴下した。滴下終了後、さらに３０分間に渡って反応溶液を８５℃に保持（熟成）して重合を完結せしめた。重合の完結後、反応溶液を５０℃まで放冷し、３５質量％過酸化水素７．３ｇ（対単量体投入量に換算すると０．２６ｇ／ｍｏｌ）を攪拌下、反応液に滴下した。３５％ＨＰの滴下終了後８０質量％ジエタノールアミン水溶液３５０．５ｇ（ＡＡ中和率２６．７％分）を撹拌下、反応溶液に徐々に滴下して中和を行い、さらに純水５８０gを加え十分に攪拌を行った。以上のようにして、本発明のポリカルボン酸系重合体（１０）の水溶液を得た。該水溶液の固形分値は４０．０％であった。ポリカルボン酸系重合体（１０）の重量平均分子量（Ｍｗ）は２００００であった。
<Example 10>
A SUS separable flask having a capacity of 5 liters equipped with a reflux condenser, a stirrer (paddle blade), and a thermometer was charged with 631.9 g of pure water and 0.0165 g of Mole salt (initial charge), and stirred at 85 ° C. The temperature was raised to. Next, under stirring, in a polymerization reaction system at a constant temperature of about 85 ° C., 900 g of an 80% by mass acrylic acid aqueous solution (that is, 10 mol%) and 46.2 g of a 15% by mass aqueous sodium persulfate aqueous solution (in terms of the amount of monomer added, the amount is 0. 7 g / mol) and 85.7 g of a 35 mass% aqueous sodium bisulfite solution (3.0 g / mol when converted to the amount of monomer charged) were dropped from separate dropping nozzles. The dropping time was 80% AA for 120 minutes, 15% NaPS for 150 minutes, and 35% SBS for 115 minutes. Further, during each dropping time, the dropping rate of each component was kept constant, and dropping was continuously performed. After completion of the dropwise addition, the reaction solution was kept at 85 ° C. (ripening) for 30 minutes to complete the polymerization. After completion of the polymerization, the reaction solution was allowed to cool to 50 ° C., and 7.3 g of 35% by mass hydrogen peroxide (0.26 g / mol when converted to the amount of monomer added) was added dropwise to the reaction solution with stirring. After completion of the dropwise addition of 35% HP, 350.5 g of an 80% by mass diethanolamine aqueous solution (AA neutralization rate of 26.7%) was neutralized by gradually dropping into the reaction solution while stirring, and 580 g of pure water was further added. Was stirred. As described above, an aqueous solution of the polycarboxylic acid polymer (10) of the present invention was obtained. The solid content value of the aqueous solution was 40.0%. The weight average molecular weight (Mw) of the polycarboxylic acid polymer (10) was 20000.
＜実施例１１＞
還流冷却器、撹拌機（パドル翼）、温度計を備えた容量５リットルのＳＵＳ製セパラブルフラスコに、純水６３７．４ｇとモール塩０．０１６５ｇを仕込み（初期仕込）、撹拌下、８５℃まで昇温した。次いで撹拌下、約８５℃一定状態の重合反応系中に８０質量％アクリル酸水溶液９００ｇ（すなわち１０ｍｏｌ％）、１５質量％過硫酸ナトリウム水溶液４６．２ｇ（対単量体投入量に換算すると０．７ｇ／ｍｏｌ）、３５質量％重亜硫酸ナトリウム水溶液７７．１ｇ（対単量体投入量に換算すると２．７ｇ／ｍｏｌ）、をそれぞれ別個の滴下ノズルより滴下した。それぞれの滴下時間は、８０％ＡＡを１２０分間、１５％ＮａＰＳを１５０分間、３５％ＳＢＳを１１５分間とした。また、それぞれの滴下時間の間、各成分の滴下速度は一定とし、連続的に滴下した。滴下終了後、さらに３０分間に渡って反応溶液を８５℃に保持（熟成）して重合を完結せしめた。重合の完結後、反応溶液を放冷しながら８０質量％ジエタノールアミン水溶液３５０．５ｇ（ＡＡ中和率２６．７％分）を撹拌下、反応溶液に徐々に滴下して中和を行った。反応溶液を５０℃まで放冷し、３５質量％過酸化水素６．６ｇ（対単量体投入量に換算すると０．２３ｇ／ｍｏｌ）を攪拌下、反応液に滴下し、さらに純水５７６gを加え十分に攪拌を行った。以上のようにして、本発明のポリカルボン酸系重合体（１１）の水溶液を得た。該水溶液の固形分値は４０．０％であった。ポリカルボン酸系重合体（１１）の重量平均分子量（Ｍｗ）は２３０００であった。
<Example 11>
A SUS separable flask having a capacity of 5 liters equipped with a reflux condenser, a stirrer (paddle blade), and a thermometer was charged with 637.4 g of pure water and 0.0165 g of Mole salt (initial charge), and stirred at 85 ° C. The temperature was raised to. Next, under stirring, in a polymerization reaction system at a constant temperature of about 85 ° C., 900 g of an 80% by mass acrylic acid aqueous solution (that is, 10 mol%) and 46.2 g of a 15% by mass aqueous sodium persulfate aqueous solution (in terms of the amount of monomer added, the amount is 0. 7 g / mol) and 77.1 g of a 35% by mass aqueous sodium bisulfite solution (2.7 g / mol when converted to the amount of monomer charged) were added dropwise from separate dropping nozzles. The dropping time was 80% AA for 120 minutes, 15% NaPS for 150 minutes, and 35% SBS for 115 minutes. Further, during each dropping time, the dropping rate of each component was kept constant, and dropping was continuously performed. After completion of the dropwise addition, the reaction solution was kept at 85 ° C. (ripening) for 30 minutes to complete the polymerization. After completion of the polymerization, the reaction solution was allowed to cool, and 350.5 g of an 80% by mass diethanolamine aqueous solution (AA neutralization rate: 26.7% min) was gradually added dropwise to the reaction solution while stirring to effect neutralization. The reaction solution was allowed to cool to 50 ° C., and 6.6 g of 35% by mass hydrogen peroxide (0.23 g / mol when converted to the amount of monomer added) was added dropwise to the reaction solution with stirring, and 576 g of pure water was further added. In addition, sufficient stirring was performed. As described above, an aqueous solution of the polycarboxylic acid polymer (11) of the present invention was obtained. The solid content value of the aqueous solution was 40.0%. The weight average molecular weight (Mw) of the polycarboxylic acid polymer (11) was 23000.
＜実施例１２＞
還流冷却器、撹拌機（パドル翼）、温度計を備えた容量５リットルのＳＵＳ製セパラブルフラスコに、純水６３１．９ｇとモール塩０．０１６５ｇを仕込み（初期仕込）、撹拌下、８５℃まで昇温した。次いで撹拌下、約８５℃一定状態の重合反応系中に８０質量％アクリル酸水溶液９００ｇ（すなわち１０ｍｏｌ％）、１５質量％過硫酸ナトリウム水溶液４６．２ｇ（対単量体投入量に換算すると０．７ｇ／ｍｏｌ）、３５質量％重亜硫酸ナトリウム水溶液１００．０ｇ（対単量体投入量に換算すると３．５ｇ／ｍｏｌ）、をそれぞれ別個の滴下ノズルより滴下した。それぞれの滴下時間は、８０％ＡＡを１２０分間、１５％ＮａＰＳを１５０分間、３５％ＳＢＳを１１５分間とした。また、それぞれの滴下時間の間、各成分の滴下速度は一定とし、連続的に滴下した。滴下終了後、さらに３０分間に渡って反応溶液を８５℃に保持（熟成）して重合を完結せしめた。重合の完結後、反応溶液を放冷しながら８０質量％ジエタノールアミン水溶液３５０．５ｇ（ＡＡ中和率２６．７％分）を撹拌下、反応溶液に徐々に滴下して中和を行った。反応溶液を５０℃まで放冷し、３５質量％過酸化水素８．４ｇ（対単量体投入量に換算すると０．３ｇ／ｍｏｌ）を攪拌下、反応液に滴下し、さらに純水５７７gを加え十分に攪拌を行った。以上のようにして、本発明のポリカルボン酸系重合体（１２）の水溶液を得た。該水溶液の固形分値は４０．０％であった。ポリカルボン酸系重合体（１２）の重量平均分子量（Ｍｗ）は１５０００であった。
<Example 12>
A SUS separable flask having a capacity of 5 liters equipped with a reflux condenser, a stirrer (paddle blade), and a thermometer was charged with 631.9 g of pure water and 0.0165 g of Mole salt (initial charge), and stirred at 85 ° C. The temperature was raised to. Next, under stirring, in a polymerization reaction system at a constant temperature of about 85 ° C., 900 g of an 80% by mass acrylic acid aqueous solution (that is, 10 mol%) and 46.2 g of a 15% by mass aqueous sodium persulfate aqueous solution (in terms of the amount of monomer added, the amount is 0. 7 g / mol) and 100.0 g of 35% by mass aqueous sodium bisulfite solution (3.5 g / mol when converted to the amount of monomer added) were dropped from separate dropping nozzles. The dropping time was 80% AA for 120 minutes, 15% NaPS for 150 minutes, and 35% SBS for 115 minutes. Further, during each dropping time, the dropping rate of each component was kept constant, and dropping was continuously performed. After completion of the dropwise addition, the reaction solution was kept at 85 ° C. (ripening) for 30 minutes to complete the polymerization. After completion of the polymerization, the reaction solution was allowed to cool, and 350.5 g of an 80% by mass diethanolamine aqueous solution (AA neutralization rate: 26.7% min) was gradually added dropwise to the reaction solution while stirring to effect neutralization. The reaction solution was allowed to cool to 50 ° C., and 8.4 g of 35% by mass hydrogen peroxide (0.3 g / mol when converted to the amount of monomer added) was added dropwise to the reaction solution with stirring, and 577 g of pure water was further added. In addition, sufficient stirring was performed. As described above, an aqueous solution of the polycarboxylic acid polymer (12) of the present invention was obtained. The solid content value of the aqueous solution was 40.0%. The weight average molecular weight (Mw) of the polycarboxylic acid polymer (12) was 15000.
＜比較例１＞
還流冷却器、撹拌機（パドル翼）、温度計を備えた容量５リットルのＳＵＳ製セパラブルフラスコに、純水１０００．０ｇを仕込み（初期仕込）、撹拌下、沸点まで昇温した。次いで撹拌下、沸点還流状態の重合反応系中に８０質量％アクリル酸水溶液９００ｇ（すなわち１０ｍｏｌ）、１５質量％過硫酸ナトリウム水溶液３００．０ｇ（対単量体投入量に換算すると４．５ｇ／ｍｏｌ）をそれぞれ別個の滴下ノズルより滴下した。それぞれの滴下時間は、８０％ＡＡを１８０分間、１５％ＮａＰＳを１９０分間とした。また、それぞれの滴下時間の間、各成分の滴下速度は一定とし、連続的に滴下した。滴下終了後、さらに３０分間に渡って反応溶液を沸点還流状態に保持（熟成）した。その後、反応溶液を放冷しながら８０質量％ジエタノールアミン水溶液３５０．５ｇ（ＡＡ中和率２６．７％分）を撹拌下、反応溶液に徐々に滴下して中和を行い、さらに純水２７．８gを加え十分に攪拌を行った。以上のようにして、比較ポリカルボン酸系重合体（１）の水溶液を得た。該水溶液の個形分値は４０．５％であった。比較ポリカルボン酸系重合体（１）の重量平均分子量（Ｍｗ）は１００００であった。
<Comparative Example 1>
1000.0 g of pure water was charged into an SUS separable flask having a capacity of 5 liters equipped with a reflux condenser, a stirrer (paddle blade), and a thermometer (initial charge), and the temperature was raised to the boiling point with stirring. Next, under stirring, 900 g (ie 10 mol) of an 80% by weight aqueous acrylic acid solution and 300.0 g of 15% by weight aqueous sodium persulfate solution (4.5 g / mol in terms of monomer charge) in the polymerization reaction system at the boiling point reflux state. ) Were dropped from separate drop nozzles. The dropping time was 80% AA for 180 minutes and 15% NaPS for 190 minutes. Further, during each dropping time, the dropping rate of each component was kept constant, and dropping was continuously performed. After completion of the dropwise addition, the reaction solution was kept at the boiling point reflux state (aged) for another 30 minutes. Thereafter, while the reaction solution was allowed to cool, 350.5 g of an 80% by mass diethanolamine aqueous solution (AA neutralization rate: 26.7% min) was gradually added dropwise to the reaction solution with stirring, followed by neutralization. 8 g was added and sufficiently stirred. As described above, an aqueous solution of the comparative polycarboxylic acid polymer (1) was obtained. The individual fraction value of the aqueous solution was 40.5%. The weight average molecular weight (Mw) of the comparative polycarboxylic acid polymer (1) was 10,000.
＜比較例２＞
還流冷却器、撹拌機（パドル翼）、温度計を備えた容量５リットルのＳＵＳ製セパラブルフラスコに、純水１１３８．０ｇを仕込み（初期仕込）、撹拌下、沸点まで昇温した。次いで撹拌下、沸点還流状態の重合反応系中に８０質量％アクリル酸水溶液９００ｇ（すなわち１０ｍｏｌ）、１５質量％過硫酸ナトリウム水溶液１８０．０ｇ（対単量体投入量に換算すると２．７ｇ／ｍｏｌ）をそれぞれ別個の滴下ノズルより滴下した。それぞれの滴下時間は、８０％ＡＡを３６０分間、１５％ＮａＰＳを３７０分間とした。また、それぞれの滴下時間の間、各成分の滴下速度は一定とし、連続的に滴下した。滴下終了後、さらに３０分間に渡って反応溶液を沸点還流状態に保持（熟成）した。その後、反応溶液を放冷しながら８０質量％ジエタノールアミン水溶液３５０．５ｇ（ＡＡ中和率２６．７％分）を撹拌下、反応溶液に徐々に滴下して中和を行った。以上のようにして、比較ポリカルボン酸系重合体（２）の水溶液を得た。該水溶液の個形分値は４０．０％であった。比較ポリカルボン酸系重合体（２）の重量平均分子量（Ｍｗ）は３８０００であった。
<Comparative example 2>
In a 5-liter SUS separable flask equipped with a reflux condenser, a stirrer (paddle blade), and a thermometer, 1138.0 g of pure water was charged (initial charge), and the temperature was raised to the boiling point with stirring. Next, under stirring, in a polymerization reaction system in a boiling point reflux state, 900 g of an 80% by mass acrylic acid aqueous solution (that is, 10 mol), 180.0 g of 15% by mass aqueous sodium persulfate aqueous solution (2.7 g / mol when converted to the amount of monomer charged). ) Were dropped from separate drop nozzles. Each dropping time was set to 360% for 80% AA and 370 minutes for 15% NaPS. Further, during each dropping time, the dropping rate of each component was kept constant, and dropping was continuously performed. After completion of the dropwise addition, the reaction solution was kept at the boiling point reflux state (aged) for another 30 minutes. Thereafter, while the reaction solution was allowed to cool, 350.5 g of an 80% by mass diethanolamine aqueous solution (AA neutralization rate: 26.7%) was gradually added dropwise to the reaction solution while stirring to effect neutralization. As described above, an aqueous solution of the comparative polycarboxylic acid polymer (2) was obtained. The solid fraction value of the aqueous solution was 40.0%. The weight average molecular weight (Mw) of the comparative polycarboxylic acid polymer (2) was 38000.
＜比較例３＞
還流冷却器、撹拌機（パドル翼）、温度計を備えた容量５リットルのＳＵＳ製セパラブルフラスコに、純水１１４１．１ｇを仕込み（初期仕込）、撹拌下、沸点まで昇温した。次いで撹拌下、沸点還流状態の重合反応系中に８０質量％アクリル酸水溶液９００ｇ（すなわち１０ｍｏｌ）、１５質量％過硫酸アンモニウム水溶液１７３．４ｇ（対単量体投入量に換算すると２．６ｇ／ｍｏｌ）をそれぞれ別個の滴下ノズルより滴下した。それぞれの滴下時間は、８０％ＡＡを３６０分間、１５％ＮａＰＳを３７０分間とした。また、それぞれの滴下時間の間、各成分の滴下速度は一定とし、連続的に滴下した。滴下終了後、さらに３０分間に渡って反応溶液を沸点還流状態に保持（熟成）した。その後、反応溶液を放冷しながら８０質量％ジエタノールアミン水溶液３５０．５ｇ（ＡＡ中和率２６．７％分）を撹拌下、反応溶液に徐々に滴下して中和を行った。以上のようにして、比較ポリカルボン酸系重合体（３）の水溶液を得た。該水溶液の個形分値は４０．０％であった。比較ポリカルボン酸系重合体（３）の重量平均分子量（Ｍｗ）は３９０００であった。
<Comparative Example 3>
In a 5-liter SUS separable flask equipped with a reflux condenser, a stirrer (paddle blade), and a thermometer, 1141.1 g of pure water was charged (initial charge), and the temperature was raised to the boiling point with stirring. Next, 900 g (ie, 10 mol) of an 80% by mass acrylic acid aqueous solution and 173.4 g of an aqueous 15% by mass ammonium persulfate aqueous solution (2.6 g / mol in terms of monomer charge) in a polymerization reaction system in a boiling point reflux state with stirring. Were dropped from separate dropping nozzles. Each dropping time was set to 360% for 80% AA and 370 minutes for 15% NaPS. Further, during each dropping time, the dropping rate of each component was kept constant, and dropping was continuously performed. After completion of the dropwise addition, the reaction solution was kept at the boiling point reflux state (aged) for another 30 minutes. Thereafter, while the reaction solution was allowed to cool, 350.5 g of an 80% by mass diethanolamine aqueous solution (AA neutralization rate: 26.7%) was gradually added dropwise to the reaction solution while stirring to effect neutralization. As described above, an aqueous solution of the comparative polycarboxylic acid polymer (3) was obtained. The solid fraction value of the aqueous solution was 40.0%. The weight average molecular weight (Mw) of the comparative polycarboxylic acid polymer (3) was 39000.
表１から明らかなように、本発明の重合体（組成物）は、従来の重合体（組成物）に比して、優れた色調（着色が少ない）を有していることが明らかとなった。よって、本発明の重合体は、洗剤ビルダー等として好ましく使用できることが明らかとなった。 As is apparent from Table 1, the polymer (composition) of the present invention has an excellent color tone (less coloring) as compared with the conventional polymer (composition). It was. Therefore, it was revealed that the polymer of the present invention can be preferably used as a detergent builder or the like.
Claims (2)
カルボキシル基の一部が有機アミン基であり、
該有機アミンで中和されているカルボキシル基が、１〜７０モル％であり、
重量平均分子量が７，９００〜２００，０００である、
ポリカルボン酸系重合体。 It has a sulfonic acid (salt) group at the end of the main chain,
A part of the carboxyl group is an organic amine group,
The carboxyl group neutralized with the organic amine is 1 to 70 mol%,
Weight average molecular weight of 7,900 to 200,000,
Polycarboxylic acid polymer.
過硫酸塩および重亜硫酸塩の存在下で重合する工程と、
重合前、重合中、重合後のいずれかの段階で有機アミンを添加する工程を含み、
全単量体（カルボキシル基含有単量体とその他の単量体の合計）１モルに対して、連鎖移動剤と上記重合開始剤の合計の使用量が、２．０ｇ以上、１０．０ｇ以下である、
ポリカルボン酸系重合体の製造方法。
Only acrylic acid ,
Polymerizing in the presence of persulfate and bisulfite;
Including a step of adding an organic amine at any stage before, during or after polymerization,
The total amount of the chain transfer agent and the polymerization initiator used is 2.0 g or more and 10.0 g or less with respect to 1 mol of all monomers (total of carboxyl group-containing monomers and other monomers). Is,
A method for producing a polycarboxylic acid polymer.
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