JP6721417B2 - Sulfur-containing polymer composition and method for producing the same - Google Patents
Sulfur-containing polymer composition and method for producing the same Download PDFInfo
- Publication number
- JP6721417B2 JP6721417B2 JP2016109527A JP2016109527A JP6721417B2 JP 6721417 B2 JP6721417 B2 JP 6721417B2 JP 2016109527 A JP2016109527 A JP 2016109527A JP 2016109527 A JP2016109527 A JP 2016109527A JP 6721417 B2 JP6721417 B2 JP 6721417B2
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- Prior art keywords
- sulfur
- polymer composition
- containing polymer
- methacrylic acid
- polymer
- Prior art date
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- 229920000642 polymer Polymers 0.000 title claims description 132
- 229910052717 sulfur Inorganic materials 0.000 title claims description 123
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims description 112
- 239000011593 sulfur Substances 0.000 title claims description 112
- 239000000203 mixture Substances 0.000 title claims description 82
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 239000000178 monomer Substances 0.000 claims description 60
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 42
- 150000001875 compounds Chemical class 0.000 claims description 39
- 239000003599 detergent Substances 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims description 27
- 238000006116 polymerization reaction Methods 0.000 claims description 22
- 125000004434 sulfur atom Chemical group 0.000 claims description 20
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 9
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 9
- 235000011152 sodium sulphate Nutrition 0.000 claims description 9
- 238000004458 analytical method Methods 0.000 claims description 8
- 238000005259 measurement Methods 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 6
- 238000004364 calculation method Methods 0.000 claims description 5
- 238000009616 inductively coupled plasma Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000003480 eluent Substances 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000004993 emission spectroscopy Methods 0.000 claims description 2
- 238000004255 ion exchange chromatography Methods 0.000 claims description 2
- 238000000691 measurement method Methods 0.000 claims 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 45
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical group CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 20
- 125000004432 carbon atom Chemical group C* 0.000 description 16
- -1 Amine salts Chemical class 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 12
- 229920001223 polyethylene glycol Polymers 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 229920002818 (Hydroxyethyl)methacrylate Chemical group 0.000 description 11
- 239000002202 Polyethylene glycol Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 11
- 230000032683 aging Effects 0.000 description 10
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 239000004094 surface-active agent Substances 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 8
- 239000012986 chain transfer agent Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 229920001748 polybutylene Polymers 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000013329 compounding Methods 0.000 description 7
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 7
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 7
- 229920001451 polypropylene glycol Polymers 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 229920001515 polyalkylene glycol Polymers 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 230000002431 foraging effect Effects 0.000 description 4
- 125000004437 phosphorous atom Chemical group 0.000 description 4
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 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 3
- 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 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-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
- PAKCOSURAUIXFG-UHFFFAOYSA-N 3-prop-2-enoxypropane-1,2-diol Chemical compound OCC(O)COCC=C PAKCOSURAUIXFG-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical group CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-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
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-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
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 125000005641 methacryl group Chemical group 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- CMSVOQYCGCZLPU-UHFFFAOYSA-N 2-(sulfanylmethyl)decanoic acid Chemical compound CCCCCCCCC(CS)C(O)=O CMSVOQYCGCZLPU-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
- BXYOLIGRUFQZKR-UHFFFAOYSA-N 2-hydroxybut-3-ene-1-sulfonic acid Chemical compound C=CC(O)CS(O)(=O)=O BXYOLIGRUFQZKR-UHFFFAOYSA-N 0.000 description 1
- QENRKQYUEGJNNZ-UHFFFAOYSA-N 2-methyl-1-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound CC(C)C(S(O)(=O)=O)NC(=O)C=C QENRKQYUEGJNNZ-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical group CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-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
- 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
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-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
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 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
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229950005228 bromoform Drugs 0.000 description 1
- SKGVGRLWZVRZDC-UHFFFAOYSA-N butyl 2-sulfanylacetate Chemical compound CCCCOC(=O)CS SKGVGRLWZVRZDC-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 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
- ZNEWHQLOPFWXOF-UHFFFAOYSA-N coenzyme M Chemical compound OS(=O)(=O)CCS ZNEWHQLOPFWXOF-UHFFFAOYSA-N 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000006866 deterioration 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
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-N dithionous acid Chemical compound OS(=O)S(O)=O GRWZHXKQBITJKP-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical group CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000001530 fumaric acid Substances 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
- 150000004820 halides Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas 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
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical compound CC(=C)CCO CPJRRXSHAYUTGL-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 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
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- MADOXCFISYCULS-UHFFFAOYSA-N octyl 2-sulfanylacetate Chemical compound CCCCCCCCOC(=O)CS MADOXCFISYCULS-UHFFFAOYSA-N 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
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 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
- 239000000843 powder Substances 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical group CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical group CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 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
- 229930000044 secondary metabolite Natural products 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- 229940035024 thioglycerol Drugs 0.000 description 1
- 150000003573 thiols Chemical group 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- 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
- 229920002554 vinyl polymer Polymers 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Detergent Compositions (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
本発明は、硫黄含有重合体組成物およびその製造方法に関する。より詳しくは、洗剤の原料として好適に用いることができる硫黄含有重合体組成物およびその製造方法に関する。 The present invention relates to a sulfur-containing polymer composition and a method for producing the same. More specifically, it relates to a sulfur-containing polymer composition that can be suitably used as a raw material for detergents, and a method for producing the same.
メタクリル酸及びそのエステルを原料として得られる重合体は、様々な用途に幅広く用いられている樹脂の一種であり、例えば、従来よりセメントの流動性等を向上させるためのセメント分散剤として用いられている（特許文献１参照）。
このようなメタクリル酸系重合体の用途の１つに、洗剤分野がある。従来、衣料類や食器等の洗浄に用いられる洗剤には、洗浄効果を向上させることを目的として、ゼオライト、カルボキシメチルセルロース、ポリエチレングリコールなどの洗剤ビルダー（洗剤助剤）を配合することが行われているが、近年では、メタクリル酸とメタクリル酸エステルとの共重合体等のポリカルボン酸塩等を洗剤ビルダーとして洗剤組成物に配合したものが開示されている（例えば、特許文献２）。
Polymer obtained from methacrylic acid and its ester as a raw material is a kind of resin that is widely used in various applications, for example, it has been used as a cement dispersant for improving the fluidity of cement and the like. (See Patent Document 1).
One of the applications of such methacrylic acid-based polymers is in the detergent field. Conventionally, detergents used for washing clothes, dishes, etc. have been blended with detergent builders (detergent aids) such as zeolite, carboxymethyl cellulose, and polyethylene glycol for the purpose of improving the washing effect. However, in recent years, there has been disclosed one in which a polycarboxylic acid salt such as a copolymer of methacrylic acid and a methacrylic acid ester is blended in a detergent composition as a detergent builder (for example, Patent Document 2).
メタクリル酸系重合体を洗剤用途に用いる場合、洗剤組成物に安定的に配合できることが求められる。上記特許文献２に記載のメタクリル酸系重合体は、配合安定性の点で充分とはいえず、改善する余地があった。 When the methacrylic acid-based polymer is used for detergents, it is required that it can be stably blended in a detergent composition. The methacrylic acid-based polymer described in Patent Document 2 is not sufficient in terms of compounding stability, and there is room for improvement.
本発明は、上記現状に鑑みてなされたものであり、洗剤組成物への配合安定性に優れたメタクリル酸系重合体を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a methacrylic acid-based polymer having excellent compounding stability in a detergent composition.
本発明者は、メタクリル酸系重合体の洗剤組成物への配合安定性を向上させる方法について種々検討したところ、メタクリル酸由来の構造単位とメタクリル酸エステル由来の構造単位とを含み、重合体の構造中に硫黄原子を含む硫黄含有重合体と、該硫黄含有重合体とは異なる硫黄含有化合物とを含む硫黄含有重合体組成物の形態とし、かつ、硫黄含有重合体の構造中に含まれる硫黄原子の割合、及び、硫黄含有重合体組成物中における硫黄含有化合物の含有割合を所定の割合とすると、洗剤組成物への配合安定性の高い組成物となることを見いだし、上記課題をみごとに解決することができることに想到し、本発明に到達したものである。 The present inventor has made various studies on a method for improving the compounding stability of a methacrylic acid-based polymer in a detergent composition, and it has been found that the polymer contains a methacrylic acid-derived structural unit and a methacrylic acid ester-derived structural unit. A sulfur-containing polymer having a sulfur atom in the structure, and a sulfur-containing polymer composition containing a sulfur-containing compound different from the sulfur-containing polymer, and sulfur contained in the structure of the sulfur-containing polymer Atom ratio, and, when the content ratio of the sulfur-containing compound in the sulfur-containing polymer composition is set to a predetermined ratio, it was found that the composition has high compounding stability in a detergent composition, and the above-mentioned problems are excellent. The present invention has been made based on the idea that it can be solved.
すなわち本発明は、構造中に硫黄原子を含む硫黄含有重合体と、上記硫黄含有重合体とは異なる硫黄含有化合物とを含む硫黄含有重合体組成物であって、上記硫黄含有重合体は、メタクリル酸由来の構造単位とメタクリル酸エステル由来の構造単位とを含み、重合体の構造中に含まれる硫黄原子の割合が４００ｐｐｍ以上であり、上記硫黄含有重合体組成物中における硫黄含有化合物の含有割合が、硫酸ナトリウム換算で２００００ｐｐｍ以下であることを特徴とする硫黄含有重合体組成物である。
以下に本発明を詳述する。
なお、以下において記載する本発明の個々の好ましい形態を２つ以上組み合わせたものもまた、本発明の好ましい形態である。
That is, the present invention is a sulfur-containing polymer composition containing a sulfur-containing polymer having a sulfur atom in the structure, and a sulfur-containing compound different from the sulfur-containing polymer, wherein the sulfur-containing polymer is methacrylic Containing a structural unit derived from an acid and a structural unit derived from a methacrylic acid ester, the ratio of sulfur atoms contained in the structure of the polymer is 400 ppm or more, the content ratio of the sulfur-containing compound in the sulfur-containing polymer composition Is 20,000 ppm or less in terms of sodium sulfate, which is a sulfur-containing polymer composition.
The present invention will be described in detail below.
It should be noted that a combination of two or more of the individual preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.
本発明の硫黄含有重合体組成物は、メタクリル酸由来の構造単位とメタクリル酸エステル由来の構造単位とを含み、重合体の構造中に含まれる硫黄原子の割合が４００ｐｐｍ以上である硫黄含有重合体を含み、更に、硫黄含有重合体とは異なる硫黄含有化合物の含有割合が硫酸ナトリウム換算で２００００ｐｐｍ以下であることを特徴とする。このような割合を満たすことで、洗剤組成物に含まれる界面活性剤との相溶性が高く、洗剤組成物に対する配合安定性の高い組成物となる。
本発明の該硫黄含有重合体の構造中に含まれる硫黄原子の割合は、４００ｐｐｍ以上であり、好ましくは、５００ｐｐｍ以上であり、更に好ましくは、６００ｐｐｍ以上である。また、該硫黄含有重合体の構造中に含まれる硫黄原子の割合は、１２００ｐｐｍ以下であることが好ましい。より好ましくは、１０００ｐｐｍ以下であり、更に好ましくは、９００ｐｐｍ以下である。
硫黄含有重合体の構造中に含まれる硫黄原子の割合は、実施例に記載の方法で測定することができる。
The sulfur-containing polymer composition of the present invention contains a methacrylic acid-derived structural unit and a methacrylic acid ester-derived structural unit, and the proportion of sulfur atoms contained in the polymer structure is 400 ppm or more. Further, the content ratio of the sulfur-containing compound different from the sulfur-containing polymer is 20000 ppm or less in terms of sodium sulfate. By satisfying such a ratio, the composition has high compatibility with the surfactant contained in the detergent composition and high compounding stability with respect to the detergent composition.
The proportion of sulfur atoms contained in the structure of the sulfur-containing polymer of the present invention is 400 ppm or more, preferably 500 ppm or more, more preferably 600 ppm or more. Further, the proportion of sulfur atoms contained in the structure of the sulfur-containing polymer is preferably 1200 ppm or less. It is more preferably 1000 ppm or less, and further preferably 900 ppm or less.
The proportion of sulfur atoms contained in the structure of the sulfur-containing polymer can be measured by the method described in Examples.
本発明の硫黄含有重合体組成物は、硫黄含有重合体とは異なる硫黄含有化合物の含有割合が硫酸ナトリウム換算で２００００ｐｐｍ以下であるが、該硫黄含有重合体とは異なる硫黄含有化合物の含有割合は、硫酸ナトリウム換算で１５０００ｐｐｍ以下であることが好ましい。より好ましくは、１３０００ｐｐｍ以下であり、更に好ましくは、１２０００ｐｐｍ以下である。
本発明の硫黄含有重合体組成物中の硫黄含有化合物の含有割合は、実施例に記載の方法により測定することができる。
The sulfur-containing polymer composition of the present invention, the content of the sulfur-containing compound different from the sulfur-containing polymer is 20,000 ppm or less in terms of sodium sulfate, the content of the sulfur-containing compound different from the sulfur-containing polymer is It is preferably 15,000 ppm or less in terms of sodium sulfate. It is more preferably 13000 ppm or less, still more preferably 12000 ppm or less.
The content ratio of the sulfur-containing compound in the sulfur-containing polymer composition of the present invention can be measured by the method described in Examples.
本発明における硫黄含有重合体は、メタクリル酸由来の構造単位とメタクリル酸エステル由来の構造単位とを含むメタクリル酸系重合体である。
該メタクリル酸系重合体におけるメタクリル酸由来の構造単位の含有割合は、メタクリル酸系重合体の全構造単位１００質量％に対して、２０〜８０質量％であることが好ましい。このような割合で含むことで、硫黄含有重合体が洗剤ビルダーとしてより好適なものとなる。メタクリル酸由来の構造単位の含有割合は、より好ましくは、２５〜７０質量％であり、更に好ましくは、３０〜６０質量％である。
また、該メタクリル酸系重合体におけるメタクリル酸エステル由来の構造単位の含有割合は、メタクリル酸系重合体の全構造単位１００質量％に対して、２０〜８０質量％であることが好ましい。このような割合で含むことで、硫黄含有重合体が洗剤ビルダーとしてより好適なものとなる。メタクリル酸エステル由来の構造単位の含有割合は、より好ましくは、３０〜７５質量％であり、更に好ましくは、４０〜７０質量％である。
なお、本発明において、メタクリル酸由来の構造単位は、メタクリル酸塩由来の構造単位であってもよい。その場合の塩としては、リチウム、ナトリウム、カリウム等の一価金属塩；カルシウム、マグネシウム等の二価金属塩；アンモニウム塩；およびエタノールアミン、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、トリエチルアミン等の有機アミン塩が挙げられる。
The sulfur-containing polymer in the present invention is a methacrylic acid-based polymer containing a methacrylic acid-derived structural unit and a methacrylic acid ester-derived structural unit.
The content ratio of the structural unit derived from methacrylic acid in the methacrylic acid-based polymer is preferably 20 to 80% by mass based on 100% by mass of all the structural units of the methacrylic acid-based polymer. By including it in such a ratio, the sulfur-containing polymer becomes more suitable as a detergent builder. The content ratio of the structural unit derived from methacrylic acid is more preferably 25 to 70% by mass, further preferably 30 to 60% by mass.
Further, the content ratio of the structural unit derived from the methacrylic acid ester in the methacrylic acid-based polymer is preferably 20 to 80% by mass based on 100% by mass of all the structural units of the methacrylic acid-based polymer. By including it in such a ratio, the sulfur-containing polymer becomes more suitable as a detergent builder. The content ratio of the structural unit derived from methacrylic acid ester is more preferably 30 to 75% by mass, further preferably 40 to 70% by mass.
In the present invention, the structural unit derived from methacrylic acid may be a structural unit derived from methacrylic acid salt. In that case, the salts include monovalent metal salts such as lithium, sodium and potassium; divalent metal salts such as calcium and magnesium; ammonium salts; and organic alkanolamines such as ethanolamine, diethanolamine and triethanolamine, and triethylamine. Amine salts may be mentioned.
上記メタクリル酸系重合体におけるメタクリル酸由来の構造単位の含有割合は、メタクリル酸系重合体の全構造単位１００モル％に対して、５０〜９９モル％であることが好ましい。このような割合で含むことで、硫黄含有重合体が洗剤ビルダーとしてより好適なものとなる。メタクリル酸由来の構造単位の含有割合は、より好ましくは、６０〜９８モル％であり、更に好ましくは、７０〜９７モル％である。
また、該メタクリル酸系重合体におけるメタクリル酸エステル由来の構造単位の含有割合は、メタクリル酸系重合体の全構造単位１００モル％に対して、１〜５０モル％であることが好ましい。このような割合で含むことで、硫黄含有重合体が洗剤ビルダーとしてより好適なものとなる。メタクリル酸エステル由来の構造単位の含有割合は、より好ましくは、２〜４０モル％であり、更に好ましくは、３〜３０モル％である。
The content ratio of the structural unit derived from methacrylic acid in the methacrylic acid-based polymer is preferably 50 to 99 mol% with respect to 100 mol% of all the structural units of the methacrylic acid-based polymer. By including it in such a ratio, the sulfur-containing polymer becomes more suitable as a detergent builder. The content ratio of the structural unit derived from methacrylic acid is more preferably 60 to 98 mol%, further preferably 70 to 97 mol%.
The content ratio of the structural unit derived from methacrylic acid ester in the methacrylic acid-based polymer is preferably 1 to 50 mol% based on 100 mol% of all the structural units of the methacrylic acid-based polymer. By including it in such a ratio, the sulfur-containing polymer becomes more suitable as a detergent builder. The content ratio of the structural unit derived from a methacrylic acid ester is more preferably 2 to 40 mol%, further preferably 3 to 30 mol%.
上記メタクリル酸エステルとしては、メチルメタクリレート、エチルメタクリレート、プロピルメタクリレート、イソプロピルメタクリレート、ブチルメタクリレート、イソブチルメタクリレート、ｔｅｒｔ−ブチルメタクリレート、ヒドロキシエチルメタクリレート、ヒドロキシプロピルメタクリレート等の置換基を有していてもよい炭素数１〜２０のアルキル基を有するアルキルメタクリレートや、下記式（１）で表される（アルコキシ）ポリアルキレングリコールメタクリレート等が挙げられる。なお、「（アルコキシ）ポリアルキレングリコールメタクリレート」とは、ポリアルキレングリコールメタクリレート及び／又はアルコキシポリアルキレングリコールメタクリレートを意味する。
上記置換基としては、水酸基、カルボキシル基、スルホン基、アミン基等が挙げられる。
As the methacrylic acid ester, the number of carbon atoms that may have a substituent such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate. Examples thereof include alkyl methacrylates having 1 to 20 alkyl groups and (alkoxy)polyalkylene glycol methacrylates represented by the following formula (1). In addition, "(alkoxy) polyalkylene glycol methacrylate" means polyalkylene glycol methacrylate and/or alkoxy polyalkylene glycol methacrylate.
Examples of the substituent include a hydroxyl group, a carboxyl group, a sulfone group, an amine group and the like.
（式中、Ｒ１は、同一又は異なって、炭素数１〜５のアルキレン基を表す。Ｒ２は、水素原子又は炭素数１〜２０のアルキル基を表す。ｎは、１〜７０の数を表す。）
上記式（１）におけるＲ１としては、炭素数１〜４のアルキレン基が好ましい。より好ましくは、炭素数１〜３のアルキレン基であり、更に好ましくは、炭素数２〜３のアルキレン基、最も好ましくは、炭素数２のアルキレン基、すなわち、エチレン基である。
上記式（１）におけるＲ２の炭素数１〜２０のアルキル基としては、炭素数１〜１２のアルキル基が好ましい。より好ましくは、炭素数１〜８のアルキル基であり、更に好ましくは、炭素数１〜４のアルキル基であり、更に好ましくは、炭素数１〜３のアルキル基であり、最も好ましくは、炭素数１〜２のアルキル基である。
上記式（１）におけるｎは、１〜５０であることが好ましい。より好ましくは、３〜４０であり、更に好ましくは、５〜３０である。
(In the formula, R 1 is the same or different and represents an alkylene group having 1 to 5 carbon atoms. R 2 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. n is a number of 1 to 70. Represents.)
As R 1 in the above formula (1), an alkylene group having 1 to 4 carbon atoms is preferable. More preferably, it is an alkylene group having 1 to 3 carbon atoms, still more preferably an alkylene group having 2 to 3 carbon atoms, and most preferably an alkylene group having 2 carbon atoms, that is, an ethylene group.
As the alkyl group having 1 to 20 carbon atoms for R 2 in the above formula (1), an alkyl group having 1 to 12 carbon atoms is preferable. More preferably, it is an alkyl group having 1 to 8 carbon atoms, further preferably an alkyl group having 1 to 4 carbon atoms, further preferably an alkyl group having 1 to 3 carbon atoms, and most preferably carbon. It is an alkyl group of the numbers 1-2.
N in the above formula (1) is preferably 1 to 50. It is more preferably 3 to 40, further preferably 5 to 30.
上記式（１）で表される（アルコキシ）ポリアルキレングリコールメタクリレートの具体例としては、（メトキシ）ポリエチレングリコールメタクリレート、（メトキシ）ポリプロピレングリコールメタクリレート、（メトキシ）ポリブチレングリコールメタクリレート、（メトキシ）ポリエチレングリコールポリプロピレングリコールメタクリレート、（メトキシ）ポリエチレングリコールポリブチレングリコールメタクリレート、（メトキシ）ポリプロピレングリコールポリブチレングリコールメタクリレート、（メトキシ）ポリエチレングリコールポリプロピレングリコールポリブチレングリコールメタクリレート、（エトキシ）ポリエチレングリコールメタクリレート、（エトキシ）ポリプロピレングリコールメタクリレート、（エトキシ）ポリブチレングリコールメタクリレート、（エトキシ）ポリエチレングリコールポリプロピレングリコールメタクリレート、（エトキシ）ポリエチレングリコールポリブチレングリコールメタクリレート、（エトキシ）ポリプロピレングリコールポリブチレングリコールメタクリレート、および（エトキシ）ポリエチレングリコールポリプロピレングリコールポリブチレングリコールメタクリレート等が挙げられる。 Specific examples of the (alkoxy) polyalkylene glycol methacrylate represented by the above formula (1) include (methoxy) polyethylene glycol methacrylate, (methoxy) polypropylene glycol methacrylate, (methoxy) polybutylene glycol methacrylate and (methoxy) polyethylene glycol polypropylene. Glycol methacrylate, (Methoxy) polyethylene glycol polybutylene glycol methacrylate, (methoxy) polypropylene glycol polybutylene glycol methacrylate, (methoxy) polyethylene glycol polypropylene glycol polybutylene glycol methacrylate, (ethoxy) polyethylene glycol methacrylate, (ethoxy) polypropylene glycol methacrylate, ( (Ethoxy) polybutylene glycol methacrylate, (ethoxy) polyethylene glycol polypropylene glycol methacrylate, (ethoxy) polyethylene glycol polybutylene glycol methacrylate, (ethoxy) polypropylene glycol polybutylene glycol methacrylate, and (ethoxy) polyethylene glycol polypropylene glycol polybutylene glycol methacrylate Can be mentioned.
本発明における硫黄含有重合体は、メタクリル酸由来の構造単位とメタクリル酸エステル由来の構造単位のみからなるものであってもよく、その他の単量体由来の構造単位を含んでいてもよい。
その他の単量体としては、アクリル酸、プロピオン酸、マレイン酸、フマル酸、シトラコン酸等の炭素数３〜１０の不飽和カルボン酸又はその塩；（メタ）アクリルアミド、（メタ）アクリルアルキルアミドなどの炭素数２〜１０の不飽和アミド；スチレン等の炭素数８〜１５の芳香族ビニル；ビニルスルホン酸、スチレンスルホン酸、（メタ）アリルスルホン酸、（メタ）アクリルアミド−２−メチルプロパンスルホン酸、２−ヒドロキシ−３−（メタ）アリルオキシプロパンスルホン酸ナトリウム、イソプレンスルホン酸、スルホエチル（メタ）アクリレート、スルホプロピル（メタ）アクリレート、２−ヒドロキシ−３−ブテンスルホン酸等の炭素数２〜２０の不飽和スルホン酸又はその塩；３−（メタ）アリルオキシ−１，２−ジヒドロキシプロパン、３−アリルオキシ−１，２−ジヒドロキシプロパン、３−アリルオキシ−１，２−ジヒドロキシプロパン、（メタ）アリルアルコール、イソプレノール等の水酸基含有不飽和単量体にエチレンオキサイドを６〜２００モル付加させた化合物（３−アリルオキシ−１，２−ジ（ポリ）オキシエチレンエーテルプロパン等）等が挙げられ、これらの１種又は２種以上を用いることができる。
不飽和カルボン酸や不飽和スルホン酸の塩としては、上述したメタクリル酸塩と同様の塩が挙げられる。
The sulfur-containing polymer in the present invention may consist only of a structural unit derived from methacrylic acid and a structural unit derived from a methacrylic acid ester, or may contain structural units derived from other monomers.
Other monomers include unsaturated carboxylic acids having 3 to 10 carbon atoms such as acrylic acid, propionic acid, maleic acid, fumaric acid and citraconic acid, or salts thereof; (meth)acrylamide, (meth)acrylalkylamide, etc. An unsaturated amide having 2 to 10 carbon atoms; an aromatic vinyl having 8 to 15 carbon atoms such as styrene; vinyl sulfonic acid, styrene sulfonic acid, (meth)allyl sulfonic acid, (meth)acrylamido-2-methylpropane sulfonic acid , Sodium 2-hydroxy-3-(meth)allyloxypropane sulfonate, isoprene sulfonic acid, sulfoethyl (meth)acrylate, sulfopropyl (meth)acrylate, 2-hydroxy-3-butene sulfonic acid and the like having 2 to 20 carbon atoms. Unsaturated sulfonic acids or salts thereof; 3-(meth)allyloxy-1,2-dihydroxypropane, 3-allyloxy-1,2-dihydroxypropane, 3-allyloxy-1,2-dihydroxypropane, (meth)allyl alcohol , A compound obtained by adding 6 to 200 mol of ethylene oxide to a hydroxyl group-containing unsaturated monomer such as isoprenol (3-allyloxy-1,2-di(poly)oxyethylene ether propane etc.) and the like. One kind or two or more kinds can be used.
Examples of the salts of unsaturated carboxylic acids and unsaturated sulfonic acids include the same salts as the above-mentioned methacrylates.
上記その他の単量体由来の構造単位の含有割合は、メタクリル酸系重合体の全構造単位１００質量％に対して、３０質量％以下であることが好ましい。より好ましくは、２０質量％以下であり、更に好ましくは、１０質量％以下である。
また上記その他の単量体由来の構造単位の含有割合は、メタクリル酸系重合体の全構造単位１００モル％に対して、３０モル％以下であることが好ましい。より好ましくは、２０モル％以下であり、更に好ましくは、１０モル％以下である。
The content ratio of the structural unit derived from the other monomer is preferably 30% by mass or less based on 100% by mass of all structural units of the methacrylic acid-based polymer. It is more preferably 20% by mass or less, and further preferably 10% by mass or less.
The content ratio of the structural units derived from the other monomers is preferably 30 mol% or less based on 100 mol% of all structural units of the methacrylic acid polymer. It is more preferably 20 mol% or less, and further preferably 10 mol% or less.
本発明における硫黄含有重合体は、重量平均分子量が５０００〜２０００００であることが好ましい。このような分子量であると、洗剤用途により好適なものとなる。硫黄含有重合体の重量平均分子量は、より好ましくは、１００００〜１０００００であり、更に好ましくは、２００００〜８００００であり、特に好ましくは、３００００〜６００００である。
硫黄含有重合体の重量平均分子量は、ＧＰＣにより、後述する実施例に記載の条件により測定することができる。
The sulfur-containing polymer in the present invention preferably has a weight average molecular weight of 5,000 to 200,000. Such a molecular weight is more suitable for detergent applications. The weight average molecular weight of the sulfur-containing polymer is more preferably 10,000 to 100,000, further preferably 20,000 to 80,000, and particularly preferably 30,000 to 60,000.
The weight average molecular weight of the sulfur-containing polymer can be measured by GPC under the conditions described in Examples described later.
本発明の硫黄含有重合体組成物は、上記硫黄含有重合体とは異なる硫黄含有化合物（以下においては、単に硫黄含有化合物とも記載する）を含む。該硫黄含有化合物は、構造中に硫黄原子を含む化合物である限り、その構造は特に制限されないが、硫黄含有化合物が硫黄含有重合体を製造する際に使用される連鎖移動剤由来の化合物であることは、本発明の硫黄含有重合体組成物の好適な形態の１つである。後述するように、連鎖移動剤として使用できる化合物の中には、亜硫酸水素ナトリウムをはじめとして構造中に硫黄原子を含むものがあり、それらを連鎖移動剤として使用した場合には、得られる硫黄含有重合体組成物がそれらの化合物由来の硫黄含有化合物を含むことになる。中でも、後述するように本発明の硫黄含有重合体組成物は、単量体成分とともに亜硫酸水素ナトリウムを使用して重合反応を行うことで製造されることが好ましい。この場合、得られる硫黄含有重合体組成物は、硫黄含有化合物として硫酸ナトリウムを含むものとなる。したがって、該硫黄含有化合物が硫酸ナトリウムであることは本発明の硫黄含有重合体組成物の好適な形態の１つある。 The sulfur-containing polymer composition of the present invention contains a sulfur-containing compound different from the above-mentioned sulfur-containing polymer (hereinafter, also simply referred to as a sulfur-containing compound). The structure of the sulfur-containing compound is not particularly limited as long as it is a compound containing a sulfur atom in the structure, but the sulfur-containing compound is a compound derived from a chain transfer agent used in producing a sulfur-containing polymer. This is one of the preferable forms of the sulfur-containing polymer composition of the present invention. As will be described later, among compounds that can be used as a chain transfer agent, there are those containing a sulfur atom in the structure including sodium bisulfite, and when they are used as a chain transfer agent, the sulfur-containing compound obtained is obtained. The polymer composition will include sulfur-containing compounds derived from those compounds. Among them, as described later, the sulfur-containing polymer composition of the present invention is preferably produced by carrying out a polymerization reaction using sodium bisulfite together with the monomer component. In this case, the obtained sulfur-containing polymer composition contains sodium sulfate as the sulfur-containing compound. Therefore, it is one of the preferable forms of the sulfur-containing polymer composition of the present invention that the sulfur-containing compound is sodium sulfate.
本発明の硫黄含有重合体組成物は、構造中に硫黄原子を含む硫黄含有重合体、該硫黄含有重合体とは異なる硫黄含有化合物、及び、溶媒以外のその他の成分を含んでいてもよい。その他の成分としては、未反応の単量体、重合促進剤等が挙げられる。
本発明の硫黄含有重合体組成物におけるその他の成分の含有割合は、硫黄含有重合体組成物全体１００質量％に対して、３質量％以下であることが好ましい。より好ましくは、２質量％以下であり、更に好ましくは、１質量％以下である。
The sulfur-containing polymer composition of the present invention may contain a sulfur-containing polymer having a sulfur atom in the structure, a sulfur-containing compound different from the sulfur-containing polymer, and other components other than the solvent. Other components include unreacted monomers, polymerization accelerators and the like.
The content ratio of the other components in the sulfur-containing polymer composition of the present invention is preferably 3% by mass or less based on 100% by mass of the entire sulfur-containing polymer composition. It is more preferably 2% by mass or less, and even more preferably 1% by mass or less.
本発明の硫黄含有重合体組成物は、固形分濃度が２０〜７０質量％であることが好ましい。より好ましくは、２５〜６５質量％であり、更に好ましくは、３０〜６０質量％である。固形分濃度がこのような範囲であると、生産性を損なわず、また反応溶液の粘度上昇を抑えることで取扱い性が向上する。
硫黄含有重合体組成物の固形分濃度は、実施例に記載の方法により測定することができる。
本発明の硫黄含有重合体組成物が含む溶媒としては、後述する硫黄含有重合体組成物の製造時に使用されるが挙げられる。
The sulfur-containing polymer composition of the present invention preferably has a solid content concentration of 20 to 70% by mass. It is more preferably 25 to 65% by mass, and further preferably 30 to 60% by mass. When the solid content concentration is in such a range, the productivity is not impaired and the handleability is improved by suppressing the increase in the viscosity of the reaction solution.
The solid content concentration of the sulfur-containing polymer composition can be measured by the method described in Examples.
Examples of the solvent contained in the sulfur-containing polymer composition of the present invention include those used during the production of the sulfur-containing polymer composition described later.
上述したように、本発明の硫黄含有重合体組成物は、洗剤組成物に対する配合安定性が高い組成物であることから、洗剤用途に好適に用いることができる。このように、本発明の硫黄含有重合体組成物が、洗剤用途に用いられることは本発明の好適な実施形態の１つである。更に、本発明の硫黄含有重合体組成物を含む洗剤組成物もまた、本発明の１つである。
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、洗剤分野において一般的に知られているものを用いることができる。また、上記洗剤組成物は、粉末洗剤組成物であってもよいし、液体洗剤組成物であってもよい。
As described above, the sulfur-containing polymer composition of the present invention is a composition having high compounding stability with respect to a detergent composition, and thus can be suitably used for detergent applications. As described above, it is one of the preferred embodiments of the present invention that the sulfur-containing polymer composition of the present invention is used for detergent applications. Further, a detergent composition containing the sulfur-containing polymer composition of the present invention is also one of the present invention.
The detergent composition usually contains surfactants and additives used in detergents. The specific form of these surfactants and additives is not particularly limited, and those generally known in the detergent field can be used. The detergent composition may be a powder detergent composition or a liquid detergent composition.
本発明の硫黄含有重合体組成物を製造する方法は特に制限されないが、メタクリル酸とメタクリル酸エステルとを含む単量体成分に対して、亜硫酸水素ナトリウムを０．１〜６ｇ／ｍｏｌの割合で使用して重合反応を行う工程を含む方法が好ましい。このようにすると、本発明の重合体の構造中に含まれる硫黄原子の割合及び硫黄含有化合物の含有量を満たす硫黄含有重合体組成物を簡便に製造することができる。
このような硫黄含有重合体組成物の製造方法、すなわち、構造中に硫黄原子を含む硫黄含有重合体と、該硫黄含有重合体とは異なる硫黄含有化合物とを含む硫黄含有重合体組成物を製造する方法であって、該製造方法は、メタクリル酸とメタクリル酸エステルとを含む単量体成分を原料とし、該単量体成分に含まれる単量体に対して、亜硫酸水素ナトリウムを０．１〜６ｇ／ｍｏｌの割合で使用して重合反応を行う工程を含むことを特徴とする硫黄含有重合体組成物の製造方法もまた、本発明の１つである。
The method for producing the sulfur-containing polymer composition of the present invention is not particularly limited, but sodium bisulfite is added at a ratio of 0.1 to 6 g/mol to a monomer component containing methacrylic acid and a methacrylic acid ester. A method comprising the step of carrying out a polymerization reaction is preferred. By doing so, a sulfur-containing polymer composition satisfying the ratio of the sulfur atom contained in the structure of the polymer of the present invention and the content of the sulfur-containing compound can be easily produced.
A method for producing such a sulfur-containing polymer composition, that is, a sulfur-containing polymer composition containing a sulfur-containing polymer containing a sulfur atom in the structure and a sulfur-containing compound different from the sulfur-containing polymer In the method for producing, a monomer component containing methacrylic acid and a methacrylic acid ester is used as a raw material, and sodium bisulfite is added to the monomer contained in the monomer component at 0.1%. A method for producing a sulfur-containing polymer composition, which comprises the step of carrying out a polymerization reaction at a rate of ˜6 g/mol, is also one aspect of the present invention.
本発明の硫黄含有重合体組成物の製造方法は、メタクリル酸とメタクリル酸エステルとを含む単量体成分に含まれる全単量体に対して、亜硫酸水素ナトリウムを０．１〜６ｇ／ｍｏｌの割合で使用して重合反応を行う工程を含む。亜硫酸水素ナトリウムは、連鎖移動剤としてはたらくものであり、亜硫酸水素ナトリウムを使用して重合反応を行うことで、重合体の主鎖末端に硫黄原子を含む構造部位を有する重合体を得ることができる。また、反応後の重合体には、亜硫酸水素ナトリウム由来の硫酸ナトリウムが含まれることになる。
本発明の硫黄含有重合体組成物の製造方法の重合工程に使用される亜硫酸水素ナトリウムの割合は、単量体成分に含まれる全単量体に対して１〜５ｇ／ｍｏｌであることが好ましい。より好ましくは、１．５〜４．５ｇ／ｍｏｌであり、更に好ましくは、２〜４ｇ／ｍｏｌである。
なお、本発明でいう「単量体成分に含まれる単量体に対して」とは、単量体成分に含まれる全ての単量体の合計を意味する。
In the method for producing a sulfur-containing polymer composition of the present invention, sodium bisulfite is added in an amount of 0.1 to 6 g/mol based on all the monomers contained in the monomer component containing methacrylic acid and methacrylic acid ester. It is used in a ratio to carry out a polymerization reaction. Sodium bisulfite acts as a chain transfer agent, and by carrying out a polymerization reaction using sodium bisulfite, a polymer having a structural site containing a sulfur atom at the main chain terminal of the polymer can be obtained. .. Further, the polymer after the reaction contains sodium sulfate derived from sodium hydrogen sulfite.
The proportion of sodium hydrogen sulfite used in the polymerization step of the method for producing a sulfur-containing polymer composition of the present invention is preferably 1 to 5 g/mol with respect to all monomers contained in the monomer component. .. The amount is more preferably 1.5 to 4.5 g/mol, and further preferably 2 to 4 g/mol.
The term “relative to the monomer contained in the monomer component” in the present invention means the sum of all the monomers contained in the monomer component.
上記重合工程は、亜硫酸水素ナトリウムに加え、それ以外の連鎖移動剤を用いて行ってもよい。それ以外の連鎖移動剤としては、メルカプトエタノール、チオグリセロール、チオグリコール酸、２−メルカプトプロピオン酸、３−メルカプトプロピオン酸、チオリンゴ酸、チオグリコール酸オクチル、３−メルカプトプロピオン酸オクチル、２−メルカプトエタンスルホン酸、ｎ−ドデシルメルカプタン、オクチルメルカプタン、ブチルチオグリコレート等の、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ナトリウム塩やカリウム塩；亜硫酸、亜二チオン酸、メタ重亜硫酸及びそのナトリウム塩やカリウム塩等が挙げられる。
亜硫酸水素ナトリウム以外の連鎖移動剤を用いる場合、亜硫酸水素ナトリウムとそれ以外の連鎖移動剤の使用量の合計が単量体成分に含まれる単量体に対して１〜２０ｇ／ｍｏｌとなることが好ましい。より好ましくは、２〜１５ｇ／ｍｏｌとなることである。
The above polymerization step may be performed using a chain transfer agent other than sodium bisulfite. Other chain transfer agents include mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, octyl thioglycolate, octyl 3-mercaptopropionic acid, 2-mercaptoethane. Thiol chain transfer agents such as sulfonic acid, n-dodecyl mercaptan, octyl mercaptan, and butylthioglycolate; halides such as carbon tetrachloride, methylene chloride, bromoform, and bromotrichloroethane; secondary compounds such as isopropanol and glycerin. Examples thereof include alcohols; phosphorous acid, hypophosphorous acid, and sodium salts and potassium salts thereof; sulfurous acid, dithionous acid, metabisulfite, and sodium salts and potassium salts thereof.
When a chain transfer agent other than sodium bisulfite is used, the total amount of sodium bisulfite and the other chain transfer agent used may be 1 to 20 g/mol with respect to the monomer contained in the monomer component. preferable. It is more preferably 2 to 15 g/mol.
上記重合工程では、亜硫酸水素ナトリウムに加え、それ以外の連鎖移動剤を用いて行ってもよいが、亜リン酸、次亜リン酸及びそのナトリウム塩やカリウム塩等のリン原子含有化合物の使用量が単量体成分に含まれる単量体に対して０．５ｇ／ｍｏｌ以下であることが好ましい。リン原子含有化合物の使用量が０．５ｇ／ｍｏｌ以下であることで、得られる硫黄含有重合体組成物に含まれるリン成分の含有量が充分に低くなり、環境への負荷が低く、洗剤用途により好適な組成物となる。リン原子含有化合物の使用量はより好ましくは、０〜０．３ｇ／ｍｏｌである。最も好ましくは、０ｇ／ｍｏｌ、すなわち、リン原子含有化合物を使用しないことである。 In the polymerization step, in addition to sodium hydrogen sulfite, may be carried out using other chain transfer agents, the amount of phosphorous acid, hypophosphorous acid and the phosphorus atom-containing compound such as sodium salt or potassium salt thereof used Is preferably 0.5 g/mol or less with respect to the monomer contained in the monomer component. When the amount of the phosphorus atom-containing compound used is 0.5 g/mol or less, the content of the phosphorus component contained in the obtained sulfur-containing polymer composition is sufficiently low, the load on the environment is low, and the use as a detergent is possible. It becomes a more suitable composition. The amount of the phosphorus atom-containing compound used is more preferably 0 to 0.3 g/mol. Most preferably, 0 g/mol, that is, no phosphorus atom-containing compound is used.
上記メタクリル酸とメタクリル酸エステルとを含む単量体成分に含まれるメタクリル酸の割合は、単量体成分に含まれる全単量体１００質量％に対して、２０〜８０質量％であることが好ましい。より好ましくは、２５〜７０質量％であり、更に好ましくは、３０〜６０質量％である。
また、単量体成分に含まれるメタクリル酸エステルの割合は、単量体成分に含まれる全単量体１００質量％に対して、２０〜８０質量％であることが好ましい。より好ましくは、３０〜７５質量％であり、更に好ましくは、４０〜７０質量％である。
またメタクリル酸とメタクリル酸エステルとを含む単量体成分は、メタクリル酸とメタクリル酸エステルとを含む限り、その他の単量体を含んでもよい。その他の単量体の割合は、単量体成分に含まれる全単量体１００質量％に対して、３０質量％以下であることが好ましい。より好ましくは、２０質量％以下であり、更に好ましくは、１０質量％以下である。
The proportion of methacrylic acid contained in the monomer component containing the methacrylic acid and the methacrylic acid ester may be 20 to 80 mass% with respect to 100 mass% of all the monomers contained in the monomer component. preferable. It is more preferably 25 to 70% by mass, and further preferably 30 to 60% by mass.
Further, the ratio of the methacrylic acid ester contained in the monomer component is preferably 20 to 80 mass% with respect to 100 mass% of all the monomers contained in the monomer component. It is more preferably 30 to 75% by mass, and further preferably 40 to 70% by mass.
Further, the monomer component containing methacrylic acid and methacrylic acid ester may contain other monomers as long as it contains methacrylic acid and methacrylic acid ester. The proportion of other monomers is preferably 30% by mass or less based on 100% by mass of all the monomers contained in the monomer component. It is more preferably 20% by mass or less, and further preferably 10% by mass or less.
上記メタクリル酸とメタクリル酸エステルとを含む単量体成分に含まれるメタクリル酸の割合は、単量体成分に含まれる全単量体１００モル％に対して、５０〜９９モル％であることが好ましい。より好ましくは、６０〜９８モル％であり、更に好ましくは、７０〜９７モル％である。
また、単量体成分に含まれるメタクリル酸エステルの割合は、単量体成分に含まれる全単量体１００モル％に対して、１〜５０モル％であることが好ましい。より好ましくは、２〜４０モル％であり、更に好ましくは、３〜３０モル％である。
またメタクリル酸とメタクリル酸エステルとを含む単量体成分は、メタクリル酸とメタクリル酸エステルとを含む限り、その他の単量体を含んでもよい。その他の単量体の割合は、単量体成分に含まれる全単量体１００モル％に対して、３０モル％以下であることが好ましい。より好ましくは、２０モル％以下であり、更に好ましくは、１０モル％以下である。
上記単量体成分に含まれるメタクリル酸エステルやその他の単量体の具体例や好ましい化合物は、上述した本発明における硫黄含有重合体のメタクリル酸エステル由来の構造単位を形成するメタクリル酸エステルやその他の単量体由来の構造単位を形成するその他の単量体の具体例や好ましい化合物と同様である。
The proportion of methacrylic acid contained in the monomer component containing methacrylic acid and methacrylic acid ester may be 50 to 99 mol% with respect to 100 mol% of all the monomers contained in the monomer component. preferable. It is more preferably 60 to 98 mol %, and even more preferably 70 to 97 mol %.
The ratio of the methacrylic acid ester contained in the monomer component is preferably 1 to 50 mol% with respect to 100 mol% of all the monomers contained in the monomer component. It is more preferably 2 to 40 mol %, still more preferably 3 to 30 mol %.
Further, the monomer component containing methacrylic acid and methacrylic acid ester may contain other monomers as long as it contains methacrylic acid and methacrylic acid ester. The proportion of the other monomers is preferably 30 mol% or less based on 100 mol% of all the monomers contained in the monomer component. It is more preferably 20 mol% or less, and further preferably 10 mol% or less.
Specific examples and preferred compounds of the methacrylic acid ester and other monomers contained in the above-mentioned monomer component are methacrylic acid ester and other which form a structural unit derived from the methacrylic acid ester of the sulfur-containing polymer in the present invention described above. This is the same as the specific examples and preferable compounds of other monomers forming the structural unit derived from the above monomer.
上記重合工程は、重合開始剤を用いて行ってもよい。重合開始剤としては、通常用いられるものを使用することができ、具体的には、過酸化水素；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；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−ブチルパーオキシド、クメンヒドロパーオキシド等の有機過酸化物等の１種又は２種以上を用いることができる。
重合開始剤の使用量は、単量体成分に含まれる単量体に対して１〜１２ｇ／ｍｏｌであることが好ましい。より好ましくは、２〜８ｇ／ｍｏｌである。
You may perform the said superposition|polymerization process using a superposition|polymerization initiator. As the polymerization initiator, those usually used can be used, and specifically, hydrogen peroxide; persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate; 2,2′-azobis(2 -Amidinopropane) hydrochloride, 4,4'-azobis-4-cyanoparellic acid, azobisisobutyronitrile, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) and other azo compounds One or more of organic peroxides such as benzoyl peroxide, lauroyl peroxide, peracetic acid, di-t-butyl peroxide and cumene hydroperoxide can be used.
The amount of the polymerization initiator used is preferably 1 to 12 g/mol with respect to the monomer contained in the monomer component. More preferably, it is 2 to 8 g/mol.
上記製造方法においては、重合開始剤等の使用量を低減する等の目的で反応促進剤（重合促進剤）を加えてもよい。反応促進剤としては、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、ルテニウム等の重金属イオンが挙げられ、これらの１種又は２種以上を用いることができる。反応促進剤を用いる場合、溶液中で溶解してこれらの重金属イオンを生成する金属化合物を用いることが取り扱い性の点から好ましく、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できる。中でも、モール塩を用いることは、本発明の硫黄含有重合体組成物の製造方法の好適な形態の１つである。
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、取り扱い性に優れたものとなる。
反応促進剤の使用量は、反応液全量に対して１〜１００ｐｐｍとなる量であることが好ましく、より好ましくは１０〜７０ｐｐｍとなる量である。
In the above production method, a reaction accelerator (polymerization accelerator) may be added for the purpose of reducing the amount of the polymerization initiator or the like used. Examples of the reaction accelerator include heavy metal ions such as iron, cobalt, manganese, chromium, molybdenum, tungsten, copper, silver, gold, lead, platinum, iridium, osmium, palladium, rhodium and ruthenium. One kind or two or more kinds can be used. When a reaction accelerator is used, it is preferable to use a metal compound that dissolves in a solution to generate these heavy metal ions from the viewpoint of handleability. When iron is used as the heavy metal ion, Mohr salt (Fe(NH 4 ) 2 (SO 4) 2 · 6H 2 O), ferrous sulfate heptahydrate, ferrous chloride, can be used a heavy metal compounds such as ferric chloride. Among them, using Mohr's salt is one of the preferable modes of the method for producing the sulfur-containing polymer composition of the present invention.
When manganese is used as the heavy metal ion, manganese chloride or the like can be preferably used. Since all of these are water-soluble compounds, they can be used in the form of an aqueous solution and have excellent handleability.
The amount of the reaction accelerator used is preferably 1 to 100 ppm, more preferably 10 to 70 ppm, based on the total amount of the reaction solution.
上記重合工程は、溶媒を用いて行ってもよい。その場合の溶媒としては、水、アルコール、グリコール、グリセリン、ポリエチレングリコール類等の水性の溶媒の１種又は２種以上を用いることができる。中でも、水が好ましい。
溶媒の使用量は、単量体成分に含まれる単量体１００質量％に対して、４０〜３００質量％であることが好ましい。より好ましくは、４５〜２５０質量％である。溶媒の使用量が全単量体の総量１００質量％に対して４０質量％未満の場合には、得られる重合体の分子量が高くなりすぎるおそれがあり、３００質量％を超える場合には、重合工程後に場合によっては溶媒除去が必要となるおそれがある。
You may perform the said superposition|polymerization process using a solvent. As the solvent in that case, one or two or more kinds of aqueous solvents such as water, alcohol, glycol, glycerin, and polyethylene glycols can be used. Of these, water is preferred.
The amount of the solvent used is preferably 40 to 300 mass% with respect to 100 mass% of the monomer contained in the monomer component. More preferably, it is 45 to 250 mass %. When the amount of the solvent used is less than 40% by mass relative to 100% by mass of the total amount of all monomers, the molecular weight of the resulting polymer may be too high, and when it exceeds 300% by mass, polymerization may occur. In some cases, it may be necessary to remove the solvent after the step.
上記単量体成分、重合開始剤、連鎖移動剤、反応促進剤は、いずれも反応容器に一括添加してもよく、逐次添加してもよいが、得られる重合体の分子量分布を狭く（シャープに）することができることから、逐次添加することが好ましい。 The above-mentioned monomer component, polymerization initiator, chain transfer agent, and reaction accelerator may all be added to the reaction vessel all at once or may be added sequentially, but the molecular weight distribution of the resulting polymer is narrow (sharp). It is preferable to add them sequentially.
上記重合工程における重合反応の温度は、２５〜２００℃であることが好ましい。より好ましくは、５０〜１５０℃である。
また、重合工程における重合反応の時間は、３０〜４２０分であることが好ましい。より好ましくは、６０〜３６０分である。
重合工程は、常圧（大気圧）下、減圧下、加圧下のいずれの条件で行ってもよく、反応系内の雰囲気は、空気雰囲気のままで行ってもよいし、不活性ガス雰囲気としてもよい。
The temperature of the polymerization reaction in the polymerization step is preferably 25 to 200°C. More preferably, it is 50 to 150°C.
Further, the polymerization reaction time in the polymerization step is preferably 30 to 420 minutes. More preferably, it is 60 to 360 minutes.
The polymerization step may be performed under any conditions of normal pressure (atmospheric pressure), reduced pressure, and increased pressure, and the atmosphere in the reaction system may be an air atmosphere or an inert gas atmosphere. Good.
本発明の硫黄含有重合体組成物の製造方法は、上記重合工程以外のその他の工程を含んでいてもよい。その他の工程としては、熟成工程、中和工程等が挙げられる。
熟成工程を行う場合、熟成時間は、好ましくは１〜１２０分間、より好ましくは５〜９０分間、更に好ましくは３０〜６０分間である。熟成時間が１分間未満の場合には、熟成が不十分なために単量体成分が残存することがあり、残存モノマーに起因する不純物によって性能低下等を招くおそれがある。熟成時間が１２０分間を超える場合には、重合体溶液の着色のおそれがある。
The method for producing the sulfur-containing polymer composition of the present invention may include other steps than the above-mentioned polymerization step. Examples of other steps include an aging step and a neutralization step.
When the aging step is performed, the aging time is preferably 1 to 120 minutes, more preferably 5 to 90 minutes, and further preferably 30 to 60 minutes. When the aging time is less than 1 minute, the monomer component may remain because the aging is insufficient, and the impurities resulting from the remaining monomer may cause performance deterioration. If the aging time exceeds 120 minutes, the polymer solution may be colored.
中和工程を行う場合に用いられるアルカリ成分としては例えば、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属の水酸化物；水酸化カルシウム、水酸化マグネシウムなどのアルカリ土類金属の水酸化物；アンモニア；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などの有機アミン類；などが挙げられる。このようなアルカリ成分は、１種のみを用いても良いし、２種以上を用いても良い。また重合体の中和度は、好ましくは１モル％〜１００モル％であり、より好ましくは３０モル％〜９９モル％であり、最も好ましくは５０モル％〜９５モル％である。 Examples of the alkali component used in the neutralization step include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; ammonia. Organic amines such as monoethanolamine, diethanolamine and triethanolamine; and the like. Such alkali components may be used alone or in combination of two or more. The degree of neutralization of the polymer is preferably 1 mol% to 100 mol%, more preferably 30 mol% to 99 mol%, and most preferably 50 mol% to 95 mol%.
本発明の硫黄含有重合体組成物は、上述の構成よりなり、界面活性剤との相溶性が高く、洗剤組成物に対する配合安定性が高いことから、洗剤ビルダーとして好適に用いることができる。 The sulfur-containing polymer composition of the present invention has the above-mentioned constitution, has high compatibility with a surfactant, and has high compounding stability with respect to a detergent composition, and thus can be suitably used as a detergent builder.
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「重量部」を、「％」は「質量％」を意味するものとする。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "part" means "part by weight" and "%" means "mass %".
＜重量平均分子量の測定条件＞
下記条件にてＧＰＣ分析を行うことで測定した。
装置：東ソー社製ＨＬＣ−８３２０ＧＰＣ
検出器：ＲＩ
カラム：東ソー社製α−２５００、α−ｍ
カラム温度：４０℃
流速：０．５ｍｌ／ｍｉｎ．
検量線：ジーエルサイエンス（クラボウ社製）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）
<Measurement conditions for weight average molecular weight>
It was measured by performing GPC analysis under the following conditions.
Equipment: Tosoh HLC-8320GPC
Detector: RI
Column: Tosoh α-2500, α-m
Column temperature: 40°C
Flow rate: 0.5 ml/min.
Calibration curve: GL Sciences (Kurabo Co., Ltd.) POLYACRYLIC ACID STANDARD
Eluent: 0.1N sodium acetate/acetonitrile=3/1 (mass ratio)
＜重合体組成物の固形分測定方法＞
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１．０ｇ）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（％）を算出した。
<Method for measuring solid content of polymer composition>
The polymer composition (1.0 g of polymer composition+1.0 g of water) was left to stand in an oven heated to 130° C. for 1 hour to be dried. The solid content (%) was calculated from the weight change before and after drying.
＜ＳＯ３ ２−イオン濃度およびＳＯ４ ２−イオン濃度測定条件＞
下記条件にてイオンクロマト分析を行うことで測定した。
装置：東ソー社製 ＩＯＮＣＨＲＯＭＡＴＯＧＲＡＰＨ ＩＣ−２０１０
検出器：ＣＭ検出器
検出方法：電気伝導度検出器、４極電極法
イオン分析方式：サプレッサー法
カラム：Ｓｈｏｄｅｘ ＩＣ ＳＩ−９０ ４Ｅ
ガードカラム：Ｓｈｏｄｅｘ ＳＩ−９０ Ｇ
カラム温度：２５℃
溶離液：１ｍＭ Ｎａ２ＣＯ３＋４ｍＭ ＮａＨＣＯ３＋５％アセトン
流速：１．２ｍＬ／ｍｉｎ．
<SO 3 2- ion concentration and SO 4 2- ion concentration measurement conditions>
It was measured by performing ion chromatography analysis under the following conditions.
Device: Tosoh IONCHROMATO GRAPH IC-2010
Detector: CM detector Detection method: electric conductivity detector, quadrupole electrode method, ion analysis method: suppressor method Column: Shodex IC SI-904E
Guard column: Shodex SI-90 G
Column temperature: 25°C
Eluent: 1 mM Na 2 CO 3 +4 mM NaHCO 3 +5% acetone Flow rate: 1.2 mL/min.
＜硫黄含有化合物の含有割合の算出方法＞
硫黄含有化合物の含有割合は以下の計算より算出される。
<Calculation method of content ratio of sulfur-containing compound>
The content ratio of the sulfur-containing compound is calculated by the following calculation.
＜ＩＣＰによる重合体組成物中の硫黄量分析＞
重合体組成物中の硫黄量を誘導結合プラズマ（Ｉｎｄｕｃｔｉｖｅｌｙ Ｃｏｕｐｌｅｄ Ｐｌａｓｍａ，ＩＣＰ）発光分光分析法によって定量した。
装置：ＳＨＩＭＡＤＺＵ ＩＣＰＥ−９０００
測定波長：１８２．６２５ｎｍ
<Analysis of sulfur content in polymer composition by ICP>
The amount of sulfur in the polymer composition was quantified by inductively coupled plasma (ICP) emission spectroscopy.
Device: SHIMADZU ICPE-9000
Measurement wavelength: 182.625 nm
＜重合体の構造中に含まれる硫黄原子の割合算出方法＞
重合体の構造中に含まれる硫黄原子の割合は以下の計算より算出される。
<Method of calculating ratio of sulfur atoms contained in polymer structure>
The proportion of sulfur atoms contained in the polymer structure is calculated by the following calculation.
＜界面活性剤との相溶性の評価＞
以下に示す条件（１）および条件（２）の界面活性剤水溶液３ｇに重合体組成物０．３ｇ（固形分）を混合した後に１時間静置し、目視で確認して以下の基準により評価した。
濁りがない場合を◎、
やや濁っている場合を○、
濁っている場合を×とした。
濁りがないことは、重合体組成物を添加した洗剤が長期間に渡って均一に保たれうること
を示す。
条件（１）：ネオペレックスＧ−６５（花王社製）を３０．８ｇ秤量し、純水で希釈して、１００ｇの水溶液に調整したものを界面活性剤水溶液として使用した。
条件（２）：ネオペレックスＧ−１５（花王社製）を１５ｇ、ＮＣ２３２０（日本乳化剤社製）を１５ｇ秤量し、純水で希釈して、１００ｇの水溶液に調整したものを界面活性剤水溶液として使用した。
<Evaluation of compatibility with surfactant>
0.3 g of the polymer composition (solid content) was mixed with 3 g of the aqueous surfactant solution under the conditions (1) and (2) shown below, and the mixture was allowed to stand for 1 hour, visually confirmed, and evaluated according to the following criteria. did.
◎ if there is no turbidity,
○ when it is slightly cloudy
When it was cloudy, it was designated as x.
The absence of turbidity indicates that the detergent containing the polymer composition can be kept uniform over a long period of time.
Condition (1): 30.8 g of Neoperex G-65 (manufactured by Kao Corporation) was weighed, diluted with pure water, and adjusted to 100 g of an aqueous solution, which was used as a surfactant aqueous solution.
Condition (2): 15 g of Neoperex G-15 (manufactured by Kao Corporation) and 15 g of NC2320 (manufactured by Nippon Emulsifier Co., Ltd.) were weighed and diluted with pure water to prepare an aqueous solution of 100 g, which was used as a surfactant aqueous solution. used.
＜実施例１＞
還流冷却管、攪拌機を備えた容量５００ｍＬのガラス製セパラブルフラスコに純水１１０．９ｇ、モール塩０．００８ｇを仕込み、攪拌下８０℃に昇温した後、７０％メタクリル酸（以下、７０％ＭＡＡと略す。）１２３．０ｇ、１００％メタクリル酸メトキシポリエチレングリコール（ＥＯ鎖の平均付加モル数９モル、以下１００％ＰＧＭ−９ＥＯと略す）８６．１ｇ、４８％水酸化ナトリウム（以下４８％ＮａＯＨと略す）２５．０ｇ、１０％過硫酸ナトリウム水溶液（以下、１０％ＮａＰＳと略す。）３０．５ｇ、３５％亜硫酸水素ナトリウム水溶液（以下、３５％ＳＢＳと略す。）１１．７ｇ、純水１０．０ｇをそれぞれ別の滴下口より滴下した。それぞれの滴下時間は、７０％ＭＡＡが１８０分間、１００％ＰＧＭ−９ＥＯが１８０分間、４８％ＮａＯＨが１８０分間、１０％ＮａＰＳが２１０分間、３５％ＳＢＳが１８０分間、そして純水が１８０分間とした。なお、滴下開始はすべて同時とした。１０％ＮａＰＳ滴下終了までの間、温度は８０℃を維持した。さらに同温度を１０％ＮａＰＳ滴下終了後３０分間にわたって維持して熟成を行い、共重合体水溶液（１）を得た。
<Example 1>
A glass separable flask having a capacity of 500 mL equipped with a reflux condenser and a stirrer was charged with 110.9 g of pure water and 0.008 g of Mohr's salt, heated to 80° C. with stirring, and then 70% methacrylic acid (hereinafter, 70%). MAA) 123.0 g, 100% methoxypolyethylene glycol methacrylate (average number of moles of EO chain added: 9 mol, hereinafter 100% PGM-9EO) 86.1 g, 48% sodium hydroxide (48% NaOH) 25.0 g, 10% sodium persulfate aqueous solution (hereinafter abbreviated as 10% NaPS) 30.5 g, 35% sodium hydrogen sulfite aqueous solution (hereinafter abbreviated as 35% SBS) 11.7 g, pure water 10 0.0 g was added dropwise from separate dropping ports. 70% MAA for 180 minutes, 100% PGM-9EO for 180 minutes, 48% NaOH for 180 minutes, 10% NaPS for 210 minutes, 35% SBS for 180 minutes, and pure water for 180 minutes. did. The start of dropping was the same at all times. The temperature was maintained at 80° C. until the 10% NaPS dropping was completed. Further, the same temperature was maintained for 30 minutes after completion of the dropwise addition of 10% NaPS, and aging was carried out to obtain an aqueous copolymer solution (1).
＜実施例２＞
還流冷却管、攪拌機を備えた容量５００ｍＬのガラス製セパラブルフラスコに純水１２６．２ｇ、モール塩０．００９ｇを仕込み、攪拌下８０℃に昇温した後、７０％ＭＡＡ７３．８ｇ、８０％メタクリル酸メトキシポリエチレングリコール（ＥＯ鎖の平均付加モル数２３モル、以下８０％ＰＧＭ−２３ＥＯと略す）１５０．７ｇ、４８％ＮａＯＨ１５．０ｇ、８％ＮａＰＳ２３．２ｇ、３５％ＳＢＳ７．５ｇ、純水１０．０ｇをそれぞれ別の滴下口より滴下した。それぞれの滴下時間は、７０％ＭＡＡが１８０分間、８０％ＰＧＭ−２３ＥＯが１８０分間、４８％ＮａＯＨが１８０分間、８％ＮａＰＳが２１０分間、３５％ＳＢＳが１８０分間、そして純水が１８０分間とした。なお、滴下開始はすべて同時とした。８％ＮａＰＳ滴下終了までの間、温度は８０℃を維持した。さらに同温度を８％ＮａＰＳ滴下終了後３０分間にわたって維持して熟成を行い、共重合体水溶液（２）を得た。
<Example 2>
A glass separable flask having a capacity of 500 mL equipped with a reflux condenser and a stirrer was charged with 126.2 g of pure water and 0.009 g of Mohr's salt, heated to 80° C. with stirring, and then 73.8 g of 70% MAA and 80% methacryl. Acid methoxy polyethylene glycol (average number of moles of EO chain added: 23 moles, abbreviated as 80% PGM-23EO hereinafter) 150.7 g, 48% NaOH 15.0 g, 8% NaPS 23.2 g, 35% SBS 7.5 g, pure water 10. 0 g of each was dropped from different dropping ports. 70% MAA for 180 minutes, 80% PGM-23EO for 180 minutes, 48% NaOH for 180 minutes, 8% NaPS for 210 minutes, 35% SBS for 180 minutes, and pure water for 180 minutes. did. The start of dropping was the same at all times. The temperature was maintained at 80° C. until the dropping of 8% NaPS was completed. Further, the same temperature was maintained for 30 minutes after the dropping of 8% NaPS, and aging was carried out to obtain an aqueous copolymer solution (2).
＜実施例３＞
還流冷却管、攪拌機を備えた容量５００ｍＬのガラス製セパラブルフラスコに純水９０．０ｇ、モール塩０．００８ｇを仕込み、攪拌下８０℃に昇温した後、８０％ＭＡＡ１０７．６ｇ、８０％ＰＧＭ−２３ＥＯ１０７．６ｇ、４８％ＮａＯＨ１６．７ｇ、１０％ＮａＰＳ２８．１ｇ、３５％ＳＢＳ１０．８ｇ、純水１０．０ｇをそれぞれ別の滴下口より滴下した。それぞれの滴下時間は、８０％ＭＡＡが１８０分間、８０％ＰＧＭ−２３ＥＯが１８０分間、４８％ＮａＯＨが１８０分間、８％ＮａＰＳが２１０分間、３５％ＳＢＳが１８０分間、そして純水が１８０分間とした。なお、滴下開始はすべて同時とした。１０％ＮａＰＳ滴下終了までの間、温度は８０℃を維持した。さらに同温度を１０％ＮａＰＳ滴下終了後３０分間にわたって維持して熟成を行い、共重合体水溶液（３）を得た。
<Example 3>
A 500 mL glass separable flask equipped with a reflux condenser and a stirrer was charged with 90.0 g of pure water and 0.008 g of Mohr's salt, heated to 80° C. with stirring, and then 80% MAA 107.6 g, 80% PGM. -23EO, 107.6 g, 48% NaOH, 16.7 g, 10% NaPS, 28.1 g, 35% SBS, 10.8 g, and pure water, 10.0 g were added dropwise from separate dropping ports. 80% MAA for 180 minutes, 80% PGM-23EO for 180 minutes, 48% NaOH for 180 minutes, 8% NaPS for 210 minutes, 35% SBS for 180 minutes, and pure water for 180 minutes. did. The start of dropping was the same at all times. The temperature was maintained at 80° C. until the 10% NaPS dropping was completed. Further, the same temperature was maintained for 30 minutes after completion of the dropwise addition of 10% NaPS for aging to obtain an aqueous copolymer solution (3).
＜実施例４＞
還流冷却管、攪拌機を備えた容量５００ｍＬのガラス製セパラブルフラスコに純水９３．９ｇ、モール塩０．００７ｇを仕込み、攪拌下８０℃に昇温した後、７０％ＭＡＡ１２３．０ｇ、８０％ＰＧＭ−２３ＥＯ４６．１ｇ、４８％ＮａＯＨ２５．０ｇ、１０％ＮａＰＳ２６．９ｇ、３５％ＳＢＳ１０．３ｇ、純水１５．０ｇをそれぞれ別の滴下口より滴下した。それぞれの滴下時間は、７０％ＡＡが１８０分間、８０％ＰＧＭ−２３ＥＯが１８０分間、４８％ＮａＯＨが１８０分間、８％ＮａＰＳが２１０分間、３５％ＳＢＳが１８０分間、そして純水が１８０分間とした。なお、滴下開始はすべて同時とした。１０％ＮａＰＳ滴下終了までの間、温度は８０℃を維持した。さらに同温度を１０％ＮａＰＳ滴下終了後３０分間にわたって維持して熟成を行い、共重合体水溶液（４）を得た。
<Example 4>
A glass separable flask having a capacity of 500 mL equipped with a reflux condenser and a stirrer was charged with 93.9 g of pure water and 0.007 g of Mohr's salt, heated to 80° C. under stirring, and then 123.0 g of 70% MAA and 80% PGM. -23EO46.1 g, 48% NaOH 25.0 g, 10% NaPS 26.9 g, 35% SBS 10.3 g, and pure water 15.0 g were dropped from different dropping ports. The respective dropping times were 180% for 70% AA, 180 minutes for 80% PGM-23EO, 180 minutes for 48% NaOH, 210 minutes for 8% NaPS, 180 minutes for 35% SBS, and 180 minutes for pure water. did. The start of dropping was the same at all times. The temperature was maintained at 80° C. until the 10% NaPS dropping was completed. Further, the same temperature was maintained for 30 minutes after completion of the dropwise addition of 10% NaPS for aging to obtain an aqueous copolymer solution (4).
＜実施例５＞
還流冷却管、攪拌機を備えた容量５００ｍＬのガラス製セパラブルフラスコに純水１０２．６ｇ、モール塩０．００９ｇを仕込み、攪拌下８０℃に昇温した後、７０％ＭＡＡ１０４．５ｇ、５２％メタクリル酸メトキシポリエチレングリコール（ＥＯ鎖の平均付加モル数４５モル、以下ＰＧＭ−４５ＥＯと略す）１４２．１ｇ、４８％ＮａＯＨ２１．３ｇ、１０％ＮａＰＳ２３．３ｇ、３５％ＳＢＳ９．５ｇ、純水１０．０ｇをそれぞれ別の滴下口より滴下した。それぞれの滴下時間は、７０％ＡＡが１８０分間、５２％ＰＧＭ−４５ＥＯが１８０分間、４８％ＮａＯＨが１８０分間、８％ＮａＰＳが２１０分間、３５％ＳＢＳが１８０分間、そして純水が１８０分間とした。なお、滴下開始はすべて同時とした。１０％ＮａＰＳ滴下終了までの間、温度は８０℃を維持した。さらに同温度を１０％ＮａＰＳ滴下終了後３０分間にわたって維持して熟成を行い、共重合体水溶液（５）を得た。
<Example 5>
A glass separable flask having a capacity of 500 mL equipped with a reflux condenser and a stirrer was charged with 102.6 g of pure water and 0.009 g of Mohr's salt, heated to 80° C. with stirring, and then 104.5 g of 70% MAA and 52% methacryl. Acid methoxy polyethylene glycol (average number of moles of EO chain added: 45 moles, abbreviated as PGM-45EO hereinafter) 142.1 g, 48% NaOH 21.3 g, 10% NaPS 23.3 g, 35% SBS 9.5 g, pure water 10.0 g Each was dripped from a different drip port. 70% AA for 180 minutes, 52% PGM-45EO for 180 minutes, 48% NaOH for 180 minutes, 8% NaPS for 210 minutes, 35% SBS for 180 minutes, and pure water for 180 minutes. did. The start of dropping was the same at all times. The temperature was maintained at 80° C. until the 10% NaPS dropping was completed. Further, the same temperature was maintained for 30 minutes after completion of the dropwise addition of 10% NaPS for aging to obtain an aqueous copolymer solution (5).
＜実施例６＞
還流冷却管、攪拌機を備えた容量５００ｍＬのガラス製セパラブルフラスコに純水１６０．５ｇ、モール塩０．００８ｇを仕込み、攪拌下８０℃に昇温した後、６０％ＭＡＡ５０．２ｇ、１００％ＰＧＭ−９ＥＯ１１３．４ｇ、４８％ＮａＯＨ８．８ｇ、７％ＮａＰＳ２１．５ｇ、３５％ＳＢＳ５．８ｇ、純水１５．０ｇをそれぞれ別の滴下口より滴下した。それぞれの滴下時間は、６０％ＭＡＡが１８０分間、１００％ＰＧＭ−９ＥＯが１８０分間、４８％ＮａＯＨが１８０分間、７％ＮａＰＳが２１０分間、３５％ＳＢＳが１８０分間、そして純水が１８０分間とした。なお、滴下開始はすべて同時とした。７％ＮａＰＳ滴下終了までの間、温度は８０℃を維持した。さらに同温度を７％ＮａＰＳ滴下終了後３０分間にわたって維持して熟成を行い、共重合体水溶液（６）を得た。
<Example 6>
A 500 mL capacity glass separable flask equipped with a reflux condenser and a stirrer was charged with 160.5 g of pure water and 0.008 g of Mohr's salt, heated to 80° C. with stirring, and then 60% MAA 50.2 g, 100% PGM. -9EO113.4 g, 48% NaOH 8.8 g, 7% NaPS 21.5 g, 35% SBS 5.8 g, and pure water 15.0 g were dropped from different dropping ports. 60% MAA for 180 minutes, 100% PGM-9EO for 180 minutes, 48% NaOH for 180 minutes, 7% NaPS for 210 minutes, 35% SBS for 180 minutes, and pure water for 180 minutes. did. The start of dropping was the same at all times. The temperature was maintained at 80° C. until the completion of 7% NaPS dropping. Further, the same temperature was maintained for 30 minutes after the completion of dropwise addition of 7% NaPS, and aging was carried out to obtain an aqueous copolymer solution (6).
＜比較例１＞
特許５５９５２６３号の実施例４に準じて、重合体を得た。
還流冷却管、攪拌機を備えた容量５００ｍＬのガラス製セパラブルフラスコに純水１３５．２ｇ、亜リン酸２．２ｇを仕込み、攪拌下１００℃に昇温した後、１００％ＭＡＡ１０．８ｇ、１００％アクリル酸（以下、１００％ＡＡと略す。）２７．２ｇ、１００％ＰＧＭ−２３ＥＯ３６．９ｇ、１０％ＮａＰＳ４０．４ｇ、４０％ＳＢＳ１０．２ｇ、純水９７．３ｇをそれぞれ別の滴下口より滴下した。それぞれの滴下時間は、１００％ＭＡＡが１８０分間、１００％ＡＡが１８０分間、１００％ＰＧＭ−２３ＥＯが１８０分間、１０％ＮａＰＳが２１０分間、４０％ＳＢＳが１８０分間、そして純水が１８０分間とした。なお、滴下開始はすべて同時とした。１０％ＮａＰＳ滴下終了までの間、温度は１００℃を維持した。さらに同温度を１０％ＮａＰＳ滴下終了後１００分間にわたって維持して熟成を行い、重合を完結した。重合の完結後、反応溶液を放冷してから、５０％ＮａＯＨ４２．０ｇを加えて中和した。このようにして、比較共重合体水溶液（１）を得た。
<Comparative Example 1>
A polymer was obtained according to Example 4 of Japanese Patent No. 5595263.
A glass separable flask having a capacity of 500 mL equipped with a reflux condenser and a stirrer was charged with 135.2 g of pure water and 2.2 g of phosphorous acid, heated to 100° C. under stirring, and then 100% MAA 10.8 g, 100% Acrylic acid (hereinafter abbreviated as 100% AA) 27.2 g, 100% PGM-23EO 36.9 g, 10% NaPS 40.4 g, 40% SBS 10.2 g, and pure water 97.3 g were dropped from separate dropping ports. .. The respective dropping times were 100% MAA for 180 minutes, 100% AA for 180 minutes, 100% PGM-23EO for 180 minutes, 10% NaPS for 210 minutes, 40% SBS for 180 minutes, and pure water for 180 minutes. did. The start of dropping was the same at all times. The temperature was maintained at 100° C. until the end of 10% NaPS dropping. Further, the same temperature was maintained for 100 minutes after the completion of dropping of 10% NaPS, aging was carried out, and the polymerization was completed. After completion of the polymerization, the reaction solution was allowed to cool and then neutralized by adding 42.0 g of 50% NaOH. Thus, a comparative copolymer aqueous solution (1) was obtained.
＜比較例２＞
特許３１７９０２２号の実施例２に準じて、重合体を得た。
還流冷却管、攪拌機を備えた容量５００ｍＬのガラス製セパラブルフラスコに純水１２１．０ｇを仕込み、攪拌下５０℃に昇温した後、１００％ＭＡＡ１５．０ｇ、１００％メタクリル酸ナトリウム（以下、１００％ＳＭＡＡと略す。）２．１ｇ、１００％ＰＧＭ−９ＥＯ６２．９ｇ、１０％過硫酸アンモニウム水溶液（以下、１０％ＡＰＳと略す）３９．８ｇ、５％ＳＢＳ３９．８ｇ、純水１１９．４ｇをそれぞれ別の滴下口より滴下した。それぞれの滴下時間は、１００％ＭＡＡが２４０分間、１００％ＳＭＡＡが２４０分間、１００％ＰＧＭ−９ＥＯが２４０分間、１０％ＮａＰＳが３００分間、４０％ＳＢＳが３０００分間、そして純水が２４０分間とした。なお、滴下開始はすべて同時とした。１０％ＮａＰＳ滴下終了までの間、温度は５０℃を維持した。さらに同温度を１０％ＮａＰＳ滴下終了後６０分間にわたって維持して熟成を行い、比較共重合体水溶液（２）を得た。
<Comparative example 2>
A polymer was obtained according to Example 2 of Japanese Patent No. 3179022.
A glass separable flask having a capacity of 500 mL equipped with a reflux condenser and a stirrer was charged with 121.0 g of pure water and heated to 50° C. under stirring, and then 15.0 g of 100% MAA and 100% sodium methacrylate (hereinafter, 100%). % SMAA) 2.1 g, 100% PGM-9EO62.9 g, 10% ammonium persulfate aqueous solution (hereinafter abbreviated as 10% APS) 39.8 g, 5% SBS 39.8 g, and pure water 119.4 g, respectively. It was dripped from the dropping port. The respective dropping times were 240 minutes for 100% MAA, 240 minutes for 100% SMAA, 240 minutes for 100% PGM-9EO, 300 minutes for 10% NaPS, 3000 minutes for 40% SBS, and 240 minutes for pure water. did. The start of dropping was the same at all times. The temperature was kept at 50° C. until the end of 10% NaPS dropping. Further, the same temperature was maintained for 60 minutes after completion of the dropwise addition of 10% NaPS for aging to obtain a comparative copolymer aqueous solution (2).
実施例１〜６で得られた共重合体水溶液（１）〜（６）及び比較例１、２で得られた比較共重合体水溶液（１）、（２）について、上述した各種測定を行った結果を、共重合体の製造条件等とともに表１に示す。
表１の結果から、構造中の硫黄原子の含有割合が４００ｐｐｍ以上であるメタクリル酸系重合体を含み、硫黄含有化合物の含有量が硫酸ナトリウム換算で２００００ｐｐｍ以下である組成物は、条件（１）、（２）のいずれにおいても界面活性剤との良好な相溶性を示すことが確認された。
For the copolymer aqueous solutions (1) to (6) obtained in Examples 1 to 6 and the comparative copolymer aqueous solutions (1) and (2) obtained in Comparative Examples 1 and 2, the above-described various measurements were performed. The results are shown in Table 1 together with the copolymer production conditions and the like.
From the results of Table 1, the composition containing a methacrylic acid-based polymer having a sulfur atom content of 400 ppm or more in the structure and having a sulfur-containing compound content of 20000 ppm or less in terms of sodium sulfate was obtained under the condition (1). It was confirmed that both of (1) and (2) show good compatibility with the surfactant.
Claims (2)
該硫黄含有重合体は、メタクリル酸由来の構造単位とメタクリル酸エステル由来の構造単位とを含み、下記の方法により得られる、重合体の構造中に含まれる硫黄原子の割合が４００ｐｐｍ以上、１２００ｐｐｍ以下であり、
下記の方法により得られる、該硫黄含有重合体組成物中における硫黄含有化合物の含有割合が、硫酸ナトリウム換算で２００００ｐｐｍ以下であり、
該硫黄含有重合体組成物は、洗剤用途に用いられることを特徴とする硫黄含有重合体組成物。
＜硫黄含有重合体組成物中における硫黄含有化合物の含有割合＞
下記重合体組成物の固形分測定方法により得られた重合体の固形分、及び、下記ＳＯ ３ ２− イオン濃度およびＳＯ ４ ２− イオン濃度測定条件での測定により得られたＳＯ ３ ２− イオン濃度およびＳＯ ４ ２− イオン濃度を用いて、以下の計算より算出する。
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１．０ｇ）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（％）を算出する。
＜ＳＯ ３ ２− イオン濃度およびＳＯ ４ ２− イオン濃度測定条件＞
下記条件にてイオンクロマト分析を行うことで測定する。
装置：東ソー社製 ＩＯＮＣＨＲＯＭＡＴＯＧＲＡＰＨ ＩＣ−２０１０
検出器：ＣＭ検出器
検出方法：電気伝導度検出器、４極電極法
イオン分析方式：サプレッサー法
カラム：Ｓｈｏｄｅｘ ＩＣ ＳＩ−９０ ４Ｅ
ガードカラム：Ｓｈｏｄｅｘ ＳＩ−９０ Ｇ
カラム温度：２５℃
溶離液：１ｍＭ Ｎａ ２ ＣＯ ３ ＋４ｍＭ ＮａＨＣＯ ３ ＋５％アセトン
流速：１．２ｍＬ／ｍｉｎ．
＜重合体の構造中に含まれる硫黄原子の割合算出方法＞
下記ＩＣＰによる重合体組成物中の硫黄量分析により得られた重合体組成物中の硫黄量、上記硫黄含有重合体組成物中における硫黄含有化合物の含有割合、及び、上記重合体組成物の固形分測定方法により得られた重合体の固形分を用いて、以下の計算より算出する。
重合体組成物中の硫黄量を誘導結合プラズマ（Ｉｎｄｕｃｔｉｖｅｌｙ Ｃｏｕｐｌｅｄ Ｐｌａｓｍａ，ＩＣＰ）発光分光分析法によって定量する。
装置：ＳＨＩＭＡＤＺＵ ＩＣＰＥ−９０００
測定波長：１８２．６２５ｎｍ A sulfur-containing polymer composition containing a sulfur-containing polymer having a sulfur atom in the structure, and a sulfur-containing compound different from the sulfur-containing polymer,
The sulfur-containing polymer contains a structural unit derived from methacrylic acid and a structural unit derived from methacrylic acid ester , obtained by the following method , the proportion of sulfur atoms contained in the structure of the polymer is 400ppm or more, 1200ppm or less And
The following method is obtained, the content of sulfur-containing compounds in the sulfur-containing polymer composition is state, and are less 20000ppm with sodium sulfate terms,
Sulfur-containing polymer composition, the sulfur-containing polymer composition characterized Rukoto used detergent applications.
<Content ratio of sulfur-containing compound in sulfur-containing polymer composition>
The following polymer compositions polymer solids of obtained by the solid content measurement method, and, SO 3 2-ion obtained by the measurement of the following SO 3 2-ion concentration and SO 4 2-ion concentration measuring conditions It is calculated from the following calculation using the concentration and the SO 4 2− ion concentration.
The polymer composition (1.0 g of polymer composition+1.0 g of water) was left to stand in an oven heated to 130° C. for 1 hour to be dried. The solid content (%) is calculated from the weight change before and after drying.
<SO 3 2- ion concentration and SO 4 2- ion concentration measurement conditions>
It is measured by performing ion chromatography analysis under the following conditions.
Device: IONCHROMATO GRAPH IC-2010 manufactured by Tosoh Corporation
Detector: CM detector
Detection method: Electric conductivity detector, 4-pole electrode method
Ion analysis method: suppressor method
Column: Shodex IC SI-904E
Guard column: Shodex SI-90 G
Column temperature: 25°C
Eluent: 1 mM Na 2 CO 3 +4 mM NaHCO 3 +5% acetone
Flow rate: 1.2 mL/min.
<Method of calculating ratio of sulfur atoms contained in polymer structure>
The amount of sulfur in the polymer composition obtained by analysis of the amount of sulfur in the polymer composition by the following ICP, the content ratio of the sulfur-containing compound in the sulfur-containing polymer composition, and the solid content of the polymer composition It is calculated by the following calculation using the solid content of the polymer obtained by the content measurement method.
The amount of sulfur in the polymer composition is quantified by inductively coupled plasma (ICP) emission spectroscopy.
Device: SHIMADZU ICPE-9000
Measurement wavelength: 182.625 nm
該製造方法は、メタクリル酸とメタクリル酸エステルとを含む単量体成分を原料とし、該単量体成分に含まれる単量体に対して、亜硫酸水素ナトリウムを０．１〜６ｇ／ｍｏｌの割合で使用して重合反応を行う工程を含むことを特徴とする洗剤用途に用いられる硫黄含有重合体組成物の製造方法。 A method for producing a sulfur-containing polymer composition for use in detergent applications, comprising a sulfur-containing polymer having a sulfur atom in its structure, and a sulfur-containing compound different from the sulfur-containing polymer,
The manufacturing method uses a monomer component containing methacrylic acid and a methacrylic acid ester as a raw material, and sodium bisulfite is contained in a proportion of 0.1 to 6 g/mol with respect to the monomer contained in the monomer component. A method for producing a sulfur-containing polymer composition for use in detergents , comprising the step of carrying out a polymerization reaction according to 1.
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