JP5445831B2 - Water-soluble polymer dispersion, paper strength enhancer, paper drainage improver and paper yield improver - Google Patents
Water-soluble polymer dispersion, paper strength enhancer, paper drainage improver and paper yield improver Download PDFInfo
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- JP5445831B2 JP5445831B2 JP2009136794A JP2009136794A JP5445831B2 JP 5445831 B2 JP5445831 B2 JP 5445831B2 JP 2009136794 A JP2009136794 A JP 2009136794A JP 2009136794 A JP2009136794 A JP 2009136794A JP 5445831 B2 JP5445831 B2 JP 5445831B2
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- water
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- polymer dispersion
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- 229920003169 water-soluble polymer Polymers 0.000 title claims description 80
- 239000004815 dispersion polymer Substances 0.000 title claims description 64
- 239000003623 enhancer Substances 0.000 title claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 59
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 55
- 239000000178 monomer Substances 0.000 claims description 46
- 239000002270 dispersing agent Substances 0.000 claims description 43
- 229920000642 polymer Polymers 0.000 claims description 36
- 150000003839 salts Chemical class 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 20
- 239000006185 dispersion Substances 0.000 claims description 14
- 239000012266 salt solution Substances 0.000 claims description 13
- 238000010526 radical polymerization reaction Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000012674 dispersion polymerization Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 79
- 229910052757 nitrogen Inorganic materials 0.000 description 54
- 238000004519 manufacturing process Methods 0.000 description 52
- 239000000123 paper Substances 0.000 description 41
- 238000006116 polymerization reaction Methods 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- 239000003505 polymerization initiator Substances 0.000 description 27
- 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 25
- 238000010438 heat treatment Methods 0.000 description 25
- 238000010992 reflux Methods 0.000 description 25
- 238000003756 stirring Methods 0.000 description 25
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 22
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 22
- 235000011130 ammonium sulphate Nutrition 0.000 description 22
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 21
- 238000000034 method Methods 0.000 description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 16
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 16
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 14
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 14
- -1 N, N-dimethylaminoethyl Chemical group 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 7
- 229940073608 benzyl chloride Drugs 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 125000002091 cationic group Chemical group 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- FYBFGAFWCBMEDG-UHFFFAOYSA-N 1-[3,5-di(prop-2-enoyl)-1,3,5-triazinan-1-yl]prop-2-en-1-one Chemical compound C=CC(=O)N1CN(C(=O)C=C)CN(C(=O)C=C)C1 FYBFGAFWCBMEDG-UHFFFAOYSA-N 0.000 description 4
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 3
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 238000000149 argon plasma sintering Methods 0.000 description 3
- 238000010835 comparative analysis Methods 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000013055 pulp slurry Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000001302 tertiary amino group Chemical group 0.000 description 3
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- ASFFINXMVZLDKE-UHFFFAOYSA-N 1-(1,3,5-triazinan-1-yl)prop-2-en-1-one Chemical compound C=CC(=O)N1CNCNC1 ASFFINXMVZLDKE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 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
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000008351 acetate buffer Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 2
- 229940018557 citraconic acid Drugs 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229940059574 pentaerithrityl Drugs 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001374 small-angle light scattering Methods 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 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
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 1
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- NZEDMAWEJPYWCD-UHFFFAOYSA-N 3-prop-2-enylsulfonylprop-1-ene Chemical compound C=CCS(=O)(=O)CC=C NZEDMAWEJPYWCD-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N DEAEMA Natural products CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-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
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 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
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- IIRDTKBZINWQAW-UHFFFAOYSA-N hexaethylene glycol Chemical compound OCCOCCOCCOCCOCCOCCO IIRDTKBZINWQAW-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002156 mixing Methods 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
- 230000003287 optical effect Effects 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Paper (AREA)
Description
本発明は、水溶性重合体分散液、紙力増強剤、製紙用濾水性向上剤および製紙用歩留向上剤に関する。 The present invention relates to a water-soluble polymer dispersion, a paper strength enhancer, a papermaking drainage improver, and a papermaking yield improver.
紙は、リサイクル可能な資源として注目されており、さまざまな用途に用いられるようになってきている。用途によっては紙に対し、強度が求められることがあり、強度が必要となる用途においては、紙の強度を高めるために紙力増強剤が多用されている。 Paper is attracting attention as a recyclable resource, and has been used for various purposes. Depending on the application, strength may be required for paper. In applications that require strength, paper strength enhancers are frequently used to increase the strength of the paper.
紙力増強剤としては、アクリルアミド系高分子が広く用いられており、通常アクリルアミド系高分子は水溶液中でアクリルアミド等を他の重合性単量体と共重合させることにより得られ、本出願人も様々な紙力増強剤を提案している。（例えば、特許文献１および２など参照）しかし、紙をリサイクルして繰り返し使用することで紙の原料であるパルプの短繊維化及び劣化が進み、また、紙製造系内の無機物や夾雑物の濃度が上昇し、強度・濾水性・歩留り性を向上させるのが困難になるなどの問題があった。 As a paper strength enhancer, acrylamide polymers are widely used, and acrylamide polymers are usually obtained by copolymerizing acrylamide or the like with other polymerizable monomers in an aqueous solution. Various paper strength enhancers have been proposed. (For example, refer to Patent Documents 1 and 2, etc.) However, by recycling and repeatedly using paper, the pulp that is the raw material of paper is shortened and deteriorated, and the inorganic material and impurities in the paper manufacturing system There was a problem that the concentration increased and it was difficult to improve strength, drainage, and yield.
上述の問題のうち、濾水性、歩留り性の低下に対する解決策として、塩水溶液中で分散重合させた水溶性高分子の分散体を歩留り向上剤、濾水向上剤として用いることも提案されている。（特許文献３および４参照）当該方法によれば、濾水性、歩留性を向上させることができる分散液が得られるものの、当該方法で得られる分散液を用いた場合には、紙の強度向上が十分でなく、また均一な分散液が得られないために得られる紙の地合いが不十分となるといった問題があった。 Among the above-mentioned problems, as a solution to the decrease in drainage and yield, it has also been proposed to use a dispersion of a water-soluble polymer dispersed and polymerized in a salt solution as a yield improver and drainage improver. . (Refer to Patent Documents 3 and 4) According to the method, although a dispersion that can improve drainage and retention can be obtained, the strength of the paper is obtained when the dispersion obtained by the method is used. There is a problem in that the improvement is not sufficient and a uniform dispersion is not obtained, resulting in insufficient paper texture.
本発明は、粒子径が均一で、保存安定性が良好で、得られる紙の地合いを乱さず、かつ、紙力を高く維持することができる水溶性重合体分散液、紙力増強剤、製紙用濾水性向上剤および製紙用歩留向上剤を提供することを目的とする。 The present invention provides a water-soluble polymer dispersion, a paper strength enhancer, and papermaking that have a uniform particle size, good storage stability, do not disturb the texture of the resulting paper, and can maintain high paper strength. An object of the present invention is to provide a freeness improving agent for paper and a yield improving agent for papermaking.
本発明者は、前記課題を解決すべく鋭意検討したところ、分岐構造を有する高分子分散剤を用い、水溶性重合体を、高濃度の塩水溶液中に特定の粒子径となるように分散させた特定の粘度を有する水溶性重合体分散液を紙力増強剤として用いることで、得られる紙の地合いが良好となることを見出し、特に、分散重合法を用いることにより容易に粒子径が均一で、安定な水溶性重合体分散液が得られることを見出し、本発明を完成させた。 The present inventor has intensively studied to solve the above-mentioned problems. As a result, a polymer dispersant having a branched structure is used, and a water-soluble polymer is dispersed in a high-concentration salt aqueous solution so as to have a specific particle size. The water-soluble polymer dispersion having a specific viscosity is used as a paper strength enhancer, and the resulting paper has a good texture. In particular, the particle diameter is easily uniformed by using the dispersion polymerization method. The inventors have found that a stable water-soluble polymer dispersion can be obtained, and completed the present invention.
すなわち、本発明は、塩濃度が１０重量％以上飽和濃度以下の塩水溶液中に、水溶性重合体（Ａ）を、分岐構造を有する高分子分散剤（Ｂ）を用いて平均粒子径が０．１〜１５０μｍとなるように分散させた水溶性重合体の分散液であって、水溶性重合体（Ａ）の含有量が１０〜４０重量％で、２５℃における分散液の粘度が１００〜３００００ｍＰａ・ｓであり、水溶性重合体（Ａ）が、５〜２０モル％のカチオン性ラジカル重合性単量体（ａ１）、０〜７．５モル％のアニオン性ラジカル重合性単量体（ａ２）、０〜１モル％の架橋性単量体（ａ３）および２０〜９７モル％の（メタ）アクリルアミド（ａ４）を共重合して得られる共重合体であり、分岐構造を有する高分子分散剤（Ｂ）が、３０〜９９．９９９モル％のカチオン性ラジカル重合性単量体（ｂ１）、０〜５モル％のアニオン性ラジカル重合単量体（ｂ２）、０．００１〜１モル％の架橋性単量体（ｂ３）および０〜７０モル％の（メタ）アクリルアミド（ｂ４）を共重合させて得られる共重合体である水溶性重合体分散液；当該水溶性重合体分散液を含有する紙力増強剤；当該水溶性重合体分散液を含有する製紙用濾水性向上剤；当該水溶性重合体分散液を含有する製紙用歩留向上剤に関する。 That is, according to the present invention, an average particle size of 0 is obtained by using a polymer dispersant (B) having a branched structure and a water-soluble polymer (A) in a salt aqueous solution having a salt concentration of 10% by weight or more and a saturated concentration or less. A dispersion of a water-soluble polymer dispersed so as to be 1 to 150 μm, wherein the content of the water-soluble polymer (A) is 10 to 40% by weight, and the viscosity of the dispersion at 25 ° C. is 100 to 30000 mPa · s der is, a water-soluble polymer (a) is 5 to 20 mole% of the cationic radical-polymerizable monomer (a1), 0 to 7.5 mole% anionic radical-polymerizable monomer (A2), a copolymer obtained by copolymerizing 0 to 1 mol% of a crosslinkable monomer (a3) and 20 to 97 mol% of (meth) acrylamide (a4), and having a branched structure The cationic dispersant containing 30 to 99.999 mol% of the molecular dispersant (B) Polymerizable monomer (b1), 0 to 5 mol% of an anionic radical polymerizable monomer (b2), 0.001 to 1 mol% of a crosslinkable monomer (b3) and 0 to 70 mol% of Water-soluble polymer dispersion which is a copolymer obtained by copolymerizing (meth) acrylamide (b4) ; paper strength enhancer containing the water-soluble polymer dispersion; containing the water-soluble polymer dispersion The present invention relates to a papermaking drainage improver; a papermaking yield improver containing the water-soluble polymer dispersion.
本発明の水溶性重合体分散液を紙力増強剤として用いることにより、地合を乱すことなく、紙に紙力を付与することができる。また、本発明の水溶性重合体分散液を添加することにより、無機填料や紙の原料であるパルプスラリーの歩留が向上するため、製紙用歩留向上剤としても用いることができる。また、本発明の水溶性重合体分散液を添加することにより、抄紙の際の濾水性が向上するため、製紙用濾水性向上剤としても用いることができる。 By using the water-soluble polymer dispersion of the present invention as a paper strength enhancer, paper strength can be imparted to paper without disturbing formation. Moreover, since the yield of the pulp slurry which is a raw material of an inorganic filler or paper improves by adding the water-soluble polymer dispersion liquid of this invention, it can be used also as a yield improver for paper manufacture. Moreover, since the drainage at the time of papermaking improves by adding the water-soluble polymer dispersion liquid of this invention, it can also be used as a drainage improver for papermaking.
本発明の水溶性重合体分散液は、塩濃度が１０重量％以上飽和濃度以下の塩水溶液中に、水溶性重合体（Ａ）（以下、（Ａ）成分という）を、分岐構造を有する高分子分散剤（Ｂ）（以下、（Ｂ）成分という）を用いて平均粒子径が０．１〜１５０μｍ程度となるように分散させた水溶性重合体の分散液であって、水溶性重合体（Ａ）の含有量が１０〜４０重量％程度で、２５℃における分散液の粘度が１００〜３００００ｍＰａ・ｓ程度であることを特徴とする。平均粒子径が０．１μｍ未満の場合には、粒子径の影響により粘度が高くなる傾向があり、また、粒子径が小さすぎることで表面積が増大し粒子が凝集するなど保存安定性に問題を引き起こす可能性もあるため好ましくなく、１５０μｍを超える場合には、粒子が沈降しやすくなるなど保存安定性に問題が生じるため好ましくない。また、粘度が、１００ｍＰａ・ｓ未満の場合には、粒子が沈降しやすくなるなど保存安定性に問題が生じるため好ましくなく、３００００ｍＰａ・ｓを超える場合には、流動性がなくなるなどハンドリング上の問題が生じるため好ましくない。 The water-soluble polymer dispersion of the present invention is a highly water-soluble polymer (A) (hereinafter referred to as component (A)) having a branched structure in a salt aqueous solution having a salt concentration of 10% by weight or more and a saturated concentration or less. A water-soluble polymer dispersion in which an average particle diameter is about 0.1 to 150 μm using a molecular dispersant (B) (hereinafter referred to as component (B)), and the water-soluble polymer The content of (A) is about 10 to 40% by weight, and the viscosity of the dispersion at 25 ° C. is about 100 to 30000 mPa · s. When the average particle size is less than 0.1 μm, the viscosity tends to increase due to the influence of the particle size, and when the particle size is too small, the surface area increases and the particles aggregate, causing problems in storage stability. Since it may cause, it is not preferable, and when exceeding 150 micrometers, since a problem arises in storage stability, such as particle | grains becoming easy to settle, it is not preferable. In addition, when the viscosity is less than 100 mPa · s, it is not preferable because the storage stability causes problems such as particles being easily settled. When the viscosity exceeds 30000 mPa · s, it is not preferable. Is not preferable.
本発明で用いられる（Ａ）成分は、例えば、ラジカル重合成分（ａ）（以下、（ａ）成分という）を公知の方法で重合させることにより得られる。（ａ）成分としては、特に限定されないが、例えば、カチオン性ラジカル重合性単量体（ａ１）（以下、（ａ１）成分という）、アニオン性ラジカル重合性単量体（ａ２）（以下、（ａ２）成分という）、架橋性単量体（ａ３）（以下、（ａ３）成分という）および（メタ）アクリルアミド（ａ４）（以下、（ａ４）成分という）などが挙げられる。 The component (A) used in the present invention can be obtained, for example, by polymerizing the radical polymerization component (a) (hereinafter referred to as component (a)) by a known method. Although it does not specifically limit as (a) component, For example, cationic radically polymerizable monomer (a1) (henceforth (a1) component), anionic radically polymerizable monomer (a2) (henceforth, ( a2) component), crosslinkable monomer (a3) (hereinafter referred to as component (a3)) and (meth) acrylamide (a4) (hereinafter referred to as component (a4)).
（ａ１）成分としては、アミノ基や第４級アンモニウム基のようなカチオン性官能基を少なくとも１つ有し、ラジカル重合性官能基を１つ有するものであれば特に限定されず、公知のものを使用することができる。具体的には、例えば、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリルアミド、Ｎ，Ｎ−ジエチルアミノプロピル（メタ）アクリルアミド等の第３級アミノ基含有（メタ）アクリル系モノマー、当該第３級アミノ基含有（メタ）アクリル系モノマーの塩、当該第３級アミノ基含有（メタ）アクリル系モノマーと四級化剤を反応させて得られる第４級アンモニウム塩含有（メタ）アクリル系モノマーなどが挙げられる。塩は、塩酸塩、硫酸塩等の無機酸塩であっても、酢酸塩等の有機酸塩であってもよい。また、４級化剤としては、メチルクロライド、ベンジルクロライド、ジメチル硫酸、エピクロルヒドリン等が挙げられる。これら（ａ１）成分は、１種を単独で使用しても２種以上を混合して用いてもよい。これらの中では、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレートのベンジルクロライド４級化物が重合体とした際、疎水性が高く塩溶液に溶解しにくくなる点で好ましい。 The component (a1) is not particularly limited as long as it has at least one cationic functional group such as an amino group or a quaternary ammonium group and one radical polymerizable functional group. Can be used. Specifically, for example, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) ) Tertiary amino group-containing (meth) acrylic monomers such as acrylamide, salts of the tertiary amino group-containing (meth) acrylic monomers, quaternized with the tertiary amino group-containing (meth) acrylic monomers And a quaternary ammonium salt-containing (meth) acrylic monomer obtained by reacting an agent. The salt may be an inorganic acid salt such as hydrochloride or sulfate, or an organic acid salt such as acetate. Examples of the quaternizing agent include methyl chloride, benzyl chloride, dimethyl sulfate, epichlorohydrin and the like. These (a1) components may be used individually by 1 type, or 2 or more types may be mixed and used for them. Among these, when a benzyl chloride quaternized product of N, N-dimethylaminoethyl (meth) acrylate is used as a polymer, it is preferable in that it is highly hydrophobic and difficult to dissolve in a salt solution.
（ａ２）成分としては、アニオン性官能基を少なくとも１つ有し、ラジカル重合性官能基を１つ有するものであれば特に限定されず、公知のものを使用することができる。具体的には、例えば、（メタ）アクリル酸、フマル酸、マレイン酸、無水マレイン酸、イタコン酸、無水イタコン酸、シトラコン酸、無水シトラコン酸等のカルボキシル基含有単量体、（メタ）アリルスルホン酸等のスルホン酸基含有単量体、２−メタクリロイルオキシエチルアシッドホスフェート、ビニルホスホン酸、などのリン酸基含有単量体などが挙げられる。なお、これらはアルカリ金属類やアミン等の塩になっていてもよい。これらは、１種を単独で使用しても２種以上を混合して用いてもよい。これらの中では、イタコン酸が、水溶性重合体分散液の凝集性、脱水性能を向上させることができるため好ましい。 The component (a2) is not particularly limited as long as it has at least one anionic functional group and one radical polymerizable functional group, and a known one can be used. Specifically, for example, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic acid and other carboxyl group-containing monomers, (meth) allylsulfone Examples thereof include sulfonic acid group-containing monomers such as acids, and phosphoric acid group-containing monomers such as 2-methacryloyloxyethyl acid phosphate and vinylphosphonic acid. These may be salts of alkali metals or amines. These may be used individually by 1 type, or 2 or more types may be mixed and used for them. Of these, itaconic acid is preferred because it can improve the cohesiveness and dehydration performance of the water-soluble polymer dispersion.
（ａ３）成分としては、ラジカル重合性官能基を少なくとも２つ有するものであれば特に限定されず、公知のものを使用することができる。具体的には、例えば、メチレンビス（メタ）アクリルアミド等の多官能（メタ）アクリルアミド類、ヘキサンジオールジ（メタ）アクリレート、１，９−ノナンジオールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ヘキサエチレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ジシクロペンタニルジ（メタ）アクリレート等のジ（メタ）アクリレート類、３つ以上のビニル基を有する多官能ビニルモノマーとしてはトリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、１，３，５−トリ（メタ）アクリロイルヘキサヒドロ−１，３，５−トリアジン、トリ（メタ）アリルイソシアヌレート、トリ（メタ）アリルアミン、テトラメチロールメタンテトラ（メタ）アクリレート等、ジビニルベンゼン等の芳香族ポリビニル化合物などが挙げられる。これらは、１種を単独で使用しても２種以上を混合して用いてもよい。これらの中では、メチレンビス（メタ）アクリルアミドや１，３，５−トリアクリロイルヘキサヒドロ−１，３，５−トリアジンが（ａ１）〜（ａ４）成分などとの共重合性が高い点で好ましい。 The component (a3) is not particularly limited as long as it has at least two radical polymerizable functional groups, and known components can be used. Specifically, for example, polyfunctional (meth) acrylamides such as methylenebis (meth) acrylamide, hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate Di (meth) acrylates such as hexaethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, etc., as polyfunctional vinyl monomers having three or more vinyl groups Is trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, 1,3,5-tri (meth) acryloylhexahydro-1,3,5-triazine, tri (meth) allyl isocyanurate, tri ( (Meth) allyl Min, tetramethylolmethane tetra (meth) acrylate, aromatic polyvinyl compounds such as divinylbenzene and the like. These may be used individually by 1 type, or 2 or more types may be mixed and used for them. Among these, methylenebis (meth) acrylamide and 1,3,5-triacryloylhexahydro-1,3,5-triazine are preferable in terms of high copolymerizability with the components (a1) to (a4).
なお、（ａ）成分には、（ａ１）成分〜（ａ４）成分以外のラジカル重合性官能基を１つ有するラジカル重合性単量体（ａ５）（以下、（ａ５）成分）を用いてもよい。（ａ５）成分としては、具体的には、例えば、Ｎ−置換アクリルアミド類、芳香族ビニルモノマー、アルキル（メタ）アクリレート類、カルボン酸ビニルエステル類、（メタ）アクリロニトリル、ビニルアルコールなどが挙げられる。Ｎ−置換アクリルアミド類としては、特に限定されず公知のものを用いることができる。具体的には、たとえば、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、Ｎ，Ｎ−ジエチル（メタ）アクリルアミド、Ｎ，Ｎ−ジイソプロピル（メタ）アクリルアミド、Ｎ−メチル（メタ）アクリルアミド、Ｎ−エチル（メタ）アクリルアミド、Ｎ−イソプロピル（メタ）アクリルアミド、Ｎ−ｔ−ブチル（メタ）アクリルアミドなどの単官能Ｎ−置換アクリルアミド類が挙げられる。芳香族ビニルモノマーとしては、スチレン、α−メチルスチレン、ビニルトルエンなどの分子中に芳香環を有する単官能モノマー類が挙げられる。また、アルキル（メタ）アクリレート類としては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸−２−エチルヘキシル、（メタ）アクリル酸シクロヘキシルなどの単官能モノマー類が挙げられる。カルボン酸ビニルエステル類としては、酢酸ビニル、プロピオン酸ビニル等などが挙げられる。これらは、１種を単独で使用しても２種以上を混合して用いてもよい。これらの中では、Ｎ，Ｎ−ジメチルアクリルアミドが水溶性重合体分散液を得る上で用いる（メタ）アクリルアミドとの共重合性が高く好ましい。 As the component (a), a radical polymerizable monomer (a5) having one radical polymerizable functional group other than the components (a1) to (a4) (hereinafter referred to as component (a5)) may be used. Good. Specific examples of the component (a5) include N-substituted acrylamides, aromatic vinyl monomers, alkyl (meth) acrylates, carboxylic acid vinyl esters, (meth) acrylonitrile, vinyl alcohol, and the like. N-substituted acrylamides are not particularly limited, and known ones can be used. Specifically, for example, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-diisopropyl (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meta) ) Monofunctional N-substituted acrylamides such as acrylamide, N-isopropyl (meth) acrylamide, and Nt-butyl (meth) acrylamide. Examples of the aromatic vinyl monomer include monofunctional monomers having an aromatic ring in a molecule such as styrene, α-methylstyrene, and vinyl toluene. Examples of the alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (2-ethylhexyl (meth) acrylate, And monofunctional monomers such as cyclohexyl methacrylate. Examples of the carboxylic acid vinyl esters include vinyl acetate and vinyl propionate. These may be used individually by 1 type, or 2 or more types may be mixed and used for them. Among these, N, N-dimethylacrylamide is preferable because of its high copolymerizability with (meth) acrylamide used for obtaining a water-soluble polymer dispersion.
（ａ）成分中に含まれる各成分としては、特に限定されないが、（ａ１）成分および（ａ４）成分を必須使用し、必要に応じて、（ａ２）成分、（ａ３）成分を用いることが好ましい。また、各成分の使用量は特に限定されないが、通常、（ａ１）成分を３〜４０モル％程度、（ａ２）成分を０〜４０モル％程度、（ａ３）成分を０〜１モル％程度、（ａ４）成分を２０〜９７モル％程度用い、好ましくは、（ａ１）成分を６〜２０モル％、（ａ２）成分を３〜２０モル％、（ａ３）成分を０．００１〜０．０１モル％、（ａ４）成分を２０〜９０モル％用いる。なお、（ａ５）成分を用いる場合には、その使用量は、通常１モル％程度以下、好ましくは、０．５モル％以下である。 Although it does not specifically limit as each component contained in (a) component, (a1) component and (a4) component are used essential, and (a2) component and (a3) component are used as needed. preferable. Moreover, although the usage-amount of each component is not specifically limited, Usually, (a1) component is about 3-40 mol%, (a2) component is about 0-40 mol%, (a3) component is about 0-1 mol%. The component (a4) is used in an amount of about 20 to 97 mol%, preferably the component (a1) is 6 to 20 mol%, the component (a2) is 3 to 20 mol%, and the component (a3) is 0.001 to 0.001. 01 mol%, and 20 to 90 mol% of component (a4) is used. When the component (a5) is used, the amount used is usually about 1 mol% or less, preferably 0.5 mol% or less.
（Ａ）成分は、（ａ）成分をラジカル重合させることにより得られる。このようにして得られた（Ａ）成分の重量平均分子量は、通常、１００万〜２０００万程度、好ましくは３００万〜１０００万程度である。 The component (A) can be obtained by radical polymerization of the component (a). The weight average molecular weight of the component (A) thus obtained is usually about 1 million to 20 million, preferably about 3 million to 10 million.
なお、ここでいう重量平均分子量は、ＧＰＣ−ＬＡＬＬＳ法あるいはＧＰＣ−ＲＡＬＬＳ法によるポリエチレンオキシド換算した重量平均分子量をいい、０．５ｍｏｌ／Ｌ酢酸緩衝液（０．５ｍｏｌ／Ｌ酢酸＋０．５ｍｏｌ％／Ｌ酢酸ナトリウム水溶液、ｐＨ約４．２）を溶媒（溶離液）として、ポリマー濃度０．０１２５重量％で、光散乱角５°あるいは９０°で測定した値（４０℃）をいう。なお、測定に用いたポリマーは０．５重量％に調整後ｐＨ１０〜１２になるまで苛性ソーダを添加し、８０℃以上の湯浴に４時間浸したサンプルを用いた。なお、本明細書における、重量平均分子量および数平均分子量は当該方法により測定した値である。 In addition, the weight average molecular weight here means the weight average molecular weight converted to polyethylene oxide by GPC-LALLS method or GPC-RALLS method, and 0.5 mol / L acetate buffer (0.5 mol / L acetic acid + 0.5 mol% / A value (40 ° C.) measured at a light scattering angle of 5 ° or 90 ° at a polymer concentration of 0.0125% by weight using an aqueous solution of L sodium acetate, pH of about 4.2) as a solvent (eluent). In addition, the polymer used for the measurement was adjusted to 0.5% by weight, caustic soda was added until the pH reached 10-12, and a sample immersed in a hot water bath at 80 ° C. or higher for 4 hours was used. In addition, in this specification, the weight average molecular weight and the number average molecular weight are values measured by the method.
本発明に用いられる（Ｂ）成分は、分岐構造を有するラジカル重合体であれば特に限定されず公知のものを用いることができる。ラジカル重合成分（ｂ）（以下、（ｂ）成分という）を、公知の方法で重合させることにより得られる。（ｂ）成分としては、特に限定されないが、例えば、カチオン性ラジカル重合性単量体（ｂ１）（以下、（ｂ１）成分という）、アニオン性ラジカル重合性単量体（ｂ２）（以下、（ｂ２）成分という）、架橋性単量体（ｂ３）（以下、（ｂ３）成分という）および（メタ）アクリルアミド（ｂ４）（以下、（ｂ４）成分という）などが挙げられる。 The component (B) used in the present invention is not particularly limited as long as it is a radical polymer having a branched structure, and a known one can be used. It can be obtained by polymerizing the radical polymerization component (b) (hereinafter referred to as the component (b)) by a known method. Although it does not specifically limit as (b) component, For example, cationic radically polymerizable monomer (b1) (henceforth (b1) component), anionic radically polymerizable monomer (b2) (henceforth, ( b2) component), crosslinkable monomer (b3) (hereinafter referred to as component (b3)) and (meth) acrylamide (b4) (hereinafter referred to as component (b4)).
（ｂ１）成分としては、（Ａ）成分の調製時に用いることができる（ａ１）成分と同様の単量体を用いることができる。なお、（ｂ１）成分としては、（メタ）アクリロイルオキシエチルトリメチルアンモニウムクロライドを用いることが、重合体を形成した際のカチオン量を所望の値に調整しやすい点で好ましい。 As the component (b1), the same monomer as the component (a1) that can be used when preparing the component (A) can be used. In addition, it is preferable to use (meth) acryloyloxyethyltrimethylammonium chloride as the component (b1) from the viewpoint of easily adjusting the cation amount when forming a polymer to a desired value.
（ｂ２）成分としては、（Ａ）成分の調製時に用いることができる（ａ２）成分と同様の単量体を用いることができる。なお、（ｂ２）成分として、（メタ）アリルスルホン酸を用いると、（メタ）アクリルアミドとの共重合性が高く、ラジカルの移動（連鎖移動）が生じやすくなり、分子量と架橋構造の調整が容易になる点で好ましい。 As the component (b2), the same monomer as the component (a2) that can be used when preparing the component (A) can be used. When (meth) allylsulfonic acid is used as component (b2), it is highly copolymerizable with (meth) acrylamide, radical migration (chain transfer) is likely to occur, and adjustment of molecular weight and crosslinked structure is easy. This is preferable.
（ｂ３）成分としては、（Ａ）成分の調製時に用いることができる（ａ３）成分と同様の単量体を用いることができる。なお、（ｂ３）成分としては、メチレンビス（メタ）アクリルアミドや１，３，５−トリ（メタ）アクリロイルヘキサヒドロ−１，３，５−トリアジンが（メタ）アクリルアミドとの共重合性が高い点で好ましい。 As the component (b3), the same monomer as the component (a3) that can be used when preparing the component (A) can be used. As the component (b3), methylenebis (meth) acrylamide and 1,3,5-tri (meth) acryloylhexahydro-1,3,5-triazine are highly copolymerizable with (meth) acrylamide. preferable.
なお、（ｂ）成分には、（ｂ１）成分〜（ｂ４）成分以外のラジカル重合性単量体（ｂ５）（以下、（ｂ５）成分という）を用いてもよい。（ｂ５）成分としては、（Ａ）成分の調製時に用いることができる（ａ５）成分と同様の単量体を用いることができる。これらは、１種を単独で使用しても２種以上を混合して用いてもよい。これらの中では、Ｎ，Ｎ−ジメチル（メタ）アクリルアミドが（メタ）アクリルアミドとの共重合性が高く好ましい。 The component (b) may be a radical polymerizable monomer (b5) (hereinafter referred to as the component (b5)) other than the components (b1) to (b4). As the component (b5), the same monomer as the component (a5) that can be used when preparing the component (A) can be used. These may be used individually by 1 type, or 2 or more types may be mixed and used for them. Among these, N, N-dimethyl (meth) acrylamide is preferable because of high copolymerizability with (meth) acrylamide.
（ｂ）成分中に含まれる各成分としては、特に限定されないが、（ｂ１）成分および（ｂ３）成分を必須使用し、必要に応じて、（ｂ２）成分、（ｂ４）成分を用いることが好ましい。また、各成分の使用量は特に限定されないが、通常、（ｂ１）成分を３０〜９９．９９９モル％程度、（ｂ２）成分を０〜５モル％程度、（ｂ３）成分を０．００１〜１モル％程度、（ｂ４）成分を０〜７０モル％程度用い、好ましくは、（ｂ１）成分を５０〜９９モル％、（ｂ２）成分を０．１〜１モル％、（ｂ３）成分を０．００１〜０．１モル％、（ｂ４）成分を０．５〜５０モル％用いる。なお、（ｂ５）成分を用いる場合には、その使用量は、通常５モル％程度以下、好ましくは、１モル％以下である。 Although it does not specifically limit as each component contained in (b) component, (b1) component and (b3) component are used essential, and (b2) component and (b4) component are used as needed. preferable. Moreover, although the usage-amount of each component is not specifically limited, Usually, (b1) component is about 30-99.999 mol%, (b2) component is about 0-5 mol%, (b3) component is 0.001-0.001. About 1 mol%, about (b4) component is used about 0-70 mol%, Preferably, (b1) component is 50-99 mol%, (b2) component is 0.1-1 mol%, (b3) component is used. 0.001 to 0.1 mol%, and 0.5 to 50 mol% of component (b4) is used. When the component (b5) is used, the amount used is usually about 5 mol% or less, preferably 1 mol% or less.
（Ｂ）成分は、（ｂ）成分を公知の方法でラジカル重合させることにより得られる。ラジカル重合法としては特に限定されない。このようにして得られた（Ｂ）成分は、通常、重量平均分子量が１万〜２００万程度であり、不揮発分を２０重量％に調整した場合の２５℃における粘度は１００〜３００００ｍＰａ・ｓ程度である。 The component (B) can be obtained by radical polymerization of the component (b) by a known method. The radical polymerization method is not particularly limited. The component (B) thus obtained usually has a weight average molecular weight of about 10,000 to 2,000,000, and the viscosity at 25 ° C. when the nonvolatile content is adjusted to 20% by weight is about 100 to 30,000 mPa · s. It is.
（Ａ）成分と（Ｂ）成分の使用量は特に限定されないが、通常、（Ａ）成分１００重量部に対し、（Ｂ）成分が１〜１０重量部程度用いることが好ましい。（Ａ）成分と（Ｂ）成分の使用量をかかる範囲とすることにより、より高い分散性安定性と紙力増強性能を有する重合生成物の分散液を得ることができる。 Although the usage-amount of (A) component and (B) component is not specifically limited, Usually, it is preferable to use about 1-10 weight part of (B) component with respect to 100 weight part of (A) component. By making the usage-amount of (A) component and (B) component into this range, the dispersion liquid of the polymerization product which has higher dispersibility stability and paper strength enhancement performance can be obtained.
（Ａ）成分を（Ｂ）成分を用いて、塩濃度が１０重量％以上飽和濃度以下の塩水溶液中に、分散させる方法としては、例えば、（Ａ）成分と（Ｂ）成分を混合して、機械分散等の公知の分散方法を採用することができる。なお、塩水溶液を調製する際に用いられる塩としては、（Ａ）成分を溶解しないものであれば特に限定されないが、通常は無機塩を用い、硫酸塩、リン酸塩などを用いることができる。具体的には、たとえば、硫酸アンモニウム、硫酸ナトリウム、硫酸マグネシウム、硫酸アルミニウム、リン酸水素アンモニウム、リン酸水素ナトリウム、リン酸水素カリウム等を用いることができる。 As a method of dispersing the component (A) in the salt aqueous solution having the salt concentration of 10% by weight or more and the saturation concentration or less using the component (B), for example, the component (A) and the component (B) are mixed. A known dispersion method such as mechanical dispersion can be employed. The salt used in preparing the salt aqueous solution is not particularly limited as long as it does not dissolve the component (A). Usually, inorganic salts are used, and sulfates, phosphates, and the like can be used. . Specifically, for example, ammonium sulfate, sodium sulfate, magnesium sulfate, aluminum sulfate, ammonium hydrogen phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate and the like can be used.
なお、塩濃度が１０重量％以上飽和濃度以下の塩水溶液中で、（Ｂ）成分の存在下、（ａ）成分を分散重合させることにより、本発明の水溶性重合体分散液における粒子径が均一となり、分子量分布がより狭くなるため特に好ましい。分散重合における高分子分散剤の作用は充分理解されていないが、重合生成物の析出時に作用し生成する粒子の付着・凝集を防止するためと考えられる。本発明における（Ｂ）成分は重合生成物の付着・凝集を防止する性能に優れると考えられる。なお、分散重合は、公知の方法を採用すればよいが、通常、（Ｂ）成分、塩、（ａ）成分の存在下でラジカル重合開始剤を投入し、ラジカル重合すればよい。重合温度は重合開始剤の種類により異なり重合開始剤が機能する温度であればよい。用いる塩は重合途中に添加する、重合後に混合するなど分割して添加してもよい。塩濃度が１０重量％未満であると反応液の粘度が高くなるため好ましくない。なお、（Ａ）成分および（Ｂ）成分の混合物の重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）の比（Ｍｗ／Ｍｎ）を１．０〜３．０程度とすることで、紙力増強効果を高く維持したまま、地合いの乱れをさらに低減することができるため好ましい。なお、（Ａ）成分および（Ｂ）成分の混合物の重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）の比（Ｍｗ／Ｍｎ）を１．０〜２．０とすることが、紙力増強効果が著しく向上するため、特に好ましい。 In addition, the particle diameter in the water-soluble polymer dispersion of the present invention is increased by dispersing and dispersing the component (a) in the presence of the component (B) in a salt aqueous solution having a salt concentration of 10% by weight or more and a saturation concentration or less. This is particularly preferable because it becomes uniform and the molecular weight distribution becomes narrower. Although the action of the polymer dispersant in the dispersion polymerization is not fully understood, it is considered to prevent adhesion / aggregation of particles produced by acting when the polymerization product is precipitated. The component (B) in the present invention is considered to be excellent in performance for preventing adhesion and aggregation of the polymerization product. The dispersion polymerization may be carried out by a known method. Usually, radical polymerization may be performed by introducing a radical polymerization initiator in the presence of the component (B), the salt, and the component (a). The polymerization temperature varies depending on the type of the polymerization initiator, and may be a temperature at which the polymerization initiator functions. The salt to be used may be added in the middle of polymerization or divided after mixing. A salt concentration of less than 10% by weight is not preferable because the viscosity of the reaction solution increases. The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / Mn) of the mixture of the component (A) and the component (B) is about 1.0 to 3.0. This is preferable because the disturbance of formation can be further reduced while maintaining the enhancement effect high. In addition, it is paper strength enhancement that the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the mixture of the component (A) and the component (B) is 1.0 to 2.0. Since an effect improves remarkably, it is especially preferable.
本発明の水溶性重合体分散液を紙力増強剤として用いるためには、通常、（Ａ）成分と（Ｂ）成分の混合物の重量平均分子量は３００万以上とすることが好ましく、また、固形分濃度を０．０１〜１重量％程度まで水等で希釈することが好ましい。 In order to use the water-soluble polymer dispersion of the present invention as a paper strength enhancer, it is usually preferable that the mixture of the component (A) and the component (B) has a weight average molecular weight of 3 million or more. It is preferable to dilute the partial concentration with water or the like to about 0.01 to 1% by weight.
本発明の水溶性重合体分散液を濾水性向上剤として用いるためには、通常、（Ａ）成分と（Ｂ）成分の混合物の重量平均分子量は３００万以上とすることが好ましく、また、固形分濃度を０．０１〜１重量％程度まで水等で希釈することが好ましい。 In order to use the water-soluble polymer dispersion of the present invention as a drainage improver, it is usually preferable that the weight average molecular weight of the mixture of the component (A) and the component (B) is 3 million or more, It is preferable to dilute the partial concentration with water or the like to about 0.01 to 1% by weight.
本発明の水溶性重合体分散液を歩留向上剤として用いるためには、通常、（Ａ）成分と（Ｂ）成分の混合物の重量平均分子量は３００万以上とすることが好ましく、また、固形分濃度を０．０１〜１重量％程度まで水等で希釈することが好ましい。 In order to use the water-soluble polymer dispersion of the present invention as a yield improver, it is usually preferable that the weight average molecular weight of the mixture of the component (A) and the component (B) is 3 million or more. It is preferable to dilute the partial concentration with water or the like to about 0.01 to 1 wt%.
以下、実施例および比較例を挙げて本発明をさらに具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited to these Examples.
（製造例１）高分子分散剤製造法
攪拌機、温度計、還流冷却管、窒素導入管を備えた２リットルの五つ口のセパラブルフラスコ中に、アクリロイルオキシエチルトリメチルアンモニウムクロライド（以下、ＤＭＡＥＡ−Ｑという）の８０％水溶液２４９．９９ｇ（純分１９９．９９ｇ；９９．９９５モル％）、メチレンビスアクリルアミド（以下、ＭＢＡＡという）０．００８ｇ（０．００５モル％）、イオン交換水５２９．４ｇを仕込み、６５℃に加温しながら窒素置換した。これに、重合開始剤として２，２´−アゾビス（２−アミジノプロパン）塩酸塩の３％水溶液２０ｇを加え、攪拌下で重合を行った。自己発熱により温度は上昇し、８０℃にて１時間重合し分岐構造を有する高分子分散剤を得た。得られた高分子分散剤の粘度は、２５℃に調整しビスメトロン粘度計（芝浦システム（株）製）を用いて測定した。（以下、粘度は同様の方法で測定した値である。）
Production Example 1 Polymer Dispersant Production Method Into a 2 liter five-necked separable flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen introduction tube, acryloyloxyethyltrimethylammonium chloride (hereinafter referred to as DMAEA-) was prepared. Q) 80% aqueous solution 249.99 g (pure content 199.99 g; 99.995 mol%), methylenebisacrylamide (hereinafter referred to as MBAA) 0.008 g (0.005 mol%), ion-exchanged water 529.4 g Was replaced with nitrogen while heating to 65 ° C. To this, 20 g of a 3% aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride was added as a polymerization initiator, and polymerization was carried out with stirring. The temperature rose due to self-heating, and polymerized at 80 ° C. for 1 hour to obtain a polymer dispersant having a branched structure. The viscosity of the obtained polymer dispersant was adjusted to 25 ° C. and measured using a bismetholone viscometer (manufactured by Shibaura System Co., Ltd.). (Hereinafter, the viscosity is a value measured by the same method.)
（製造例２）高分子分散剤製造法
攪拌機、温度計、還流冷却管、窒素導入管を備えた２リットルの五つ口のセパラブルフラスコ中に、ＤＭＡＥＡ−Ｑの８０％水溶液２５０ｇ（純分２００ｇ）、イオン交換水５３０ｇを仕込み、６５℃に加温しながら窒素置換した。これに、重合開始剤として２，２´−アゾビス（２−アミジノプロパン）塩酸塩の３％水溶液２０ｇを加え、攪拌下で重合を行った。自己発熱により温度は上昇し、８０℃にて１時間重合し分岐構造を有しない高分子分散剤を得た。
(Production Example 2) Polymer Dispersant Production Method In a 2 liter five-necked separable flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube, 250 g of an 80% aqueous solution of DMAEA-Q (pure content) 200 g) and 530 g of ion-exchanged water were charged, and nitrogen substitution was performed while heating to 65 ° C. To this was added 20 g of a 3% aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, and polymerization was carried out with stirring. The temperature rose due to self-heating, and polymerized at 80 ° C. for 1 hour to obtain a polymer dispersant having no branched structure.
（製造例３）高分子分散剤製造法
攪拌機、温度計、還流冷却管、窒素導入管を備えた２リットルの五つ口のセパラブルフラスコ中に、Ｎ，Ｎ−ジメチルアミノエチルアクリレートのベンジルクロライド４級化物（以下、ＤＭＡＥＡ−ＢＱという）の７５％水溶液２４９．２ｇ（純分１８６．９ｇ；７９．４９モル％）、１，３，５−トリアクリロイルヘキサヒドロ−１，３，５−トリアジン（以下、ＴＡＦという）０．０２１７ｇ（０．０１モル％）、メタリルスルフォン酸ソーダ０．６９ｇ（０．５モル％）、アクリルアミド１２．４ｇ（２０モル％）、イオン交換水５１７．３ｇを仕込み、６５℃に加温しながら窒素置換した。これに、重合開始剤として２，２´−アゾビス（２−アミジノプロパン）塩酸塩の３％水溶液２０ｇを加え、攪拌下で重合を行った。自己発熱により温度は上昇し、８０℃にて１時間重合し分岐構造を有する高分子分散剤を得た。
Production Example 3 Polymer Dispersant Production Method Benzyl chloride of N, N-dimethylaminoethyl acrylate in a 2 liter five-necked separable flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube. 249.2 g (pure content 186.9 g; 79.49 mol%) of a 75% aqueous solution of a quaternized product (hereinafter referred to as DMAEA-BQ), 1,3,5-triacryloylhexahydro-1,3,5-triazine (Hereinafter referred to as TAF) 0.0217 g (0.01 mol%), sodium methallyl sulfonate 0.69 g (0.5 mol%), acrylamide 12.4 g (20 mol%), and ion-exchanged water 517.3 g Charge and replace with nitrogen while heating to 65 ° C. To this was added 20 g of a 3% aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, and polymerization was carried out with stirring. The temperature rose due to self-heating, and polymerized at 80 ° C. for 1 hour to obtain a polymer dispersant having a branched structure.
（製造例４）高分子分散剤製造法
攪拌機、温度計、還流冷却管、窒素導入管を備えた２リットルの五つ口のセパラブルフラスコ中に、ＤＭＡＥＡ−ＢＱの７５％水溶液１４３．８４ｇ（純分１０７．９ｇ；３９．９モル％）、ＤＭＡＥＡ−Ｑの８０％水溶液９６．８３ｇ（純分７７．４６ｇ；３９．９モル％）、ＭＢＡＡ０．３０９１ｇ（０．２モル％）、メタリルスルフォン酸ソーダ０．１６ｇ（０．１モル％）、アクリルアミド１４．１８ｇ（１９．９モル％）、イオン交換水５２４．３ｇを仕込み、６５℃に加温しながら窒素置換した。これに、重合開始剤として２，２´−アゾビス（２−アミジノプロパン）塩酸塩の３％水溶液２０ｇを加え、攪拌下で重合を行った。自己発熱により温度は上昇し、８０℃にて１時間重合し分岐構造を有する高分子分散剤を得た。
(Production Example 4) Polymer Dispersant Production Method In a 2 liter five-necked separable flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen introduction tube, 143.84 g of a 75% aqueous solution of DMAEA-BQ ( Pure content 107.9 g; 39.9 mol%), DMAEA-Q 80% aqueous solution 96.83 g (pure content 77.46 g; 39.9 mol%), MBAA 0.3091 g (0.2 mol%), methallyl Sodium sulfonate 0.16 g (0.1 mol%), acrylamide 14.18 g (19.9 mol%), and ion-exchanged water 524.3 g were charged, and the atmosphere was replaced with nitrogen while heating to 65 ° C. To this, 20 g of a 3% aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride was added as a polymerization initiator, and polymerization was carried out with stirring. The temperature rose due to self-heating, and polymerized at 80 ° C. for 1 hour to obtain a polymer dispersant having a branched structure.
表中、（ｂ１）〜（ｂ４）の数字はモル％、粘度は２５℃での測定値を表し、各化合物（単量体等）略号の記載については下記の化合物を表すものとする。
ＤＭＡＥＡ−Ｑ：アクリロイルオキシエチルトリメチルアンモニウムクロライド
ＤＭＡＥＡ−ＢＱ：Ｎ，Ｎ−ジメチルアミノエチルアクリレートのベンジルクロライド４級化物
ＳＭＡＳ：メタリルスルフォン酸ソーダ
ＴＡＦ：１，３，５−トリアクリロイルヘキサヒドロー１，３，５−トリアジン
ＩＡ：イタコン酸
ＭＢＡＡ：メチレンビスアクリルアミド
ＡＭ：アクリルアミド
In the table, the numbers (b1) to (b4) represent mol%, the viscosity represents a measured value at 25 ° C., and each compound (monomer etc.) abbreviation represents the following compound.
DMAEA-Q: acryloyloxyethyltrimethylammonium chloride DMAEA-BQ: benzyl chloride quaternary product of N, N-dimethylaminoethyl acrylate SMAS: methallylsulfonic acid soda TAF: 1,3,5-triacryloylhexahydro-1, 3,5-triazine IA: itaconic acid MBAA: methylenebisacrylamide AM: acrylamide
（実施例１）水溶性重合体分散液の製造法
攪拌機、温度計、還流冷却管、窒素導入管を備えた２リットルの五つ口のセパラブルフラスコ中に、製造例１で得られた分岐構造を有する分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水９３９．８ｇに溶解した。これに、アクリルアミド１８２．９６ｇ（７４．９９５モル％）、Ｎ，Ｎ−ジメチルアミノエチルメタアクリレートのベンジルクロライド４級化物（以下、ＤＭＬという）の６０％水溶液３２４．４９ｇ（純分１９４．６９ｇ；２０モル％）、イタコン酸２２．３２ｇ（５モル％）、メチレンビスアクリルアミド（以下、ＭＢＡＡ）０．０２６５ｇ（０．００５モル％）を加え４５℃に加温しながら窒素置換した。これに重合開始剤として２，２´−アゾビス（２−アミジノプロパン）塩酸塩の２％水溶液２０ｇを加え、攪拌下で１２時間重合を行い、水溶性重合体分散液が得られた。
(Example 1) Production method of water-soluble polymer dispersion The branch obtained in Production Example 1 was placed in a 2 liter five-necked separable flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube. 110 g of the dispersant having the structure and 400 g of ammonium sulfate were dissolved in 939.8 g of ion-exchanged water. To this, 182.96 g (74.995 mol%) of acrylamide, 324.49 g of 60% aqueous solution of benzyl chloride quaternized product of N, N-dimethylaminoethyl methacrylate (hereinafter referred to as DML) (pure 194.69 g; 20 mol%), 22.32 g (5 mol%) of itaconic acid and 0.0265 g (0.005 mol%) of methylenebisacrylamide (hereinafter referred to as MBAA) were added, and the atmosphere was replaced with nitrogen while heating to 45 ° C. To this was added 20 g of a 2% aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, and polymerization was carried out for 12 hours with stirring to obtain a water-soluble polymer dispersion.
（実施例２）水溶性重合体分散液の製造法
攪拌機、温度計、還流冷却管、窒素導入管を備えた２リットルの五つ口のセパラブルフラスコ中に、製造例３で得られた分岐型構造を有する分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水９３９．８ｇに溶解した。これに、アクリルアミド１８２．９６ｇ（７４．９９５モル％）、ＤＭＬの６０％水溶液３２４．４９ｇ（純分１９４．６９ｇ；２０モル％）、イタコン酸２２．３２ｇ（５モル％）、ＭＢＡＡ ０．０２６５ｇ（０．００５モル％）を加え４５℃に加温しながら窒素置換した。これに重合開始剤として２，２‘−アゾビス（２−アミジノプロパン）塩酸塩の２％水溶液２０ｇを加え、攪拌下で１２時間重合を行い、塩水溶液に分散した微粒子の重合体が得られた。
(Example 2) Production method of water-soluble polymer dispersion The branch obtained in Production Example 3 was placed in a 2 liter five-necked separable flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube. 110 g of a dispersant having a mold structure and 400 g of ammonium sulfate were dissolved in 939.8 g of ion-exchanged water. To this, 182.96 g (74.995 mol%) of acrylamide, 324.49 g of a 60% aqueous solution of DML (pure 194.69 g; 20 mol%), 22.32 g (5 mol%) itaconic acid, 0.0265 g of MBAA (0.005 mol%) was added, and nitrogen substitution was performed while heating to 45 ° C. To this was added 20 g of a 2% aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, and polymerization was carried out for 12 hours with stirring to obtain a fine polymer dispersed in the aqueous salt solution. .
（実施例３）水溶性重合体分散液の製造法
攪拌機、温度計、還流冷却管、窒素導入管を備えた２リットルの五つ口のセパラブルフラスコ中に、製造例１で得られた分岐型構造を有する分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水９９８．６ｇに溶解した。これに、アクリルアミド２５７．５２ｇ（７９．９９モル％）、Ｎ，Ｎ−ジメチルアミノエチルメタアクリレート（以下、ＤＭという）１４２．３６ｇ（２０モル％）、ＴＡＦ ０．１１２９ｇ（０．０１モル％）を加え硫酸によりｐＨを３に調整した後４５℃に加温しながら窒素置換した。これに重合開始剤として２，２‘−アゾビス（２−アミジノプロパン）塩酸塩の２％水溶液２０ｇを加え、攪拌下で１２時間重合を行い、塩水溶液に分散した微粒子の重合体が得られた。
(Example 3) Production method of water-soluble polymer dispersion The branch obtained in Production Example 1 was placed in a 2 liter five-necked separable flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube. 110 g of a dispersant having a mold structure and 400 g of ammonium sulfate were dissolved in 998.6 g of ion-exchanged water. To this, 257.52 g (79.99 mol%) of acrylamide, 142.36 g (20 mol%) of N, N-dimethylaminoethyl methacrylate (hereinafter referred to as DM), 0.1129 g of TAF (0.01 mol%) And the pH was adjusted to 3 with sulfuric acid, followed by nitrogen substitution while heating to 45 ° C. To this was added 20 g of a 2% aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, and polymerization was carried out for 12 hours with stirring to obtain a fine polymer dispersed in the aqueous salt solution. .
（実施例４）水溶性重合体分散液の製造法
攪拌機、温度計、還流冷却管、窒素導入管を備えた２リットルの五つ口のセパラブルフラスコ中に、製造例３で得られた分岐型構造を有する分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水９９８．６ｇに溶解した。これに、アクリルアミド２５７．５２ｇ（７９．９９モル％）、ＤＭ １４２．３６ｇ（２０モル％）、ＴＡＦ ０．１１２９ｇ（０．０１モル％）を加え硫酸によりｐＨを３に調整した後４５℃に加温しながら窒素置換した。これに重合開始剤として２，２´−アゾビス（２−アミジノプロパン）塩酸塩の２％水溶液２０ｇを加え、攪拌下で１２時間重合を行い、塩水溶液に分散した微粒子の重合体が得られた。
(Example 4) Production method of water-soluble polymer dispersion The branch obtained in Production Example 3 was placed in a 2 liter five-necked separable flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube. 110 g of a dispersant having a mold structure and 400 g of ammonium sulfate were dissolved in 998.6 g of ion-exchanged water. To this was added 257.52 g (79.99 mol%) of acrylamide, 142.36 g (20 mol%) of DM, and 0.1129 g (0.01 mol%) of TAF, and the pH was adjusted to 3 with sulfuric acid, and then the temperature was increased to 45 ° C. Nitrogen was replaced while warming. To this was added 20 g of a 2% aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, and polymerization was carried out for 12 hours with stirring to obtain a fine polymer dispersed in the aqueous salt solution. .
（実施例５）水溶性重合体分散液の製造法
攪拌機、温度計、還流冷却管、窒素導入管を備えた２リットルの五つ口のセパラブルフラスコ中に、製造例１で得られた分岐構造を有する分散剤を１６０ｇ、硫酸アンモニウム４００ｇをイオン交換水９５４．１２ｇに溶解した。これに、アクリルアミド２１４．１２ｇ（７６．９９５モル％）、ＤＭＬの６０％水溶液１１０．９７ｇ（純分６６．５８２ｇ；６モル％）、ＤＭＡＥＡ−ＢＱの７５％水溶液８４．３９ｇ（純分６３．２９２ｇ；６モル％）、イタコン酸５５．９８ｇ（１１モル％）、ＭＢＡＡ ０．０３０２ｇ（０．００５モル％）を加え４０℃に加温しながら窒素置換した。これに重合開始剤として２，２‘−アゾビス（２−アミジノプロパン）塩酸塩の２％水溶液２０ｇを加え、攪拌下で１２時間重合を行い、水溶性重合体分散液が得られた。
(Example 5) Production method of water-soluble polymer dispersion The branch obtained in Production Example 1 was placed in a 2 liter five-necked separable flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube. 160 g of the dispersant having the structure and 400 g of ammonium sulfate were dissolved in 954.12 g of ion-exchanged water. To this, 214.12 g (76.995 mol%) of acrylamide, 110.97 g of a 60% aqueous solution of DML (66.582 g pure; 6 mol%), 84.39 g of a 75% aqueous solution of DMAEA-BQ (63. pure net). 292 g; 6 mol%), itaconic acid 55.98 g (11 mol%) and MBAA 0.0302 g (0.005 mol%) were added, and the atmosphere was replaced with nitrogen while heating to 40 ° C. To this was added 20 g of a 2% aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, and polymerization was carried out for 12 hours with stirring to obtain a water-soluble polymer dispersion.
（実施例６）水溶性重合体分散液の製造法
攪拌機、温度計、還流冷却管、窒素導入管を備えた２リットルの五つ口のセパラブルフラスコ中に、製造例１で得られた分岐構造を有する分散剤を５０ｇ、硫酸アンモニウム４００ｇをイオン交換水１０５９．６８ｇに溶解した。これに、アクリルアミド２６１．２９ｇ（８７．９９５モル％）、ＤＭＬの６０％水溶液１１８．４８ｇ（純分７１．０８８ｇ；６モル％）、ＤＭＡＥＡ−ＢＱの７５％水溶液９０．１１ｇ（純分６７．５８２ｇ；６モル％）、ＭＢＡＡ ０．０３２２ｇ（０．００５モル％）を加え４０℃に加温しながら窒素置換した。これに重合開始剤として２，２´−アゾビス（２−アミジノプロパン）塩酸塩の２％水溶液２０ｇを加え、攪拌下で１２時間重合を行い、水溶性重合体分散液が得られた。
Example 6 Production Method of Water-Soluble Polymer Dispersion Branched in Production Example 1 in a 2 liter five-necked separable flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube 50 g of the dispersant having the structure and 400 g of ammonium sulfate were dissolved in 1059.68 g of ion-exchanged water. To this, 261.29 g (87.995 mol%) of acrylamide, 118.48 g of a 60% aqueous solution of DML (71.088 g pure; 6 mol%), 90.11 g of a 75% aqueous solution of DMAEA-BQ (67.75 pure). 582 g; 6 mol%) and 0.0322 g (0.005 mol%) of MBAA were added and the atmosphere was replaced with nitrogen while heating to 40 ° C. To this was added 20 g of a 2% aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, and polymerization was carried out for 12 hours with stirring to obtain a water-soluble polymer dispersion.
（実施例７）水溶性重合体分散液の製造法
攪拌機、温度計、還流冷却管、窒素導入管を備えた２リットルの五つ口のセパラブルフラスコ中に、製造例１で得られた分岐構造を有する分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水１０１８．３８ｇに溶解した。これに、アクリルアミド２０９．２９ｇ（７７．５モル％）、ＤＭＡＥＡ−ＢＱの７５％水溶液２０４．８７ｇ（純分１５３．６５ｇ；１５モル％）、イタコン酸３７．０６ｇ（７．５モル％）を加え４０℃に加温しながら窒素置換した。これに重合開始剤として２，２´−アゾビス（２−アミジノプロパン）塩酸塩の２％水溶液２０ｇを加え、攪拌下で１２時間重合を行い、水溶性重合体分散液が得られた。
(Example 7) Production method of water-soluble polymer dispersion The branch obtained in Production Example 1 was placed in a 2 liter five-necked separable flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube. 110 g of the dispersant having the structure and 400 g of ammonium sulfate were dissolved in 1018.38 g of ion-exchanged water. To this, 209.29 g (77.5 mol%) of acrylamide, 204.87 g of a 75% aqueous solution of DMAEA-BQ (pure content: 153.65 g; 15 mol%), and 37.06 g (7.5 mol%) of itaconic acid were added. In addition, nitrogen was substituted while heating to 40 ° C. To this was added 20 g of a 2% aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, and polymerization was carried out for 12 hours with stirring to obtain a water-soluble polymer dispersion.
（実施例８）水溶性重合体分散液の製造法
攪拌機、温度計、還流冷却管、窒素導入管を備えた２リットルの五つ口のセパラブルフラスコ中に、製造例１で得られた分岐構造を有する分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水１０１６．１４ｇに溶解した。これに、アクリルアミド２３９．６１ｇ（８５モル％）、ＤＭＡＥＡ−ＢＱの７５％水溶液２１３．８６ｇ（純分１６０．４ｇ；１５モル％）を加え４０℃に加温しながら窒素置換した。これに重合開始剤として２，２´−アゾビス（２−アミジノプロパン）塩酸塩の２％水溶液２０ｇを加え、攪拌下で１２時間重合を行い、水溶性重合体分散液が得られた。
(Example 8) Production method of water-soluble polymer dispersion The branch obtained in Production Example 1 was placed in a 2 liter five-necked separable flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube. 110 g of the dispersant having the structure and 400 g of ammonium sulfate were dissolved in 101.14 g of ion-exchanged water. To this, 239.61 g (85 mol%) of acrylamide and 213.86 g of a 75% aqueous solution of DMAEA-BQ (pure content 160.4 g; 15 mol%) were added, and the atmosphere was replaced with nitrogen while heating to 40 ° C. To this was added 20 g of a 2% aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, and polymerization was carried out for 12 hours with stirring to obtain a water-soluble polymer dispersion.
（実施例９）水溶性重合体分散液の製造法
攪拌機、温度計、還流冷却管、窒素導入管を備えた２リットルの五つ口のセパラブルフラスコ中に、製造例１で得られた分岐型構造を有する分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水１０４９．２９ｇに溶解した。これに、アクリルアミド３３８．９２ｇ（９１．９９モル％）、ＤＭ ４０．７３ｇ（５モル％）、イタコン酸２０．２２ｇ（３モル％）、ＴＡＦ ０．１２９２ｇ（０．０１モル％）を加え硫酸によりｐＨを３に調整した後４０℃に加温しながら窒素置換した。これに重合開始剤として２，２´−アゾビス（２−アミジノプロパン）塩酸塩の２％水溶液２０ｇを加え、攪拌下で１２時間重合を行い、塩水溶液に分散した微粒子の重合体が得られた。
(Example 9) Production method of water-soluble polymer dispersion The branch obtained in Production Example 1 was placed in a 2 liter five-necked separable flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen introduction tube. 110 g of a dispersant having a mold structure and 400 g of ammonium sulfate were dissolved in 1049.29 g of ion-exchanged water. To this, 338.92 g (91.99 mol%) of acrylamide, 40.73 g (5 mol%) of DM, 20.22 g (3 mol%) of itaconic acid, and 0.1292 g (0.01 mol%) of TAF were added. Then, the pH was adjusted to 3 and then the atmosphere was replaced with nitrogen while heating to 40 ° C. To this was added 20 g of a 2% aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, and polymerization was carried out for 12 hours with stirring to obtain a fine polymer dispersed in the aqueous salt solution. .
（実施例１０）水溶性重合体分散液の製造法
攪拌機、温度計、還流冷却管、窒素導入管を備えた２リットルの五つ口のセパラブルフラスコ中に、製造例１で得られた分岐型構造を有する分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水１０４８．８１ｇに溶解した。これに、アクリルアミド３５８．１８ｇ（９４．９９モル％）、ＤＭ ４１．６８ｇ（５モル％）、ＴＡＦ ０．１３２２ｇ（０．０１モル％）を加え硫酸によりｐＨを３に調整した後４０℃に加温しながら窒素置換した。これに重合開始剤として２，２´−アゾビス（２−アミジノプロパン）塩酸塩の２％水溶液２０ｇを加え、攪拌下で１２時間重合を行い、塩水溶液に分散した微粒子の重合体が得られた。
(Example 10) Production method of water-soluble polymer dispersion The branch obtained in Production Example 1 was placed in a 2 liter five-necked separable flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube. 110 g of a dispersant having a mold structure and 400 g of ammonium sulfate were dissolved in 1048.81 g of ion-exchanged water. To this was added 358.18 g (94.99 mol%) of acrylamide, 41.68 g (5 mol%) of DM, and 0.1322 g (0.01 mol%) of TAF, and the pH was adjusted to 3 with sulfuric acid, and then heated to 40 ° C. Nitrogen was replaced while warming. To this was added 20 g of a 2% aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, and polymerization was carried out for 12 hours with stirring to obtain a fine polymer dispersed in the aqueous salt solution. .
（実施例１１）水溶性重合体分散液の製造法
攪拌機、温度計、還流冷却管、窒素導入管を備えた２リットルの五つ口のセパラブルフラスコ中に、製造例４で得られた分岐構造を有する分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水９９９．６８ｇに溶解した。これに、アクリルアミド２６１．２９ｇ（８７．９９５モル％）、ＤＭＬの６０％水溶液１１８．４８ｇ（純分７１．０８８ｇ；６モル％）、ＤＭＡＥＡ−ＢＱの７５％水溶液９０．１１ｇ（純分６７．５８２ｇ；６モル％）、ＭＢＡＡ ０．０３２２ｇ（０．００５モル％）を加え４０℃に加温しながら窒素置換した。これに重合開始剤として２，２´−アゾビス（２−アミジノプロパン）塩酸塩の２％水溶液２０ｇを加え、攪拌下で１２時間重合を行い、水溶性重合体分散液が得られた。
(Example 11) Production method of water-soluble polymer dispersion The branch obtained in Production Example 4 was placed in a 2 liter five-necked separable flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube. 110 g of the dispersant having the structure and 400 g of ammonium sulfate were dissolved in 999.68 g of ion-exchanged water. To this, 261.29 g (87.995 mol%) of acrylamide, 118.48 g of a 60% aqueous solution of DML (71.088 g pure; 6 mol%), 90.11 g of a 75% aqueous solution of DMAEA-BQ (67.75 pure). 582 g; 6 mol%) and 0.0322 g (0.005 mol%) of MBAA were added and the atmosphere was replaced with nitrogen while heating to 40 ° C. To this was added 20 g of a 2% aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, and polymerization was carried out for 12 hours with stirring to obtain a water-soluble polymer dispersion.
（実施例１２）水溶性重合体分散液の製造法
攪拌機、温度計、還流冷却管、窒素導入管を備えた２リットルの五つ口のセパラブルフラスコ中に、製造例４で得られた分岐構造を有する分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水１０１８．３８ｇに溶解した。これに、アクリルアミド２０９．２９ｇ（７７．５モル％）、ＤＭＡＥＡ−ＢＱの７５％水溶液２０４．８７ｇ（純分１５３．６５ｇ；１５モル％）、イタコン酸３７．０６ｇ（７．５モル％）を加え４０℃に加温しながら窒素置換した。これに重合開始剤として２，２´−アゾビス（２−アミジノプロパン）塩酸塩の２％水溶液２０ｇを加え、攪拌下で１２時間重合を行い、水溶性重合体分散液が得られた。
(Example 12) Production method of water-soluble polymer dispersion The branch obtained in Production Example 4 was placed in a 2 liter five-necked separable flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube. 110 g of the dispersant having the structure and 400 g of ammonium sulfate were dissolved in 1018.38 g of ion-exchanged water. To this, 209.29 g (77.5 mol%) of acrylamide, 204.87 g of a 75% aqueous solution of DMAEA-BQ (pure content: 153.65 g; 15 mol%), and 37.06 g (7.5 mol%) of itaconic acid were added. In addition, nitrogen was substituted while heating to 40 ° C. To this was added 20 g of a 2% aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, and polymerization was carried out for 12 hours with stirring to obtain a water-soluble polymer dispersion.
（実施例１３）水溶性重合体分散液の製造法
攪拌機、温度計、還流冷却管、窒素導入管を備えた２リットルの五つ口のセパラブルフラスコ中に、製造例４で得られた分岐型構造を有する分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水１０４９．２９ｇに溶解した。これに、アクリルアミド３３８．９２ｇ（９１．９９モル％）、ＤＭ ４０．７３ｇ（５モル％）、イタコン酸２０．２２ｇ（３モル％）、ＴＡＦ ０．１２９２ｇ（０．０１モル％）を加え硫酸によりｐＨを３に調整した後４０℃に加温しながら窒素置換した。これに重合開始剤として２，２´−アゾビス（２−アミジノプロパン）塩酸塩の２％水溶液２０ｇを加え、攪拌下で１２時間重合を行い、塩水溶液に分散した微粒子の重合体が得られた。
(Example 13) Production method of water-soluble polymer dispersion The branch obtained in Production Example 4 was placed in a 2 liter five-necked separable flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube. 110 g of a dispersant having a mold structure and 400 g of ammonium sulfate were dissolved in 1049.29 g of ion-exchanged water. To this, 338.92 g (91.99 mol%) of acrylamide, 40.73 g (5 mol%) of DM, 20.22 g (3 mol%) of itaconic acid, and 0.1292 g (0.01 mol%) of TAF were added. Then, the pH was adjusted to 3 and then the atmosphere was replaced with nitrogen while heating to 40 ° C. To this was added 20 g of a 2% aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, and polymerization was carried out for 12 hours with stirring to obtain a fine polymer dispersed in the aqueous salt solution. .
（比較例１）水溶性重合体分散液の製造法
攪拌機、温度計、還流冷却管、窒素導入管を備えた２リットルの五つ口のセパラブルフラスコ中に、製造例２で得られた分岐型構造を有しない分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水９３９．８ｇに溶解した。これに、アクリルアミド１８２．９６ｇ（７４．９９５モル％）、ＤＭＬの６０％水溶液３２４．４９ｇ（純分１９４．６９ｇ；２０モル％）、イタコン酸２２．３２ｇ（５モル％）、ＭＢＡＡ ０．０２６５ｇ（０．００５モル％）を加え４５℃に加温しながら窒素置換した。これに重合開始剤として２，２´−アゾビス（２−アミジノプロパン）塩酸塩の２％水溶液２０ｇを加え、攪拌下で１２時間重合を行い、塩水溶液に分散した微粒子の重合体が得られた。
Comparative Example 1 Production Method of Water-Soluble Polymer Dispersion Branched in Production Example 2 in a 2 liter five-necked separable flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube 110 g of a dispersant having no mold structure and 400 g of ammonium sulfate were dissolved in 939.8 g of ion-exchanged water. To this, 182.96 g (74.995 mol%) of acrylamide, 324.49 g of a 60% aqueous solution of DML (pure 194.69 g; 20 mol%), 22.32 g (5 mol%) itaconic acid, 0.0265 g of MBAA (0.005 mol%) was added, and nitrogen substitution was performed while heating to 45 ° C. To this was added 20 g of a 2% aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, and polymerization was carried out for 12 hours with stirring to obtain a fine polymer dispersed in the aqueous salt solution. .
（比較例２）水溶性重合体分散液の製造法
攪拌機、温度計、還流冷却管、窒素導入管を備えた２リットルの五つ口のセパラブルフラスコ中に、製造例２で得られた分岐型構造を有しない分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水９９８．６ｇに溶解した。これに、アクリルアミド２５７．５２ｇ（７９．９９モル％）、ＤＭ １４２．３６ｇ（２０モル％）、ＴＡＦ ０．１１２９ｇ（０．０１モル％）を加え硫酸によりｐＨを３に調整した後４５℃に加温しながら窒素置換した。これに重合開始剤として２，２´−アゾビス（２−アミジノプロパン）塩酸塩の２％水溶液２０ｇを加え、攪拌下で１２時間重合を行い、塩水溶液に分散した微粒子の重合体が得られた。
Comparative Example 2 Production Method of Water-Soluble Polymer Dispersion Branch obtained in Production Example 2 in a 2 liter five-necked separable flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube 110 g of a dispersant having no mold structure and 400 g of ammonium sulfate were dissolved in 998.6 g of ion-exchanged water. To this was added 257.52 g (79.99 mol%) of acrylamide, 142.36 g (20 mol%) of DM, and 0.1129 g (0.01 mol%) of TAF, and the pH was adjusted to 3 with sulfuric acid, and then the temperature was increased to 45 ° C. While warming, the atmosphere was replaced with nitrogen. To this was added 20 g of a 2% aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, and polymerization was carried out for 12 hours with stirring to obtain a fine polymer dispersed in the aqueous salt solution. .
（比較例３）水溶性重合体分散液の製造法
攪拌機、温度計、還流冷却管、窒素導入管を備えた２リットルの五つ口のセパラブルフラスコ中に、製造例２で得られた分岐構造を有しない分散剤を１６０ｇ、硫酸アンモニウム４００ｇをイオン交換水９５４．１２ｇに溶解した。これに、アクリルアミド２１４．１２ｇ（７６．９９５モル％）、ＤＭＬの６０％水溶液１１０．９７ｇ（純分６６．５８２ｇ；６モル％）、ＤＭＡＥＡ−ＢＱの７５％水溶液８４．３９ｇ（純分６３．２９２ｇ；６モル％）、イタコン酸５５．９８ｇ（１１モル％）、ＭＢＡＡ ０．０３０２ｇ（０．００５モル％）を加え４０℃に加温しながら窒素置換した。これに重合開始剤として２，２´−アゾビス（２−アミジノプロパン）塩酸塩の２％水溶液２０ｇを加え、攪拌下で１２時間重合を行い、水溶性重合体分散液が得られた。
Comparative Example 3 Production Method of Water-Soluble Polymer Dispersion Branch obtained in Production Example 2 in a 2 liter five-necked separable flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube 160 g of a dispersant having no structure and 400 g of ammonium sulfate were dissolved in 954.12 g of ion-exchanged water. To this, 214.12 g (76.995 mol%) of acrylamide, 110.97 g of a 60% aqueous solution of DML (66.582 g pure; 6 mol%), 84.39 g of a 75% aqueous solution of DMAEA-BQ (63. pure net). 292 g; 6 mol%), itaconic acid 55.98 g (11 mol%) and MBAA 0.0302 g (0.005 mol%) were added, and the atmosphere was replaced with nitrogen while heating to 40 ° C. To this was added 20 g of a 2% aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, and polymerization was carried out for 12 hours with stirring to obtain a water-soluble polymer dispersion.
（比較例４）水溶性重合体分散液の製造法
攪拌機、温度計、還流冷却管、窒素導入管を備えた２リットルの五つ口のセパラブルフラスコ中に、製造例２で得られた分岐構造を有しない分散剤を５０ｇ、硫酸アンモニウム４００ｇをイオン交換水１０５９．６８ｇに溶解した。これに、アクリルアミド２６１．２９ｇ（８７．９９５モル％）、ＤＭＬの６０％水溶液１１８．４８ｇ（純分７１．０８８ｇ；６モル％）、ＤＭＡＥＡ−ＢＱの７５％水溶液９０．１１ｇ（純分６７．５８２ｇ；６モル％）、ＭＢＡＡ ０．０３２２ｇ（０．００５モル％）を加え４０℃に加温しながら窒素置換した。これに重合開始剤として２，２´−アゾビス（２−アミジノプロパン）塩酸塩の２％水溶液２０ｇを加え、攪拌下で１２時間重合を行い、水溶性重合体分散液が得られた。
Comparative Example 4 Production Method of Water-Soluble Polymer Dispersion Branched in Production Example 2 in a 2 liter five-necked separable flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube 50 g of a dispersant having no structure and 400 g of ammonium sulfate were dissolved in 1059.68 g of ion-exchanged water. To this, 261.29 g (87.995 mol%) of acrylamide, 118.48 g of a 60% aqueous solution of DML (71.088 g pure; 6 mol%), 90.11 g of a 75% aqueous solution of DMAEA-BQ (67.75 pure). 582 g; 6 mol%) and 0.0322 g (0.005 mol%) of MBAA were added and the atmosphere was replaced with nitrogen while heating to 40 ° C. To this was added 20 g of a 2% aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, and polymerization was carried out for 12 hours with stirring to obtain a water-soluble polymer dispersion.
（比較例５）水溶性重合体分散液の製造法
攪拌機、温度計、還流冷却管、窒素導入管を備えた２リットルの五つ口のセパラブルフラスコ中に、製造例２で得られた分岐構造を有しない分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水１０１８．３８ｇに溶解した。これに、アクリルアミド２０９．２９ｇ（７７．５モル％）、ＤＭＡＥＡ−ＢＱの７５％水溶液２０４．８７ｇ（純分１５３．６５ｇ；１５モル％）、イタコン酸３７．０６ｇ（７．５モル％）を加え４０℃に加温しながら窒素置換した。これに重合開始剤として２，２´−アゾビス（２−アミジノプロパン）塩酸塩の２％水溶液２０ｇを加え、攪拌下で１２時間重合を行い、水溶性重合体分散液が得られた。
(Comparative Example 5) Production Method of Water-Soluble Polymer Dispersion Branch obtained in Production Example 2 in a 2 liter five-necked separable flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube 110 g of a dispersant having no structure and 400 g of ammonium sulfate were dissolved in 1018.38 g of ion-exchanged water. To this, 209.29 g (77.5 mol%) of acrylamide, 204.87 g of a 75% aqueous solution of DMAEA-BQ (pure content: 153.65 g; 15 mol%), and 37.06 g (7.5 mol%) of itaconic acid were added. In addition, nitrogen was substituted while heating to 40 ° C. To this was added 20 g of a 2% aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, and polymerization was carried out for 12 hours with stirring to obtain a water-soluble polymer dispersion.
（比較例６）水溶性重合体分散液の製造法
攪拌機、温度計、還流冷却管、窒素導入管を備えた２リットルの五つ口のセパラブルフラスコ中に、製造例２で得られた分岐構造を有しない分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水１０１６．１４ｇに溶解した。これに、アクリルアミド２３９．６１ｇ（８５モル％）、ＤＭＡＥＡ−ＢＱの７５％水溶液２１３．８６ｇ（純分１６０．４ｇ；１５モル％）を加え４０℃に加温しながら窒素置換した。これに重合開始剤として２，２‘−アゾビス（２−アミジノプロパン）塩酸塩の２％水溶液２０ｇを加え、攪拌下で１２時間重合を行い、水溶性重合体分散液が得られた。
Comparative Example 6 Production Method of Water-Soluble Polymer Dispersion Branched in Production Example 2 in a 2 liter five-necked separable flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube 110 g of a dispersant having no structure and 400 g of ammonium sulfate were dissolved in 101.14 g of ion-exchanged water. To this, 239.61 g (85 mol%) of acrylamide and 213.86 g of a 75% aqueous solution of DMAEA-BQ (pure content 160.4 g; 15 mol%) were added, and the atmosphere was replaced with nitrogen while heating to 40 ° C. To this was added 20 g of a 2% aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, and polymerization was carried out for 12 hours with stirring to obtain a water-soluble polymer dispersion.
（比較例７）水溶性重合体分散液の製造法
攪拌機、温度計、還流冷却管、窒素導入管を備えた２リットルの五つ口のセパラブルフラスコ中に、製造例２で得られた分岐型構造を有しない分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水１０４９．２９ｇに溶解した。これに、アクリルアミド３３８．９２ｇ（９１．９９モル％）、ＤＭ ４０．７３ｇ（５モル％）、イタコン酸２０．２２ｇ（３モル％）、ＴＡＦ ０．１２９２ｇ（０．０１モル％）を加え硫酸によりｐＨを３に調整した後４０℃に加温しながら窒素置換した。これに重合開始剤として２，２´−アゾビス（２−アミジノプロパン）塩酸塩の２％水溶液２０ｇを加え、攪拌下で１２時間重合を行い、塩水溶液に分散した微粒子の重合体が得られた。
Comparative Example 7 Production Method of Water-Soluble Polymer Dispersion Branched in Production Example 2 in a 2 liter five-necked separable flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube 110 g of a dispersant having no mold structure and 400 g of ammonium sulfate were dissolved in 1049.29 g of ion-exchanged water. To this, 338.92 g (91.99 mol%) of acrylamide, 40.73 g (5 mol%) of DM, 20.22 g (3 mol%) of itaconic acid, and 0.1292 g (0.01 mol%) of TAF were added. Then, the pH was adjusted to 3 and then the atmosphere was replaced with nitrogen while heating to 40 ° C. To this was added 20 g of a 2% aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, and polymerization was carried out for 12 hours with stirring to obtain a fine polymer dispersed in the aqueous salt solution. .
（比較例８）水溶性重合体分散液の製造法
攪拌機、温度計、還流冷却管、窒素導入管を備えた２リットルの五つ口のセパラブルフラスコ中に、製造例２で得られた分岐型構造を有しない分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水１０４８．８１ｇに溶解した。これに、アクリルアミド３５８．１８ｇ（９４．９９モル％）、ＤＭ ４１．６８ｇ（５モル％）、ＴＡＦ ０．１３２２ｇ（０．０１モル％）を加え硫酸によりｐＨを３に調整した後４０℃に加温しながら窒素置換した。これに重合開始剤として２，２´−アゾビス（２−アミジノプロパン）塩酸塩の２％水溶液２０ｇを加え、攪拌下で１２時間重合を行い、塩水溶液に分散した微粒子の重合体が得られた。
Comparative Example 8 Production Method of Water-Soluble Polymer Dispersion Branch obtained in Production Example 2 in a 2 liter five-necked separable flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube 110 g of a dispersant having no mold structure and 400 g of ammonium sulfate were dissolved in 1048.81 g of ion-exchanged water. To this was added 358.18 g (94.99 mol%) of acrylamide, 41.68 g (5 mol%) of DM, and 0.1322 g (0.01 mol%) of TAF, and the pH was adjusted to 3 with sulfuric acid, and then heated to 40 ° C. While warming, the atmosphere was replaced with nitrogen. To this was added 20 g of a 2% aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, and polymerization was carried out for 12 hours with stirring to obtain a fine polymer dispersed in the aqueous salt solution. .
実施例および比較例で得られた分散体について、平均粒径、分子量分布を測定し、また、粒子外観を観察した。その結果を表２に示す。なお、平均粒径及び粒子外観は、光学顕微鏡で観察することにより行った。粒子外観は、粒子が均一、粗大粒子が微量存在、粗大粒子が多いの３段階で評価した。分子量分布は、ゲルパーメーションクロマトグラフィー法によるポリエチレンオキシド換算値で得られた重量平均分子量および数平均分子量から測定した値である。
ゲルパーメーションクロマトグラフィーは以下の測定条件にて測定した。
ＧＰＣ本体：東ソー（株）製
カラム：東ソー（株）製ガードカラムＰＷＸＬ１本およびＧＭＰＷＸＬ２本（温度４０℃）
溶離液：０．５ｍｏｌ／ｌ酢酸緩衝液（０．５ｍｏｌ／ｌ酢酸（和光純薬工業（株）製）＋０．５ｍｏｌ／ｌ酢酸ナトリウム（キシダ化学（株）製）水溶液、ｐＨ約４．２）
流速：０．８ｍｌ／分
検出器：東ソー（株）製濃度検出器（ＲＩ−８０１０）および光散乱検出器（ＬＳ−８０００）（室温）ＬＡＬＬＳ法
ビスコテック社製ＴＤＡ ＭＯＤＥＬ３０１（濃度検出器および９０°光散乱検出器および粘度検出器（温度４０℃））ＲＡＬＬＳ法
測定サンプル：０．５重量％に調整後ｐＨ１０〜１２になるまで苛性ソーダを添加し、８０℃以上の湯浴に４時間浸した後、溶離液で０．０１２５重量％に希釈して測定した。
For the dispersions obtained in Examples and Comparative Examples, the average particle diameter and molecular weight distribution were measured, and the particle appearance was observed. The results are shown in Table 2. In addition, the average particle diameter and particle | grain appearance were performed by observing with an optical microscope. The appearance of the particles was evaluated in three stages: uniform particles, a small amount of coarse particles, and a large number of coarse particles. The molecular weight distribution is a value measured from a weight average molecular weight and a number average molecular weight obtained as a polyethylene oxide conversion value by a gel permeation chromatography method.
Gel permeation chromatography was measured under the following measurement conditions.
GPC body: Tosoh Co., Ltd. column: Tosoh Co., Ltd. guard column PWXL 1 and GMPWXL 2 (temperature 40 ° C.)
Eluent: 0.5 mol / l acetate buffer (0.5 mol / l acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.) + 0.5 mol / l sodium acetate (manufactured by Kishida Chemical Co., Ltd.), aqueous solution, pH about 4.2 )
Flow rate: 0.8 ml / min Detector: Tosoh Corporation concentration detector (RI-8010) and light scattering detector (LS-8000) (room temperature) LALLS method TDA MODEL 301 (concentration detector and 90) ° Light scattering detector and viscosity detector (temperature 40 ° C)) RALLS method measurement sample: After adjusting to 0.5% by weight, caustic soda was added until pH 10-12 and immersed in a hot water bath at 80 ° C or higher for 4 hours. Then, it diluted to 0.0125 weight% with the eluent and measured.
表中の数字はモル％。粘度は２５℃での測定値。
なお、表２中の各化合物（単量体等）略号の記載については下記の化合物を表すものとする。
ＤＭＬ：Ｎ，Ｎ−ジメチルアミノエチルメタアクリレートのベンジルクロライド４級化物
ＤＭＡＥＡ−ＢＱ：Ｎ，Ｎ−ジメチルアミノエチルアクリレートのベンジルクロライド４級化物
ＤＭ：Ｎ，Ｎ−ジメチルアミノエチルメタアクリレート
ＳＭＡＳ：メタリスルフォン酸ソーダ
ＭＢＡＡ：メチレンビスアクリルアミド
ＴＡＦ：１，３，５−トリアクリロイルヘキサヒドロ−１，３，５−トリアジン
ＡＭ：アクリルアミド
The numbers in the table are mol%. Viscosity is measured at 25 ° C.
In addition, about description of each compound (monomer etc.) abbreviation in Table 2, it shall represent the following compound.
DML: benzyl chloride quaternized product of N, N-dimethylaminoethyl methacrylate DMAEA-BQ: benzyl chloride quaternized product of N, N-dimethylaminoethyl acrylate DM: N, N-dimethylaminoethyl methacrylate SMAS: metallisulfone Acid soda MBAA: Methylenebisacrylamide TAF: 1,3,5-triacryloylhexahydro-1,3,5-triazine AM: acrylamide
評価方法１：板紙向け
（評価例１〜２６及び比較評価例１〜１０）
段ボ−ル古紙をナイアガラ式ビーターにて叩解し、カナディアン・スタンダ−ド・フリ−ネス（Ｃ．Ｓ．Ｆ）３５０ｍｌに調整した紙料に硫酸バンドを対紙料固形分量１．０重量％添加してｐＨ６．５とした。当該紙料スラリーを抄紙するにおいて、紙料濃度１．５％として実施例１から１３および比較例１から８で得られた水溶性重合体分散液を水道水で重合体（（Ａ）+（Ｂ））の固形分濃度を０．０５重量％に希釈して、対紙料固形分量０．０５重量％あるいは０．１重量％添加し、タッピ・シートマシンにて脱水し、５ｋｇ／ｃｍ２で２分間プレスして、坪量１５０ｇ／ｍ２
となるよう抄紙した。次いで回転型乾燥機で１０５℃において４分間乾燥し、２３℃、５０％Ｒ．Ｈ．の条件下に２４時間調湿したのち、比破裂強度および地合変動係数を測定した。同時に、上記の薬品添加後のパルプスラリー５００ｍｌをブリットジャー（４０メッシュ）に入れタービン羽根を備えた撹拌機を用いて撹拌しながら（２０００ｒｐｍ）下穴から濾水１００ｍｌを採取し、Ｎｏ２濾紙により吸引濾過後、１１０℃で６０分間乾燥し、乾燥後の質量を測定することにより、全歩留り（ＯＰＲ）を求めた。また、別途、上記薬品添加後のパルプスラリーの濾水量も測定した。
Evaluation method 1: For paperboard (Evaluation Examples 1 to 26 and Comparative Evaluation Examples 1 to 10)
Corrugated cardboard paper is beaten with a Niagara-type beater and adjusted to 350 ml of Canadian Standard Freeness (C.S.F.). A sulfate band is added to the paper material at a solid content of 1.0% by weight. Added to pH 6.5. In making the paper slurry, the water-soluble polymer dispersions obtained in Examples 1 to 13 and Comparative Examples 1 to 8 at a paper stock concentration of 1.5% were polymerized with tap water ((A) + ( B)) is diluted to 0.05% by weight, added to the paper solids in an amount of 0.05% or 0.1% by weight, dehydrated with a tapi sheet machine, and 5 kg / cm 2. Press for 2 minutes and basis weight 150g / m 2
Paper was made so that Subsequently, it dried for 4 minutes at 105 degreeC with a rotary dryer, and 23 degreeC and 50% R. H. After conditioned for 24 hours under the above conditions, the specific burst strength and the formation variation coefficient were measured. At the same time, 500 ml of pulp slurry after adding the above chemicals was put into a brit jar (40 mesh) and stirred using a stirrer equipped with turbine blades (2000 rpm), and 100 ml of filtrate was collected from the pilot hole and sucked with No2 filter paper. After filtration, it was dried at 110 ° C. for 60 minutes, and the mass after drying was measured to obtain the total yield (OPR). Separately, the amount of drainage of the pulp slurry after the addition of the chemical was also measured.
なお、濾水量は、ＪＩＳ Ｐ８１２１に準拠して測定し、比破裂強度は、ＪＩＳ Ｐ８１３１に準拠して測定し、地合変動係数は、得られた紙を通過する光（輝度）をパーソナル画像処理システムＨｙｐｅｒ−７００（ＯＢＳ製）に取り込み、輝度分布を統計解析することにより測定した。なお、評価例２７〜５２および比較評価例１１〜２０における内部強度（インターナルボンド）はＪ．ＴＡＰＰＩ Ｎｏ１８−２に準じて測定した。 The amount of drainage is measured in accordance with JIS P811, the specific burst strength is measured in accordance with JIS P811, and the formation variation coefficient is the light (luminance) that passes through the obtained paper for personal image processing. It was measured by taking in the system Hyper-700 (manufactured by OBS) and statistically analyzing the luminance distribution. The internal strength (internal bond) in Evaluation Examples 27 to 52 and Comparative Evaluation Examples 11 to 20 is It measured according to TAPPI No18-2.
各評価例における水溶性高分子分散体固形分の紙料固形分に対する添加率と各項目の測定結果を表３に示す。 Table 3 shows the addition rate of the water-soluble polymer dispersion solid content in each evaluation example with respect to the paper solid content and the measurement results of each item.
地合変動係数は数値が小さいほうが地合良好である。 The smaller the numerical value of the formation variation coefficient, the better the formation.
評価方法２：洋紙向け
（評価例２７〜５２及び比較評価例１１〜２０）
Ｌ−ＢＫＰをナイアガラ式ビーターにて叩解し、カナディアン・スタンダ−ド・フリ−ネス（Ｃ．Ｓ．Ｆ）４００ｍｌに調整した紙料に硫酸バンドを対紙料固形分量１．０重量％添加し、填料として軽質炭酸カルシウム（奥多摩工業株式会社製、商品名：タマパールＴＰ−１２１）を対紙料固形分量１０重量％添加し、ｐＨ７．０とした。当該紙料スラリーを抄紙するにおいて、紙料濃度１．０％として実施例１から１３および比較例１から８で得られた重合体水溶液を水道水で重合体（（Ａ）+（Ｂ））の固形分濃度を０．０５重量％に希釈して、対紙料固形分量０．０２５重量％あるいは０．０５重量％添加し、タッピ・シートマシンにて脱水し、５ｋｇ／ｃｍ２
で２分間プレスして、坪量６０ｇ／ｍ２ となるよう抄紙した。次いで回転型乾燥機で１０５℃において４分間乾燥し、２３℃、５０％Ｒ．Ｈ．の条件下に２４時間調湿したのち、内部強度を測定した。なお、濾水量、地合変動係数および全歩留りは評価方法１と同様の方法で測定した。
Evaluation method 2: For paper (Evaluation Examples 27 to 52 and Comparative Evaluation Examples 11 to 20)
L-BKP was beaten with a Niagara-type beater, and a sulfuric acid band was added to the paper stock adjusted to Canadian Standard Freeness (CSF) 400 ml. As a filler, light calcium carbonate (made by Okutama Kogyo Co., Ltd., trade name: Tama Pearl TP-121) was added at a solid content of 10% by weight to make the pH 7.0. In making the stock slurry, the polymer aqueous solutions obtained in Examples 1 to 13 and Comparative Examples 1 to 8 with a stock concentration of 1.0% were polymerized with tap water ((A) + (B)). Is diluted to 0.05 wt%, and the solid content of the paper stock is added to 0.025 wt% or 0.05 wt%, dehydrated with a tapi sheet machine, and 5 kg / cm 2.
And pressed for 2 minutes to make a paper having a basis weight of 60 g / m 2 . Subsequently, it dried for 4 minutes at 105 degreeC with a rotary dryer, and 23 degreeC and 50% R. H. After adjusting the humidity for 24 hours, the internal strength was measured. The drainage amount, the formation variation coefficient, and the total yield were measured by the same method as in the evaluation method 1.
各評価例における水溶性高分子分散体固形分の紙料固形分に対する添加率と各項目の測定結果を表４に示す。 Table 4 shows the addition rate of the water-soluble polymer dispersion solid content in each evaluation example with respect to the paper solid content and the measurement results of each item.
地合変動係数は数値が小さいほうが地合良好である。 The smaller the numerical value of the formation variation coefficient, the better the formation.
Claims (10)
水溶性重合体（Ａ）が、５〜２０モル％のカチオン性ラジカル重合性単量体（ａ１）、０〜７．５モル％のアニオン性ラジカル重合性単量体（ａ２）、０〜１モル％の架橋性単量体（ａ３）および２０〜９７モル％の（メタ）アクリルアミド（ａ４）を共重合して得られる共重合体であり、
分岐構造を有する高分子分散剤（Ｂ）が、３０〜９９．９９９モル％のカチオン性ラジカル重合性単量体（ｂ１）、０〜５モル％のアニオン性ラジカル重合単量体（ｂ２）、０．００１〜１モル％の架橋性単量体（ｂ３）および０〜７０モル％の（メタ）アクリルアミド（ｂ４）を共重合させて得られる共重合体である水溶性重合体分散液。 An average particle size of 0.1 to 150 μm is obtained by using the polymer dispersant (B) having a branched structure for the water-soluble polymer (A) in a salt aqueous solution having a salt concentration of 10 wt% or more and a saturation concentration or less. a dispersion of the water-soluble polymer dispersed as, in 10 to 40% by weight content of the water-soluble polymer (a), Ri viscosity 100~30000mPa · s der dispersion at 25 ° C. ,
The water-soluble polymer (A) is 5 to 20 mol% of the cationic radical polymerizable monomer (a1), 0 to 7.5 mol% of the anionic radical polymerizable monomer (a2), 0 to 1 It is a copolymer obtained by copolymerizing a mol% crosslinkable monomer (a3) and 20 to 97 mol% (meth) acrylamide (a4),
The polymer dispersant (B) having a branched structure is 30 to 99.999 mol% of a cationic radical polymerizable monomer (b1), 0 to 5 mol% of an anionic radical polymerizable monomer (b2), A water-soluble polymer dispersion which is a copolymer obtained by copolymerizing 0.001 to 1 mol% of a crosslinkable monomer (b3) and 0 to 70 mol% of (meth) acrylamide (b4) .
A yield improving agent for papermaking, comprising the water-soluble polymer dispersion according to any one of claims 1 to 7 .
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2009
- 2009-06-08 JP JP2009136794A patent/JP5445831B2/en active Active
- 2009-06-19 CN CN200910149695.9A patent/CN101608047B/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011168948A (en) * | 2010-01-20 | 2011-09-01 | Arakawa Chem Ind Co Ltd | Water-soluble polymer dispersion, paper strengthening agent, freeness enhancement agent for papermaking, and yield enhancement agent for papermaking |
| CN103590284A (en) * | 2013-11-06 | 2014-02-19 | 枣庄超越玉米淀粉有限公司 | Production process of starch emulsion for papermaking |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101608047B (en) | 2014-10-29 |
| JP2010024441A (en) | 2010-02-04 |
| CN101608047A (en) | 2009-12-23 |
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