JP5709043B2 - 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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- JP5709043B2 JP5709043B2 JP2011066655A JP2011066655A JP5709043B2 JP 5709043 B2 JP5709043 B2 JP 5709043B2 JP 2011066655 A JP2011066655 A JP 2011066655A JP 2011066655 A JP2011066655 A JP 2011066655A JP 5709043 B2 JP5709043 B2 JP 5709043B2
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- Prior art keywords
- water
- component
- soluble polymer
- dispersion
- mol
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- 229920003169 water-soluble polymer Polymers 0.000 title claims description 109
- 239000004815 dispersion polymer Substances 0.000 title claims description 69
- 239000003623 enhancer Substances 0.000 title claims description 10
- 239000006185 dispersion Substances 0.000 claims description 123
- 239000007864 aqueous solution Substances 0.000 claims description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 60
- 238000004519 manufacturing process Methods 0.000 claims description 57
- 239000000178 monomer Substances 0.000 claims description 47
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 42
- 229920000642 polymer Polymers 0.000 claims description 41
- 239000002270 dispersing agent Substances 0.000 claims description 36
- 239000002245 particle Substances 0.000 claims description 31
- 238000006116 polymerization reaction Methods 0.000 claims description 19
- 238000010526 radical polymerization reaction Methods 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 16
- 230000000379 polymerizing effect Effects 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 85
- 229910052757 nitrogen Inorganic materials 0.000 description 52
- 239000000123 paper Substances 0.000 description 37
- 239000003505 polymerization initiator Substances 0.000 description 28
- 239000012266 salt solution Substances 0.000 description 28
- 238000003756 stirring Methods 0.000 description 26
- 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
- 238000010992 reflux Methods 0.000 description 25
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 24
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 24
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 24
- 235000011130 ammonium sulphate Nutrition 0.000 description 24
- 238000010438 heat treatment Methods 0.000 description 24
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 24
- 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 24
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 15
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 13
- -1 N, N-dimethylaminoethyl Chemical group 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 239000013055 pulp slurry Substances 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000006467 substitution reaction Methods 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
- 125000000524 functional group Chemical group 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000012674 dispersion polymerization Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 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 4
- 239000000126 substance Substances 0.000 description 4
- 125000000542 sulfonic acid group Chemical group 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 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 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 3
- 229940018557 citraconic acid Drugs 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 3
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 125000001302 tertiary amino group Chemical group 0.000 description 3
- 238000010792 warming Methods 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
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-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
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 1
- GZBSIABKXVPBFY-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GZBSIABKXVPBFY-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- DMMSYVRRDYJQSI-UHFFFAOYSA-N 2-[2-[2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOCCOCCOC(=O)C=C DMMSYVRRDYJQSI-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
- SFSUKMJLBGPFFD-UHFFFAOYSA-N 3-[(4-amino-4-iminobutan-2-yl)diazenyl]butanimidamide;hydrochloride Chemical compound Cl.NC(=N)CC(C)N=NC(C)CC(N)=N SFSUKMJLBGPFFD-UHFFFAOYSA-N 0.000 description 1
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 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
- PGDIJTMOHORACQ-UHFFFAOYSA-N 9-prop-2-enoyloxynonyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCCCCOC(=O)C=C PGDIJTMOHORACQ-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
- 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
- VUVPCQMETIENKA-UHFFFAOYSA-N C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.CC(COC(C)COC(C)CO)O Chemical class C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.CC(COC(C)COC(C)CO)O VUVPCQMETIENKA-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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-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
- 229920003171 Poly (ethylene oxide) Polymers 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
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation 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
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- LSGUXGJUXCTZPW-UHFFFAOYSA-N bis[2-(5-methyl-4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene;hydrochloride Chemical compound Cl.N1C(C)CN=C1C(C)(C)N=NC(C)(C)C1=NCC(C)N1 LSGUXGJUXCTZPW-UHFFFAOYSA-N 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
- 239000011111 cardboard Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 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
- 230000006866 deterioration Effects 0.000 description 1
- 125000004386 diacrylate group Chemical group 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
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 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
- 238000009826 distribution Methods 0.000 description 1
- 239000013051 drainage agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- VUMVATZUXJAUHG-UHFFFAOYSA-N ethenesulfonic acid;2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=C.OS(=O)(=O)C=CC1=CC=CC=C1 VUMVATZUXJAUHG-UHFFFAOYSA-N 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
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000013054 paper strength agent Substances 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
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 238000000710 polymer precipitation Methods 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
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical group 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
- 230000009257 reactivity Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical group C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 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)
- Paper (AREA)
- Polymerisation Methods In General (AREA)
- Compositions Of Macromolecular Compounds (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、さまざまな用途に用いられ、リサイクル可能な資源として注目されている。ただし、リサイクルが進むと、紙製造時に原料であるパルプスラリーから脱水する際に水が抜けなくなる、パルプスラリーの歩留りが低下するなど問題が生じる。そのため、パルプスラリーから水を抜き、歩留を高めることで紙の生産効率を高めるために濾水剤・歩留向上剤や紙力増強剤が用いられている。 Paper is used for various purposes and is attracting attention as a recyclable resource. However, when the recycling progresses, there are problems that water cannot be drained when dewatering from the pulp slurry as a raw material during paper manufacture, and the yield of the pulp slurry is reduced. Therefore, a drainage agent, a yield improver, and a paper strength enhancer are used in order to increase the yield of paper by removing water from the pulp slurry and increasing the yield.
濾水性、歩留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向上剤、濾水向上剤として用いることが提案されている（特許文献１および２）。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ものの、得られる紙の強度が十分でないといった問題があった。 As a solution to the decrease in drainage and yield, it has 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 (Patent Document 1). And 2). According to this method, the drainage and the yield can be improved, but there is a problem that the strength of the obtained paper is not sufficient.
また、紙力増強剤としては、従来より、水溶液中でアクリルアミドを他の重合性単量体と共重合させることにより得られるアクリルアミド系高分子が広く用いられ、本出願人も様々なアクリルアミド系高分子を用いた紙力増強剤を提案している。（たとえば、特許文献３および４）。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、これらの紙力増強剤によっても紙力効果を与えるとともに濾水性・歩留性を向上させることは困難であるなどの問題があった。 As paper strength enhancers, conventionally, acrylamide polymers obtained by copolymerizing acrylamide with other polymerizable monomers in an aqueous solution have been widely used. A paper strength enhancer using molecules is proposed. (For example, Patent Documents 3 and 4). However, recycling and repeatedly using paper leads to shortening and deterioration of pulp, which is the raw material of paper, and increases the concentration of inorganic substances and impurities in the paper manufacturing system. However, there is a problem that it is difficult to give paper strength effect and improve drainage and yield.
本発明は、得られる紙の地合を乱さず、且つ濾水性と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, a paper drainage improver, and a paper yield, which can maintain high drainage and paper strength without disturbing the formation of the resulting paper. The object is to provide an improver.
本発明者は、前記課題を解決すべく鋭意検討したところ、特定のラジカル重合性単量体成分を、高分子分散剤の存在下で分散重合させて得られた水溶性重合体の分散液であって、水溶性重合体として、カチオン性ラジカル重合性単量体とアニオン性ラジカル重合性単量体のモル比が異なる少なくとも２種を含有し、その希釈分散液の特定ｐＨ範囲において示す濁度が一定範囲内となるような濁りを生ずるように分散させた水溶性重合体分散液が紙の地合を乱さず、且つ濾水性と紙力を高く維持することができることを見出し、本発明を完成させた。
The present inventors have revealed that intensive studies to solve the above problems, a specific radically polymerizable monomer component, a dispersion of the resulting water-soluble polymer by dispersion polymerization in the presence of a polymeric dispersing agent The water-soluble polymer contains at least two different molar ratios of the cationic radical polymerizable monomer and the anionic radical polymerizable monomer , and is a turbidity exhibited in a specific pH range of the diluted dispersion. The present invention has found that a water-soluble polymer dispersion dispersed so as to cause turbidity such that the degree falls within a certain range does not disturb the formation of paper and can maintain high drainage and paper strength. Was completed.
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、３〜４０モル％のカチオン性ラジカル重合性単量体（ａ１）、１〜２０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２０〜９６モル％の（メタ）アクリルアミド（ａ４）からなるラジカル重合成分（ａ）を高分子分散剤（Ｂ）の存在下、分散重合させて得られた水溶性重合体（Ａ）の分散液であって、水溶性重合体（Ａ）として、カチオン性ラジカル重合性単量体（ａ１）のアニオン性ラジカル重合性単量体（ａ２）に対するモル比〔（ａ１）／（ａ２）〕が、（ａ１）／（ａ２）≧２であるラジカル重合成分（ａ）を重合して得られた水溶性重合体（Ａ１）と、前記モル比が２＞（ａ１）/（ａ２）≧１であるラジカル重合成分（ａ）をラジカル重合して得られた水溶性重合体（Ａ２）の少なくとも２種を含有し、分散液中の前記（Ａ）成分および前記（Ｂ）成分の合計含有量を０．２重量％に水で希釈した希釈分散液とした場合において、その希釈分散液のｐＨ５〜８における濁度の最小値が１０ＮＴＵ以上、最大値が５００ＮＴＵ未満となる水溶性重合体分散液；前記水溶性重合体分散液からなる紙力増強剤、製紙用濾水性向上剤および前記水溶性重合体分散液からなる製紙用歩留向上剤、に関する。
That is, the present invention provides 3 to 40 mol% of a cationic radical polymerizable monomer (a1) and 1 to 20 mol% of an anionic radical polymerizable in an aqueous salt solution having a salt concentration of 10% by weight or more and a saturated concentration or less. monomer (a2), 0 to 1 mol% of crosslinking monomer (a3) and 20 to 96 mole% of (meth) acrylamide (a4) a radical polymerization components (a) a polymeric dispersing agent (B ) In the presence of an anionic radical of a cationic radical polymerizable monomer (a1) as a water-soluble polymer (A) dispersion. Water-soluble polymer obtained by polymerizing the radical polymerization component (a) in which the molar ratio [(a1) / (a2)] to the polymerizable monomer (a2) is (a1) / (a2) ≧ 2 (A1) and the molar ratio is 2> (a1) / (a2) ≧ 1 It contains at least two water-soluble polymers (A2) obtained by radical polymerization of the radical polymerization component (a), and the total content of the component (A) and the component (B) in the dispersion is 0. A water-soluble polymer dispersion having a minimum turbidity of 10 NTU or more and a maximum value of less than 500 NTU at a pH of 5 to 8 when the diluted dispersion is diluted to 2% by weight with water; The present invention relates to a paper strength enhancer comprising a water-soluble polymer dispersion, a paper-making drainage improver, and a paper-making yield improver comprising 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、ラジカル重合成分（ａ）を高分子分散剤（Ｂ）（以下、（Ｂ）成分という）の存在下、分散重合させて得られた水溶性重合体（Ａ）（以下、（Ａ）成分という）の分散液である。 In the water-soluble polymer dispersion of the present invention, the radical polymerization component (a) is added to the polymer dispersant (B) (hereinafter referred to as the component (B)) in an aqueous salt solution having a salt concentration of 10% by weight or more and a saturation concentration or less. Is a dispersion of a water-soluble polymer (A) (hereinafter referred to as component (A)) obtained by dispersion polymerization.
ラジカル重合成分（ａ）（以下、（ａ）成分という）としては、少なくとも、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）および（メタ）アクリルアミド（ａ４）（以下、（ａ４）成分という）を含有するものである。 The radical polymerization component (a) (hereinafter referred to as (a) component) includes at least a cationic radical polymerizable monomer (a1) (hereinafter referred to as (a1) component), an anionic radical polymerizable monomer ( a2) (hereinafter referred to as component (a2)) 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）アクリル系単量体、当該第３級アミノ基含有（メタ）アクリル系単量体の塩、当該第３級アミノ基含有（メタ）アクリル系単量体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）アクリル系単量体などが挙げられる。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、得られる重合体の疎水性が高まり、その塩水溶液に対する溶解性を低くすることができる点で好ましい。 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 such tertiary amino group-containing (meth) acrylic monomers, tertiary amino group-containing (meth) acrylic monomers Examples include quaternary ammonium salt-containing (meth) acrylic monomers obtained by reacting a monomer with a quaternizing 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, benzyl chloride quaternized product of N, N-dimethylaminoethyl (meth) acrylate is preferable because the hydrophobicity of the obtained polymer is increased and the solubility in an aqueous salt solution can be lowered.
（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、リン酸２−メタクリロイルオキシエチル、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 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.
さらに、（ａ）成分には、必要により、架橋性ラジカル単量体（ａ３）（以下、（ａ３）成分という）を使用することができる。（ａ３）成分を使用することにより、抄紙系に添加された際に、ポリマーの密度を高くすることが可能となり、濾水および歩留り性能を向上しやすいという利点がある。
（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アクリレート、１，９−ノナンジオールジアクリレート、テトラエチレングリコールジアクリレート、ヘキサエチレングリコールジアクリレート、トリプロピレングリコールジアクリレート、ジシクロペンタニルジアクリレート等のジアクリレート類、トリメチロールプロパントリアクリレート、ペンタエリスリトールトリアクリレート、１，３，５−トリアクロイルヘキサヒドロ−１，３，５−トリアジン、トリアリルイソシアヌレート、トリアリルアミン、テトラメチロールメタンテトラアクリレート等の３つ以上のビニル基を有する多官能ビニル単量体、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、メチレンビスアクリルアミドや１，３，５−トリアクロイルヘキサヒドロ−１，３，５−トリアジンが（ａ１）成分、（ａ２）〜（ａ４）成分などとの共重合性が高い点で好ましい。
Furthermore, as the component (a), a crosslinkable radical monomer (a3) (hereinafter referred to as the component (a3)) can be used as necessary. By using the component (a3), when added to the papermaking system, it becomes possible to increase the density of the polymer, and there is an advantage that drainage and yield performance are easily improved.
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 methylenebisacrylamide, hexanediol diacrylate, 1,9-nonanediol diacrylate, tetraethylene glycol diacrylate, hexaethylene glycol diacrylate, tripropylene glycol diacrylate Diacrylates such as acrylate and dicyclopentanyl diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, 1,3,5-triacroylhexahydro-1,3,5-triazine, triallyl isocyanurate, Examples thereof include polyfunctional vinyl monomers having three or more vinyl groups such as triallylamine and tetramethylolmethane tetraacrylate, and aromatic polyvinyl compounds such as divinylbenzene. These may be used individually by 1 type, or 2 or more types may be mixed and used for them. Among these, methylenebisacrylamide and 1,3,5-triacroylhexahydro-1,3,5-triazine are highly copolymerizable with the components (a1) and (a2) to (a4). This is preferable.
なお、（ａ）成分には、（ａ１）成分、（ａ２）成分、および（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、芳香族ビニル単量体、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、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、（ａ１）成分以外のものであれば、特に限定されず公知のものを用いることができる。具体的には、Ｎ，Ｎ−ジメチルアクリルアミド、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。芳香族ビニル単量体としては、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単量体類が挙げられる。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単量体類が挙げられる。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（Ａ）成分の必須成分である（ａ４）成分との共重合性が高く、好ましい。 The component (a) includes a radical polymerizable monomer (a5) having one radical polymerizable functional group other than the components (a1), (a2), and (a4) (hereinafter referred to as (a5) Component) may be used. Specific examples of the component (a5) include N-substituted acrylamides, aromatic vinyl monomers, alkyl (meth) acrylates, carboxylic acid vinyl esters, acrylonitrile, vinyl alcohol, and the like. N-substituted acrylamides are not particularly limited as long as they are other than the component (a1), and known ones can be used. Specifically, N, N-dimethylacrylamide, N, N-diethyl (meth) acrylamide, N, N-diisopropyl (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N- And monofunctional N-substituted acrylamides such as 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 the component (a4) which is an essential component of the component (A).
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１〜２０モル％程度、（ａ３）成分を０〜１モル％程度、（ａ４）成分を２０〜９６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２０〜９０．９９９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。 Moreover, although the usage-amount of each component is not specifically limited, Usually, (a1) component is about 3-40 mol%, (a2) component is about 1-20 mol%, (a3) component is about 0-1 mol%. The component (a4) is used in an amount of about 20 to 96 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%, (a4) 20-20.999 mol% of component is used. When the component (a5) is used, the amount used is usually about 1 mol% or less, preferably 0.5 mol% or less.
本発明に用いる（Ｂ）成分としては、カチオン性ラジカル重合性単量体（ｂ１）（以下、（ｂ１）成分という）を必須単量体成分として、重合させて得られたものであり、塩水溶液に溶解可能なものであれば、特に限定されない。通常、（ｂ１）成分のみを単独で、または（ｂ１）成分に後述するスルホン酸基を含有するラジカル重合性単量体（ｂ２）（以下、（ｂ２）成分という）、架橋性重合性単量体（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）などの単量体成分を共重合させて得られるもののいずれであってもよい。 The component (B) used in the present invention is obtained by polymerizing the cationic radical polymerizable monomer (b1) (hereinafter referred to as the component (b1)) as an essential monomer component, and a salt. There is no particular limitation as long as it is soluble in an aqueous solution. Usually, only the component (b1) alone or the radically polymerizable monomer (b2) (hereinafter referred to as the component (b2)) containing a sulfonic acid group described later in the component (b1), a crosslinkable polymerizable monomer Any of those obtained by copolymerizing monomer components such as body (b3) (hereinafter referred to as component (b3)) and (meth) acrylamide (b4) (hereinafter referred to as component (b4)) may be used. .
（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、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リドを用いることが、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く、重合体の塩水溶液に対する溶解性を保ち分散性能を向上させる点で好ましい。（ｂ１）成分の使用量としては、通常、（Ａ）成分の分散性を確保させる点から、３０モル％以上とすることが好ましい。 As the component (b1), the same monomer as the component (a1) that can be used when preparing the component (A) can be used. As the component (b1), acryloyloxyethyltrimethylammonium chloride is used as the component, so that the amount of cation when the polymer is formed can be easily adjusted to a desired value, and the dispersibility is maintained while maintaining the solubility in the salt solution of the polymer. It is preferable at the point which improves. The amount of the component (b1) used is preferably 30 mol% or more from the viewpoint of ensuring the dispersibility of the component (A).
（ｂ２）成分としては、スルホン酸基を少なくとも１つ有し、かつラジカル重合性官能基を１つ有する単量体および／またはその塩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、アリルスルホン酸、アリルスルホン酸ナトリウム、メタリルスルホン酸、メタリルスルホン酸ナトリウム、メタリルスルホン酸塩アンモニウムなどのアリル基を有するスルホン酸基含有不飽和単量体、ビニルスルホン酸、スチレンスルホン酸、２−アクリルアミド−２−メチルプロパンスルホン酸などが挙げられる。これらの中でも、（ｂ２）成分として、（メタ）アリルスルホン酸ナトリウムを用いると、（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）が生じやすくなり好ましい。なお、（ｂ２）成分は、後述の（ｂ３）成分を使用する場合に併用することで分子量と架橋構造の調整が容易になる点で好ましい。 The component (b2) is not particularly limited as long as it is a monomer and / or a salt thereof having at least one sulfonic acid group and one radical polymerizable functional group, and use a known one. Can do. Specifically, sulfonic acid group-containing unsaturated monomers having allyl groups such as allyl sulfonic acid, sodium allyl sulfonate, methallyl sulfonic acid, sodium methallyl sulfonate, ammonium methallyl sulfonate, vinyl sulfonic acid Styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and the like. Among these, it is preferable to use sodium (meth) allyl sulfonate as the component (b2) because it has high copolymerizability with (meth) acrylamide and easily causes radical transfer (chain transfer). In addition, (b2) component is preferable at the point which adjustment of a molecular weight and a crosslinked structure becomes easy by using together, when using the below-mentioned (b3) component.
（ｂ３）成分としては、（Ａ）成分の調製時に用いる（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、メチレンビスアクリルアミドや１，３，５−トリアクロイルヘキサヒドロ−１，３，５−トリアジンが好ましい。 As the component (b3), the same monomer as the component (a3) used when preparing the component (A) can be used. As the component (b3), methylene bisacrylamide and 1,3,5-triacroylhexahydro-1,3,5-triazine are preferable.
本発明に用いられる（Ｂ）成分は、重合成分として、更に、（ｂ４）成分を含有させることができる。（ｂ４）成分を使用することにより（Ｂ）成分の分散性能を失うことなく、粘度を所望の値に調整し易い利点がある。（ｂ４）成分の使用量は、分散性確保の観点から６９．９９９モル％程度を超えない範囲で使用することが好ましい。 The component (B) used in the present invention can further contain the component (b4) as a polymerization component. By using the component (b4), there is an advantage that the viscosity can be easily adjusted to a desired value without losing the dispersion performance of the component (B). The amount of component (b4) used is preferably within a range not exceeding about 69.999 mol% from the viewpoint of ensuring dispersibility.
（Ｂ）成分としては、（Ａ）成分の分散性を向上させる点から分岐構造を有するものであることが好ましい。分岐構造を有する（Ｂ）成分は、上記（ｂ３）を重合成分として併用することにより得られる。（ｂ１）成分と（ｂ３）成分の使用量としては（ｂ１）成分を３０〜９９．９９モル％程度、（ｂ３）成分を０．００１〜１モル％程度である。各成分の使用量をかかる範囲とすることにより、適度な分岐構造が形成され、（Ａ）成分を分散させる際に均一な粒子が得られる。
また、（ｂ３）を使用する場合には、（Ｂ）成分における過剰な架橋によるゲル化を防止し、粘度の調整を容易に行うことができる点から、（ｂ２）成分を併用することが好ましい。（ｂ２）成分の使用量としては、通常、（ｂ３）成分の使用量の０．５〜５００倍量程度（モル比）である。
The component (B) preferably has a branched structure from the viewpoint of improving the dispersibility of the component (A). The component (B) having a branched structure can be obtained by using (b3) in combination as a polymerization component. The amount of component (b1) and component (b3) used is about 30 to 99.99 mol% for component (b1) and about 0.001 to 1 mol% for component (b3). By setting the amount of each component used within such a range, an appropriate branched structure is formed, and uniform particles can be obtained when the component (A) is dispersed.
Moreover, when (b3) is used, it is preferable to use the component (b2) together from the viewpoint that gelation due to excessive crosslinking in the component (B) can be prevented and the viscosity can be easily adjusted. . The amount of component (b2) used is usually about 0.5 to 500 times (molar ratio) the amount of component (b3) used.
なお、（Ｂ）成分の重合成分としては、必要に応じて（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）を含有させてもよい。（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や、（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−ジメチルアクリルアミドが（ｂ１）〜（ｂ４）成分との共重合性が高く好ましい。（ｂ５）成分の使用量が１モル％を超えると共重合反応性が低下するため、（ｂ５）成分の使用量は、１モル％以下、好ましくは０．５モル％以下の範囲とすることが好ましい。 In addition, as a polymerization component of (B) component, you may contain radically polymerizable monomers (b5) (henceforth (b5) component) other than (b1) component-(b4) component as needed. Good. As the component (b5), the same monomer as the component (a5) that can be used when preparing the component (A), (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, anhydrous Carboxyl group-containing monomers such as itaconic acid, citraconic acid and citraconic anhydride 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-dimethylacrylamide is preferable because of high copolymerizability with the components (b1) to (b4). When the amount of component (b5) used exceeds 1 mol%, the copolymerization reactivity decreases, so the amount of component (b5) used is 1 mol% or less, preferably 0.5 mol% or less. Is preferred.
（Ｂ）成分は、上記の重合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℃における水溶液粘度は１０００〜２００００ｍＰａ・ｓであることが好ましい。（Ｂ）成分の水溶液粘度をかかる範囲とすることにより、水溶性重合体分散液の分散性を高め、製品粘度を所望の値に調整しやすく、製品の保存安定性向上の点においてより優れたものとすることができる。同様の観点から、前記水溶液粘度の範囲は、より好ましくは３０００〜２００００ｍＰａ・ｓの範囲である。 The component (B) can be obtained by radical polymerization of the above polymerization component 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 aqueous solution viscosity at 25 ° C. when the nonvolatile content is adjusted to 20% by weight is 1000 to 20000 mPa · s. It is preferable that By setting the aqueous solution viscosity of the component (B) within such a range, the dispersibility of the water-soluble polymer dispersion is increased, the product viscosity is easily adjusted to a desired value, and the product is more excellent in terms of improving the storage stability of the product. Can be. From the same viewpoint, the range of the aqueous solution viscosity is more preferably in the range of 3000 to 20000 mPa · s.
（Ａ）成分は、（Ｂ）成分の存在下、（ａ）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。（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。なお、ここでいう重量平均分子量は、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から測定した値である。
また、（Ａ）成分は、それぞれ組成の異なる（ａ）成分を重合させて得られた複数のものが含まれていてもよい。たとえば、（ａ１）成分の（ａ２）成分に対するモル比〔（ａ１）／（ａ２）〕が、（ａ１）／（ａ２）≧２であるラジカル重合成分（ａ）を重合して得られた水溶性重合体（Ａ１）と、前記モル比〔（ａ１）／（ａ２）〕が２＞（ａ１）/（ａ２）≧１である（ａ）成分をラジカル重合して得られた水溶性重合体（Ａ２）を混合するなどして調製されたものなどが挙げられる。これにより、得られる水溶性重合体の濾水性と紙力効果等を高いレベルに調整することが可能となる。
The component (A) can be obtained by radical polymerization of the component (a) by a known method in the presence of the component (B). The weight average molecular weight of the component (A) is usually about 1 million to 20 million, preferably about 3 million to 10 million. In addition, the weight average molecular weight here is a value measured from a weight average molecular weight obtained as a polyethylene oxide conversion value by a gel permeation chromatography method.
In addition, the component (A) may include a plurality of components obtained by polymerizing the components (a) having different compositions. For example, the aqueous solution obtained by polymerizing the radical polymerization component (a) in which the molar ratio [(a1) / (a2)] of the component (a1) to the component (a2) is (a1) / (a2) ≧ 2 Water-soluble polymer obtained by radical polymerization of the polymerizable polymer (A1) and the component (a) in which the molar ratio [(a1) / (a2)] is 2> (a1) / (a2) ≧ 1 Examples thereof include those prepared by mixing (A2). This makes it possible to adjust the drainage and paper strength effect of the obtained water-soluble polymer to a high level.
（Ｂ）成分の使用量は特に限定されないが、後記する所望の分散液（分散液中の前記（Ａ）成分および前記（Ｂ）成分の合計含有量を０．２重量％に水で希釈して希釈分散液とした場合において、その希釈分散液のｐＨ５〜８における濁度の最小値が１０ＮＴＵ以上、最大値が５００ＮＴＵ未満となる）を安定して得るためには、通常、ラジカル重合成分（ａ）１００重量部に対し、（Ｂ）成分を１〜１０重量部程度用いることが好ましい。 The amount of component (B) used is not particularly limited, but the desired dispersion described later (the total content of component (A) and component (B) in the dispersion is diluted to 0.2% by weight with water). In order to stably obtain a diluted dispersion, the minimum value of turbidity at pH 5 to 8 of the diluted dispersion is 10 NTU or more and the maximum value is less than 500 NTU. a) About 1 to 10 parts by weight of component (B) is preferably used with respect to 100 parts by weight.
塩濃度が１０重量％以上飽和濃度以下の塩水溶液中、（ａ）成分を、（Ｂ）成分の存在下で、分散重合させる方法としては、公知の方法により行えばよい。通常、所定量の塩、（ａ）成分、（Ｂ）成分、水等を混合した水溶液にラジカル重合開始剤を投入して、混合液を攪拌しながらラジカル重合させることにより行う。重合温度は、重合開始剤の種類により異なるが、通常、０〜８０℃の範囲であり、選択した重合開始剤が機能する温度であればよい。 As a method for dispersing and polymerizing 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, a known method may be used. Usually, a radical polymerization initiator is added to an aqueous solution in which a predetermined amount of salt, the component (a), the component (B), water, and the like are mixed, and radical polymerization is performed while stirring the mixed solution. The polymerization temperature varies depending on the type of polymerization initiator, but is usually in the range of 0 to 80 ° C., and may be any temperature at which the selected polymerization initiator functions.
重合開始剤としては、アゾ系、過酸化物系、レドックス系のいずれも使用することができる。アゾ系開始剤としては、２、２’−アゾビス（アミジノプロパン）塩酸塩、２、２’−アゾビス〔２−（５−メチル−２−イミダゾリン−２−イル）プロパン〕塩酸塩、４、４’−アゾビス（４−シアノ吉草酸）などがあげられる。またレドックス系の例としては、ペルオクソ二硫酸アンモニウムと亜硫酸ナトリウム、亜硫酸水素ナトリウム、トリメチルアミン、テトラメチルエチレンジアミンなどとの組み合わせが挙げられる。過酸化物の例としては、ペルオクソ二硫酸アンモニウムあるいはカリウム、過酸化水素、ベンゾイルペルオキサイド、ラウロイルペルオキサイドなどが挙げられる。 As the polymerization initiator, any of azo, peroxide and redox systems can be used. As the azo initiator, 2,2′-azobis (amidinopropane) hydrochloride, 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] hydrochloride, 4,4 And '-azobis (4-cyanovaleric acid). Examples of redox systems include a combination of ammonium peroxodisulfate and sodium sulfite, sodium hydrogen sulfite, trimethylamine, tetramethylethylenediamine, and the like. Examples of peroxides include ammonium or potassium peroxodisulfate, hydrogen peroxide, benzoyl peroxide, lauroyl peroxide, and the like.
重合時に使用する塩は仕込み時の混合液に全量含ませてもよいし、重合途中に段階的に添加してもよい。また、重合反応が塩濃度１０重量％以上で行われる限り、重合後にさらに添加してもよい。
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、硫酸塩、リン酸塩などの無機塩などが挙げられる。具体的には、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などが挙げられる。これらのうち、水への溶解度とポリマー析出効果の観点から、硫酸アンモニウムが好ましい。
The salt used at the time of polymerization may be entirely contained in the mixed solution at the time of charging, or may be added stepwise during the polymerization. Further, as long as the polymerization reaction is carried out at a salt concentration of 10% by weight or more, it may be further added after the polymerization.
The salt used for preparing the aqueous salt solution is not particularly limited as long as it does not dissolve the component (A), and usually includes inorganic salts such as sulfates and phosphates. Specific examples include ammonium sulfate, sodium sulfate, magnesium sulfate, aluminum sulfate, ammonium hydrogen phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, and the like. Of these, ammonium sulfate is preferred from the viewpoint of water solubility and polymer precipitation effect.
こうして得られた水溶性重合体分散液は、次のような特徴を有するものである。すなわち、
分散液中の前記（Ａ）成分および前記（Ｂ）成分の合計含有量を０．２重量％に水で希釈して希釈分散液とした場合において、その希釈分散液のｐＨ５〜８における濁度の最小値が１０ＮＴＵ以上、最大値が５００ＮＴＵ未満となる。
なお、本発明における濁度とは、濁りの度合いであって、ＡＮＡＬＩＴＥ濁度計１６０型（ＭｃＶａｎ社製）を用いて９００ｎｍの赤外光を利用した１８０度の散乱光を測定することによって得られる。ここで、本発明の濁度の測定対象は、分散重合させて得られた分散液それ自体の濁度ではなく、前記（Ａ）成分と前記（Ｂ）成分の合計含有量を０．２重量％に希釈して得られた希釈分散液を対象とする。さらに、本発明で特定される濁度は、希釈分散液のｐＨが５〜８の範囲に調整されている場合に限られる。本発明における濁度の具体的な測定方法としては、分散液中の前記（Ａ）成分と前記（Ｂ）成分の合計含有量を０．２重量％となるように水（脱イオン水が好ましい。）で希釈して希釈分散液を調製し、次いで、アルカリまたは酸を添加して希釈分散液のｐＨを変化させながら、経時的に濁度を測定し、希釈分散液のｐＨが５〜８の範囲でその希釈分散液が示した濁度の最小値と最大値を求めればよい。ｐＨの調整に用いるアルカリとしては、特に限定されないが、水酸化ナトリウム、水酸化カリウム、酸としては、硫酸、塩酸、硝酸などが挙げられ、濁度測定時にｐＨを細かく調整しやすい点から１重量％程度の水溶液として使用すればよい。なお、ｐＨの測定温度は、２５℃程度である。
The water-soluble polymer dispersion thus obtained has the following characteristics. That is,
When the total content of the component (A) and the component (B) in the dispersion is diluted to 0.2% by weight with water to obtain a diluted dispersion, the turbidity of the diluted dispersion at pH 5 to 8 The minimum value is 10 NTU or more and the maximum value is less than 500 NTU.
The turbidity in the present invention is the degree of turbidity, and is obtained by measuring 180-degree scattered light using 900 nm infrared light using an ANALITE turbidimeter 160 type (McVan). It is done. Here, the turbidity measurement target of the present invention is not the turbidity of the dispersion itself obtained by dispersion polymerization, but the total content of the component (A) and the component (B) is 0.2 weight. The target is a diluted dispersion obtained by diluting to 1%. Furthermore, the turbidity specified in the present invention is limited to the case where the pH of the diluted dispersion is adjusted to the range of 5-8. As a specific method for measuring turbidity in the present invention, water (deionized water is preferable so that the total content of the component (A) and the component (B) in the dispersion is 0.2% by weight. )) To prepare a diluted dispersion, and then the turbidity is measured over time while changing the pH of the diluted dispersion by adding alkali or acid, and the pH of the diluted dispersion is 5-8. In this range, the minimum and maximum turbidity values indicated by the diluted dispersion may be obtained. The alkali used for pH adjustment is not particularly limited. Examples of sodium hydroxide, potassium hydroxide, and acid include sulfuric acid, hydrochloric acid, nitric acid, and the like. From the viewpoint of easy adjustment of pH during turbidity measurement, 1 wt. % Aqueous solution may be used. In addition, the measurement temperature of pH is about 25 degreeC.
水溶性重合体分散液の希釈分散液の前記濁度の最小値が１０ＮＴＵ未満の場合には、水溶性重合体分散液の目標の濾水性が得られないなど問題が生じる。一方、水溶性重合体分散液の希釈分散液の前記濁度の最大値が５００ＮＴＵ以上の場合、水溶性重合体分散液の使用時に、例えば、適当濃度に希釈して使用する場合や、他の薬品と混合して使用する場合に沈殿が生じ、そのような状態では紙力増強効果や、濾水性向上効果など本来の性能を十分に発揮できない可能性がある。なお、前記濁度を呈する水溶性重合体成分の状態と本発明の効果との関係のメカニズムについては、まだ充分な理解が得られていないが、かかる状態においては、複数のポリマーが相互作用しイオンコンプレックス形成がされていることによるものと推察される。 When the minimum value of the turbidity of the diluted dispersion of the water-soluble polymer dispersion is less than 10 NTU, there arises a problem that the target drainage of the water-soluble polymer dispersion cannot be obtained. On the other hand, when the maximum value of the turbidity of the diluted dispersion of the water-soluble polymer dispersion is 500 NTU or more, when using the water-soluble polymer dispersion, for example, when diluted to an appropriate concentration, When used in combination with a chemical, precipitation occurs, and in such a state, there is a possibility that the original performance such as a paper strength enhancing effect and a drainage improving effect cannot be sufficiently exhibited. Note that the mechanism of the relationship between the state of the water-soluble polymer component exhibiting turbidity and the effect of the present invention has not yet been fully understood, but in such a state, a plurality of polymers interact. This is presumably due to the formation of ion complexes.
また、（ａ）成分を仕込み時の混合液に全量含ませずに、分散重合中に段階的に添加して重合を行ってもよい。これにより、前記特徴を有する水溶性重合体分散液をより容易に得ることができる。 Further, the polymerization may be carried out by adding stepwise during the dispersion polymerization without including the whole amount of the component (a) in the mixed solution at the time of charging. As a result, a water-soluble polymer dispersion having the above characteristics can be obtained more easily.
また、得られた水溶性重合体分散液の平均粒子径は、通常、０．１μｍ〜１５０μｍ程度である。平均粒子径をかかる範囲内とすることにより、得られる分散液の長期安定性がより優れたものとすることができる。同様の観点から、より好ましい平均粒子径は、０．１μｍ〜１００μｍである。（Ａ）成分の含有量は、通常、１０〜４０重量％で、２５℃における水溶性重合体分散液の粘度が１００〜２００００ｍＰａ・ｓであることが好ましい。（Ａ）成分の含有量と粘度をかかる範囲内に調整することにより、水溶性重合体分散液中の粒子の沈降などが抑えられ、分散状態の安定性を向上させることができる。 Moreover, the average particle diameter of the obtained water-soluble polymer dispersion is usually about 0.1 μm to 150 μm. By making the average particle diameter within such a range, the long-term stability of the resulting dispersion can be made more excellent. From the same viewpoint, the more preferable average particle diameter is 0.1 μm to 100 μm. The content of the component (A) is usually 10 to 40% by weight, and the viscosity of the water-soluble polymer dispersion at 25 ° C. is preferably 100 to 20000 mPa · s. By adjusting the content and viscosity of the component (A) within such ranges, sedimentation of particles in the water-soluble polymer dispersion can be suppressed, and the stability of the dispersion state can be improved.
本発明の水溶性重合体分散液を紙力増強剤、濾水性向上剤および歩留向上剤として用いるためには、通常、水溶性重合体分散液（（Ａ）成分および（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、（Ａ）成分および（Ｂ）成分の合計含有量を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, a freeness improver and a yield improver, usually a water-soluble polymer dispersion (mixture of (A) component and (B) component) ) Is preferably 3 million or more, and the total content of the component (A) and the component (B) is preferably diluted 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は洋紙・板紙を問わず使用することが可能であり、また他の製紙用添加剤（サイズ剤や公知の紙力剤、有機、無機の水不溶性微粒子凝集助剤）も同時に用いてもよい。 The water-soluble polymer dispersion of the present invention can be used regardless of whether it is paper or paperboard, and other paper additives (size agents, known paper strength agents, organic and inorganic water-insoluble fine particle agglomeration aids). Agent) may be used at the same time.
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リドの８０重量％水溶液２５０ｇ（純分２００ｇ）、イオン交換水５２９ｇ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５重量％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時間重合反応させて高分子分散剤を得た。
得られた高分子分散剤の粘度は、不揮発分を２０重量％に調整した後、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 An 80% by weight aqueous solution of acryloyloxyethyltrimethylammonium chloride in a 2 liter five-necked separable flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube. 250 g (pure content: 200 g) and 529 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 5 wt% 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.
The viscosity of the obtained polymer dispersant was measured using a bismetholone viscometer (manufactured by Shibaura System Co., Ltd.) after adjusting the nonvolatile content to 20% by weight and then adjusting to 25 ° C. (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、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リドの８０重量％水溶液２４９．９９ｇ（純分１９９．９９２ｇ；９９．９９５モル％）、メチレンビスアクリルアミド０．００８ｇ（０．００５モル％）、イオン交換水５２９．７ｇを仕込み、５０℃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１．５重量％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時間重合反応させて高分子分散剤を得た。
(Production Example 2) Polymer Dispersant Production Method An 80% by weight aqueous solution of acryloyloxyethyltrimethylammonium chloride in a 2 liter five-necked separable flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube. 249.999 g (pure content 199.992 g; 99.995 mol%), methylenebisacrylamide 0.008 g (0.005 mol%) and ion-exchanged water 529.7 g were charged, and the atmosphere was replaced with nitrogen while heating to 50 ° C. . To this was added 20 g of a 1.5 wt% 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.
（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、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リドの８０％重量水溶液２１５．６３ｇ（純分１７２．５ｇ；６９．８５モル％）、メチレンビスアクリルアミド０．１９６６ｇ（０．１モル％）、メタリルスルホン酸ナトリウム０．１ｇ（０．０５モル％）、アクリルアミド２７．２ｇ（３０モル％）、イオン交換水５３６．４７ｇを仕込み、６０℃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重量％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時間重合反応させて高分子分散剤を得た。
Production Example 3 Polymer Dispersant Production Method 80% by weight aqueous solution of acryloyloxyethyltrimethylammonium chloride in a 2 liter five-necked separable flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube 215.63 g (pure content 172.5 g; 69.85 mol%), methylene bisacrylamide 0.1966 g (0.1 mol%), sodium methallylsulfonate 0.1 g (0.05 mol%), acrylamide 27. 2 g (30 mol%) and 536.47 g of ion-exchanged water were charged, and nitrogen substitution was performed while heating to 60 ° C. To this was added 20 g of a 2 wt% 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.
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リド
ＭＢＡＡ：メチレンビスアクリルアミド
ＳＭＡＳ：メタリルスルホン酸ナトリウム
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 MBAA: methylenebisacrylamide SMAS: sodium methallylsulfonate 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しない高分子分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水１０４９．２５ｇに溶解した。これに、アクリルアミド２８２．１７ｇ（８５モル％）、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リドの８０％水溶液１０１．７３ｇ（純分８１．３８４ｇ；９モル％）、イタコン酸３６．４５ｇ（６モル％）を加え３０℃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重量％水溶液２０ｇを加え、攪拌下で２４時間重合反応を行い、塩水溶液に分散した水溶性重合体の分散液を得た。得られた分散液の平均粒子径と粘度を測定し、さらに、分散液中の（Ａ）成分および（Ｂ）成分の合計含有量を０．２重量％となるように水で希釈した後、希釈分散液の濁度を測定した。結果を表２に示す。
(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 a polymer dispersant having no structure and 400 g of ammonium sulfate were dissolved in 1049.25 g of ion-exchanged water. To this was added 282.17 g (85 mol%) of acrylamide, 101.73 g of 80% aqueous solution of acryloyloxyethyltrimethylammonium chloride (pure content 81.384 g; 9 mol%), and 36.45 g (6 mol%) of itaconic acid. While warming to 30 ° C., nitrogen substitution was performed. To this was added 20 g of a 2% by weight aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, and the polymerization reaction was carried out for 24 hours with stirring to disperse the water-soluble polymer dispersed in the aqueous salt solution. A liquid was obtained. After measuring the average particle size and viscosity of the obtained dispersion, and further diluted with water so that the total content of the component (A) and the component (B) in the dispersion is 0.2 wt%, The turbidity of the diluted dispersion was measured. The results are shown in Table 2.
（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１で得られた分岐構造を有しない高分子分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水１０１７．９５ｇに溶解した。これに、アクリルアミド２１５．１５ｇ（７９モル％）、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級化物の７５重量％水溶液２０６．６ｇ（純分１５４．９５ｇ；１５モル％）、イタコン酸２９．９ｇ（６モル％）を加え３０℃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重量％水溶液２０ｇを加え、攪拌下で２４時間重合を行い、塩水溶液に分散した水溶性重合体の分散液を得た。得られた分散液の平均粒子径と粘度を測定し、さらに、分散液中の（Ａ）成分および（Ｂ）成分の合計含有量を０．２重量％となるように水で希釈した後、希釈分散液の濁度を測定した。結果を表２に示す。
(Example 2) 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 polymer dispersant having no structure and 400 g of ammonium sulfate were dissolved in 1017.95 g of ion-exchanged water. To this, 215.15 g (79 mol%) of acrylamide, 206.6 g of 75% by weight aqueous solution of benzyl chloride quaternary product of N, N-dimethylaminoethyl acrylate (pure content 154.95 g; 15 mol%), itaconic acid 29 .9 g (6 mol%) was added and the atmosphere was replaced with nitrogen while heating to 30 ° C. To this was added 20 g of a 2% by weight aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, polymerized for 24 hours with stirring, and a dispersion of a water-soluble polymer dispersed in the aqueous salt solution. Got. After measuring the average particle size and viscosity of the obtained dispersion, and further diluted with water so that the total content of the component (A) and the component (B) in the dispersion is 0.2 wt%, The turbidity of the diluted dispersion was measured. The results are shown in Table 2.
（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で得られた分岐構造を有しない高分子分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水１０４３．５９ｇに溶解した。これに、アクリルアミド２６１．０１ｇ（８２モル％）、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リドの８０重量％水溶液１３０．０５ｇ（純分１０４．０４ｇ；１２モル％）、イタコン酸３４．９５ｇ（６モル％）を加え３０℃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重量％水溶液２０ｇを加え、攪拌下で２４時間重合を行い、塩水溶液に分散した水溶性重合体の分散液を得た。得られた分散液の平均粒子径と粘度を測定し、さらに、分散液中の（Ａ）成分および（Ｂ）成分の合計含有量を０．２重量％となるように水で希釈した後、希釈分散液の濁度を測定した。結果を表２に示す。
(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 polymer dispersant having no structure and 400 g of ammonium sulfate were dissolved in 1043.59 g of ion-exchanged water. To this, 261.01 g (82 mol%) of acrylamide, 130.05 g (pure content 104.04 g; 12 mol%) of 80% by weight aqueous solution of acryloyloxyethyltrimethylammonium chloride, and 34.95 g (6 mol%) of itaconic acid. In addition, nitrogen was substituted while heating to 30 ° C. To this was added 20 g of a 2% by weight aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, polymerized for 24 hours with stirring, and a dispersion of a water-soluble polymer dispersed in the aqueous salt solution. Got. After measuring the average particle size and viscosity of the obtained dispersion, and further diluted with water so that the total content of the component (A) and the component (B) in the dispersion is 0.2 wt%, The turbidity of the diluted dispersion was measured. The results are shown in Table 2.
（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２で得られた分岐構造を有する高分子分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水１０４９．２５ｇに溶解した。これに、アクリルアミド２８２．１７ｇ（８５モル％）、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リドの８０重量％水溶液１０１．７３ｇ（純分８１．３８４ｇ；９モル％）、イタコン酸３６．４５ｇ（６モル％）を加え３０℃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重量％水溶液２０ｇを加え、攪拌下で２４時間重合を行い、塩水溶液に分散した水溶性重合体の分散液が得た。得られた分散液の平均粒子径と粘度を測定し、さらに、分散液中の（Ａ）成分および（Ｂ）成分の合計含有量を０．２重量％となるように水で希釈した後、希釈分散液の濁度を測定した。結果を表２に示す。
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 110 g of the polymer dispersant having a structure and 400 g of ammonium sulfate were dissolved in 1049.25 g of ion-exchanged water. To this, 282.17 g (85 mol%) of acrylamide, 101.73 g of 80% by weight aqueous solution of acryloyloxyethyltrimethylammonium chloride (pure content 81.384 g; 9 mol%) and 36.45 g of itaconic acid (6 mol%) were added. In addition, nitrogen was substituted while heating to 30 ° C. To this was added 20 g of a 2% by weight aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, polymerized for 24 hours with stirring, and a dispersion of a water-soluble polymer dispersed in the aqueous salt solution. Got. After measuring the average particle size and viscosity of the obtained dispersion, and further diluted with water so that the total content of the component (A) and the component (B) in the dispersion is 0.2 wt%, The turbidity of the diluted dispersion was measured. The results are shown in Table 2.
（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２で得られた分岐構造を有する高分子分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水１０１７．９５ｇに溶解した。これに、アクリルアミド２１５．１５ｇ（７９モル％）、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級化物の７５重量％水溶液２０６．６ｇ（純分１５４．９５ｇ；１５モル％）、イタコン酸２９．９ｇ（６モル％）を加え３０℃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重量％水溶液２０ｇを加え、攪拌下で２４時間重合を行い、塩水溶液に分散した水溶性重合体の分散液を得た。得られた分散液の平均粒子径と粘度を測定し、さらに、分散液中の（Ａ）成分および（Ｂ）成分の合計含有量を０．２重量％となるように水で希釈した後、希釈分散液の濁度を測定した。結果を表２に示す。
(Example 5) Production method of water-soluble polymer dispersion The branch obtained in Production Example 2 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 polymer dispersant having a structure and 400 g of ammonium sulfate were dissolved in 1017.95 g of ion-exchanged water. To this, 215.15 g (79 mol%) of acrylamide, 206.6 g of 75% by weight aqueous solution of benzyl chloride quaternary product of N, N-dimethylaminoethyl acrylate (pure content 154.95 g; 15 mol%), itaconic acid 29 .9 g (6 mol%) was added and the atmosphere was replaced with nitrogen while heating to 30 ° C. To this was added 20 g of a 2% by weight aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, polymerized for 24 hours with stirring, and a dispersion of a water-soluble polymer dispersed in the aqueous salt solution. Got. After measuring the average particle size and viscosity of the obtained dispersion, and further diluted with water so that the total content of the component (A) and the component (B) in the dispersion is 0.2 wt%, The turbidity of the diluted dispersion was measured. The results are shown in Table 2.
（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２で得られた分岐構造を有する高分子分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水１０４３．５９ｇに溶解した。これに、アクリルアミド２６１．０１ｇ（８２モル％）、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リドの８０重量％水溶液１３０．０５ｇ（純分１０４．０４ｇ；１２モル％）、イタコン酸３４．９５ｇ（６モル％）を加え３０℃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重量％水溶液２０ｇを加え、攪拌下で２４時間重合を行い、塩水溶液に分散した水溶性重合体の分散液を得た。得られた分散液の平均粒子径と粘度を測定し、さらに、分散液中の（Ａ）成分および（Ｂ）成分の合計含有量を０．２重量％となるように水で希釈した後、希釈分散液の濁度を測定した。結果を表２に示す。
(Example 6) Production method of water-soluble polymer dispersion The branch obtained in Production Example 2 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 polymer dispersant having a structure and 400 g of ammonium sulfate were dissolved in 1043.59 g of ion-exchanged water. To this, 261.01 g (82 mol%) of acrylamide, 130.05 g (pure content 104.04 g; 12 mol%) of 80% by weight aqueous solution of acryloyloxyethyltrimethylammonium chloride, and 34.95 g (6 mol%) of itaconic acid. In addition, nitrogen was substituted while heating to 30 ° C. To this was added 20 g of a 2% by weight aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, polymerized for 24 hours with stirring, and a dispersion of a water-soluble polymer dispersed in the aqueous salt solution. Got. After measuring the average particle size and viscosity of the obtained dispersion, and further diluted with water so that the total content of the component (A) and the component (B) in the dispersion is 0.2 wt%, The turbidity of the diluted dispersion was measured. The results are shown in Table 2.
（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３で得られた分岐構造を有する高分子分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水１０４９．２５ｇに溶解した。これに、アクリルアミド２８２．１７ｇ（８５モル％）、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リドの８０重量％水溶液１０１．７３ｇ（純分８１．３８４ｇ；９モル％）、イタコン酸３６．４５ｇ（６モル％）を加え３０℃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重量％水溶液２０ｇを加え、攪拌下で２４時間重合を行い、塩水溶液に分散した水溶性重合体の分散液を得た。得られた分散液の平均粒子径と粘度を測定し、さらに、分散液中の（Ａ）成分および（Ｂ）成分の合計含有量を０．２重量％となるように水で希釈した後、希釈分散液の濁度を測定した。結果を表２に示す。
(Example 7) 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 introduction tube. 110 g of the polymer dispersant having a structure and 400 g of ammonium sulfate were dissolved in 1049.25 g of ion-exchanged water. To this, 282.17 g (85 mol%) of acrylamide, 101.73 g of 80% by weight aqueous solution of acryloyloxyethyltrimethylammonium chloride (pure content 81.384 g; 9 mol%) and 36.45 g of itaconic acid (6 mol%) were added. In addition, nitrogen was substituted while heating to 30 ° C. To this was added 20 g of a 2% by weight aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, polymerized for 24 hours with stirring, and a dispersion of a water-soluble polymer dispersed in the aqueous salt solution. Got. After measuring the average particle size and viscosity of the obtained dispersion, and further diluted with water so that the total content of the component (A) and the component (B) in the dispersion is 0.2 wt%, The turbidity of the diluted dispersion was measured. The results are shown in Table 2.
（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３で得られた分岐構造を有する高分子分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水１０１７．９５ｇに溶解した。これに、アクリルアミド２１５．１５ｇ（７９モル％）、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級化物の７５重量％水溶液２０６．６ｇ（純分１５４．９５ｇ；１５モル％）、イタコン酸２９．９ｇ（６モル％）を加え３０℃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重量％水溶液２０ｇを加え、攪拌下で２４時間重合を行い、塩水溶液に分散した水溶性重合体の分散液を得た。得られた分散液の平均粒子径と粘度を測定し、さらに、分散液中の（Ａ）成分および（Ｂ）成分の合計含有量を０．２重量％となるように水で希釈した後、希釈分散液の濁度を測定した。結果を表２に示す。
(Example 8) 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 the polymer dispersant having a structure and 400 g of ammonium sulfate were dissolved in 1017.95 g of ion-exchanged water. To this, 215.15 g (79 mol%) of acrylamide, 206.6 g of 75% by weight aqueous solution of benzyl chloride quaternary product of N, N-dimethylaminoethyl acrylate (pure content 154.95 g; 15 mol%), itaconic acid 29 .9 g (6 mol%) was added and the atmosphere was replaced with nitrogen while heating to 30 ° C. To this was added 20 g of a 2% by weight aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, polymerized for 24 hours with stirring, and a dispersion of a water-soluble polymer dispersed in the aqueous salt solution. Got. After measuring the average particle size and viscosity of the obtained dispersion, and further diluted with water so that the total content of the component (A) and the component (B) in the dispersion is 0.2 wt%, The turbidity of the diluted dispersion was measured. The results are shown in Table 2.
（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３で得られた分岐構造を有する高分子分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水１０４３．５９ｇに溶解した。これに、アクリルアミド２６１．０１ｇ（８２モル％）、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リドの８０重量％水溶液１３０．０５ｇ（純分１０４．０４ｇ；１２モル％）、イタコン酸３４．９５ｇ（６モル％）を加え３０℃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重量％水溶液２０ｇを加え、攪拌下で２４時間重合を行い、塩水溶液に分散した水溶性重合体の分散液を得た。得られた分散液の平均粒子径と粘度を測定し、さらに、分散液中の（Ａ）成分および（Ｂ）成分の合計含有量を０．２重量％となるように水で希釈した後、希釈分散液の濁度を測定した。結果を表２に示す。
(Example 9) 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 the polymer dispersant having a structure and 400 g of ammonium sulfate were dissolved in 1043.59 g of ion-exchanged water. To this, 261.01 g (82 mol%) of acrylamide, 130.05 g (pure content 104.04 g; 12 mol%) of 80% by weight aqueous solution of acryloyloxyethyltrimethylammonium chloride, and 34.95 g (6 mol%) of itaconic acid. In addition, nitrogen was substituted while heating to 30 ° C. To this was added 20 g of a 2% by weight aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, polymerized for 24 hours with stirring, and a dispersion of a water-soluble polymer dispersed in the aqueous salt solution. Got. After measuring the average particle size and viscosity of the obtained dispersion, and further diluted with water so that the total content of the component (A) and the component (B) in the dispersion is 0.2 wt%, The turbidity of the diluted dispersion was measured. The results are shown in Table 2.
（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３で得られた分岐構造を有する高分子分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水１０４９．２５ｇに溶解した。これに、アクリルアミド２８２．１６ｇ（８４．９９８モル％）、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リドの８０重量％水溶液１０１．７３ｇ（純分８１．３８４ｇ；９モル％）、イタコン酸３６．４５ｇ（６モル％）、メチレンビスアクリルアミド０．０１４４ｇ（０．００２モル％）を加え３０℃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重量％水溶液２０ｇを加え、攪拌下で２４時間重合を行い、塩水溶液に分散した水溶性重合体の分散液を得た。得られた分散液の平均粒子径と粘度を測定し、さらに、分散液中の（Ａ）成分および（Ｂ）成分の合計含有量を０．２重量％となるように水で希釈した後、希釈分散液の濁度を測定した。結果を表２に示す。
(Example 10) 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 the polymer dispersant having a structure and 400 g of ammonium sulfate were dissolved in 1049.25 g of ion-exchanged water. To this, 282.16 g (84.998 mol%) of acrylamide, 101.73 g of 80% by weight aqueous solution of acryloyloxyethyltrimethylammonium chloride (81.384 g of pure content; 9 mol%), 36.45 g of itaconic acid (6 mol%) ), 0.0144 g (0.002 mol%) of methylenebisacrylamide was added, and the mixture was heated to 30 ° C. and purged with nitrogen. To this was added 20 g of a 2% by weight aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, polymerized for 24 hours with stirring, and a dispersion of a water-soluble polymer dispersed in the aqueous salt solution. Got. After measuring the average particle size and viscosity of the obtained dispersion, and further diluted with water so that the total content of the component (A) and the component (B) in the dispersion is 0.2 wt%, The turbidity of the diluted dispersion was measured. The results are shown in Table 2.
（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３で得られた分岐構造を有する高分子分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水１０１７．９５ｇに溶解した。これに、アクリルアミド２１５．１４ｇ（７８．９９８モル％）、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級化物の７５重量％水溶液２０６．６ｇ（純分１５４．９５ｇ；１５モル％）、イタコン酸２９．９ｇ（６モル％）、メチレンビスアクリルアミド０．０１１８ｇ（０．００２モル％）を加え３０℃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重量％水溶液２０ｇを加え、攪拌下で２４時間重合を行い、塩水溶液に分散した水溶性重合体の分散液を得た。得られた分散液の平均粒子径と粘度を測定し、さらに、分散液中の（Ａ）成分および（Ｂ）成分の合計含有量を０．２重量％となるように水で希釈した後、希釈分散液の濁度を測定した。結果を表２に示す。
(Example 11) 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 the polymer dispersant having a structure and 400 g of ammonium sulfate were dissolved in 1017.95 g of ion-exchanged water. To this, 215.14 g (78.998 mol%) of acrylamide, 206.6 g of 75% by weight aqueous solution of benzyl chloride quaternary product of N, N-dimethylaminoethyl acrylate (pure 154.95 g; 15 mol%), itacon 29.9 g (6 mol%) of acid and 0.0118 g (0.002 mol%) of methylenebisacrylamide were added and the atmosphere was replaced with nitrogen while heating to 30 ° C. To this was added 20 g of a 2% by weight aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, polymerized for 24 hours with stirring, and a dispersion of a water-soluble polymer dispersed in the aqueous salt solution. Got. After measuring the average particle size and viscosity of the obtained dispersion, and further diluted with water so that the total content of the component (A) and the component (B) in the dispersion is 0.2 wt%, The turbidity of the diluted dispersion was measured. The results are shown in Table 2.
（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３で得られた分岐構造を有する高分子分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水１０４３．５９ｇに溶解した。これに、アクリルアミド２６１ｇ（８１．９９８モル％）、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リドの８０重量％水溶液１３０．０５ｇ（純分１０４．０４ｇ；１２モル％）、イタコン酸３４．９５ｇ（６モル％）、メチレンビスアクリルアミド０．０１３８ｇ（０．００２モル％）を加え３０℃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重量％水溶液２０ｇを加え、攪拌下で２４時間重合を行い、塩水溶液に分散した水溶性重合体の分散液を得た。得られた分散液の平均粒子径と粘度を測定し、さらに、分散液中の（Ａ）成分および（Ｂ）成分の合計含有量を０．２重量％となるように水で希釈した後、希釈分散液の濁度を測定した。結果を表２に示す。
(Example 12) 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 the polymer dispersant having a structure and 400 g of ammonium sulfate were dissolved in 1043.59 g of ion-exchanged water. To this, 261 g (81.998 mol%) of acrylamide, 130.05 g of 80% by weight aqueous solution of acryloyloxyethyltrimethylammonium chloride (pure content 104.04 g; 12 mol%), 34.95 g of itaconic acid (6 mol%), 0.0138 g (0.002 mol%) of methylene bisacrylamide was added, and nitrogen substitution was performed while heating to 30 ° C. To this was added 20 g of a 2% by weight aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, polymerized for 24 hours with stirring, and a dispersion of a water-soluble polymer dispersed in the aqueous salt solution. Got. After measuring the average particle size and viscosity of the obtained dispersion, and further diluted with water so that the total content of the component (A) and the component (B) in the dispersion is 0.2 wt%, The turbidity of the diluted dispersion was measured. The results are shown in Table 2.
（実施例１３）水溶性重合体分散液の製造法
実施例１で得られた水溶性重合体の分散液と実施例２で得られた水溶性重合体の分散液を重量比１：１で混合した。
(Example 13) Method for producing water-soluble polymer dispersion The water-soluble polymer dispersion obtained in Example 1 and the water-soluble polymer dispersion obtained in Example 2 were mixed at a weight ratio of 1: 1. Mixed.
（実施例１４）水溶性重合体分散液の製造法
実施例７で得られた水溶性重合体の分散液と実施例８で得られた水溶性重合体の分散液を重量比１：１で混合した。
(Example 14) Method for producing water-soluble polymer dispersion The water-soluble polymer dispersion obtained in Example 7 and the water-soluble polymer dispersion obtained in Example 8 were mixed at a weight ratio of 1: 1. Mixed.
（実施例１５）水溶性重合体分散液の製造法
実施例１０で得られた水溶性重合体の分散液と実施例１１で得られた水溶性重合体の分散液を重量比１：１で混合した。
(Example 15) Method for producing water-soluble polymer dispersion The water-soluble polymer dispersion obtained in Example 10 and the water-soluble polymer dispersion obtained in Example 11 were mixed at a weight ratio of 1: 1. Mixed.
（実施例１６）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しない高分子分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水１０４３．５９ｇに溶解した。これに、アクリルアミド２６１．０１ｇ（８２モル％）、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リドの８０重量％水溶液１３０．０５ｇ（純分１０４．０４ｇ；１２モル％）、イタコン酸１７．４７ｇ（３モル％）を加え３０℃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重量％水溶液２０ｇを加えた。３時間後、イタコン酸１７．４７ｇ（３モル％）を加え攪拌下で２１時間重合を行い、塩水溶液に分散した水溶性重合体の分散液を得た。得られた分散液の平均粒子径と粘度を測定し、さらに、分散液中の（Ａ）成分および（Ｂ）成分の合計含有量を０．２重量％となるように水で希釈した後、希釈分散液の濁度を測定した。結果を表２に示す。
(Example 16) 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 polymer dispersant having no structure and 400 g of ammonium sulfate were dissolved in 1043.59 g of ion-exchanged water. To this, 261.01 g (82 mol%) of acrylamide, 130.05 g (pure content 104.04 g; 12 mol%) of an 80 wt% aqueous solution of acryloyloxyethyltrimethylammonium chloride, and 17.47 g (3 mol%) of itaconic acid were added. In addition, nitrogen was substituted while heating to 30 ° C. To this was added 20 g of a 2 wt% aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator. Three hours later, 17.47 g (3 mol%) of itaconic acid was added and polymerization was carried out for 21 hours with stirring to obtain a dispersion of a water-soluble polymer dispersed in an aqueous salt solution. After measuring the average particle size and viscosity of the obtained dispersion, and further diluted with water so that the total content of the component (A) and the component (B) in the dispersion is 0.2 wt%, The turbidity of the diluted dispersion was measured. The results are shown in Table 2.
（実施例１７）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で得られた分岐構造を有する高分子分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水１０４３．５９ｇに溶解した。これに、アクリルアミド２６１．０１ｇ（８２モル％）、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リドの８０重量％水溶液１３０．０５ｇ（純分１０４．０４ｇ；１２モル％）、イタコン酸１７．４７ｇ（３モル％）を加え３０℃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重量％水溶液２０ｇを加えた。３時間後、イタコン酸１７．４７ｇ（３モル％）を加え攪拌下で２１時間重合を行い、塩水溶液に分散した水溶性重合体の分散液を得た。得られた分散液の平均粒子径と粘度を測定し、さらに、分散液中の（Ａ）成分および（Ｂ）成分の合計含有量を０．２重量％となるように水で希釈した後、希釈分散液の濁度を測定した。結果を表２に示す。
(Example 17) 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 the polymer dispersant having a structure and 400 g of ammonium sulfate were dissolved in 1043.59 g of ion-exchanged water. To this, 261.01 g (82 mol%) of acrylamide, 130.05 g (pure content 104.04 g; 12 mol%) of an 80 wt% aqueous solution of acryloyloxyethyltrimethylammonium chloride, and 17.47 g (3 mol%) of itaconic acid were added. In addition, nitrogen was substituted while heating to 30 ° C. To this was added 20 g of a 2 wt% aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator. Three hours later, 17.47 g (3 mol%) of itaconic acid was added and polymerization was carried out for 21 hours with stirring to obtain a dispersion of a water-soluble polymer dispersed in an aqueous salt solution. After measuring the average particle size and viscosity of the obtained dispersion, and further diluted with water so that the total content of the component (A) and the component (B) in the dispersion is 0.2 wt%, The turbidity of the diluted dispersion was measured. The results are shown in Table 2.
（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１で得られた分岐構造を有しない高分子分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水１０４２．５２ｇに溶解した。これに、アクリルアミド２９１．６６ｇ（８８モル％）、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リドの８０重量％水溶液１３５．４２ｇ（純分１０８．３３６ｇ；１２モル％）を加え３０℃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重量％水溶液２０ｇを加え、攪拌下で２４時間重合を行い、塩水溶液に分散した水溶性重合体の分散液を得た。得られた分散液の平均粒子径と粘度を測定し、さらに、分散液中の（Ａ）成分および（Ｂ）成分の合計含有量を０．２重量％となるように水で希釈した後、希釈分散液の濁度を測定した。結果を表２に示す。
Comparative Example 1 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 110 g of a polymer dispersant having no structure and 400 g of ammonium sulfate were dissolved in 1042.52 g of ion-exchanged water. To this was added 291.66 g (88 mol%) of acrylamide and 135.42 g of 80 wt% aqueous solution of acryloyloxyethyltrimethylammonium chloride (pure content 108.336 g; 12 mol%), and the atmosphere was replaced with nitrogen while heating to 30 ° C. . To this was added 20 g of a 2% by weight aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, polymerized for 24 hours with stirring, and a dispersion of a water-soluble polymer dispersed in the aqueous salt solution. Got. After measuring the average particle size and viscosity of the obtained dispersion, and further diluted with water so that the total content of the component (A) and the component (B) in the dispersion is 0.2 wt%, The turbidity of the diluted dispersion was measured. The results are shown in Table 2.
（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３で得られた分岐構造を有する高分子分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水１０４２．５２ｇに溶解した。これに、アクリルアミド２９１．６６ｇ（８８モル％）、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リドの８０重量％水溶液１３５．４２ｇ（純分１０８．３３６ｇ；１２モル％）を加え３０℃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重量％水溶液２０ｇを加え、攪拌下で２４時間重合を行い、塩水溶液に分散した水溶性重合体の分散液を得た。得られた分散液の平均粒子径と粘度を測定し、さらに、分散液中の（Ａ）成分および（Ｂ）成分の合計含有量を０．２重量％となるように水で希釈した後、希釈分散液の濁度を測定した。結果を表２に示す。
Comparative Example 2 Production Method of Water-Soluble Polymer Dispersion Branched in Production Example 3 in a 2 liter five-necked separable flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube 110 g of the polymer dispersant having a structure and 400 g of ammonium sulfate were dissolved in 1042.52 g of ion-exchanged water. To this was added 291.66 g (88 mol%) of acrylamide and 135.42 g of 80 wt% aqueous solution of acryloyloxyethyltrimethylammonium chloride (pure content 108.336 g; 12 mol%), and the atmosphere was replaced with nitrogen while heating to 30 ° C. . To this was added 20 g of a 2% by weight aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, polymerized for 24 hours with stirring, and a dispersion of a water-soluble polymer dispersed in the aqueous salt solution. Got. After measuring the average particle size and viscosity of the obtained dispersion, and further diluted with water so that the total content of the component (A) and the component (B) in the dispersion is 0.2 wt%, The turbidity of the diluted dispersion was measured. The results are shown in Table 2.
（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１で得られた分岐構造を有しない高分子分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水１０３７．１４ｇに溶解した。これに、アクリルアミド２７０．１３ｇ（８４．９９８モル％）、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リドの８０重量％水溶液１６２．３２ｇ（純分１２９．８５６ｇ；１５モル％）、メチレンビスアクリルアミド０．０１３８ｇ（０．００２モル％）を加え３０℃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重量％水溶液２０ｇを加え、攪拌下で２４時間重合を行い、塩水溶液に分散した水溶性重合体の分散液を得た。得られた分散液の平均粒子径と粘度を測定し、さらに、分散液中の（Ａ）成分および（Ｂ）成分の合計含有量を０．２重量％となるように水で希釈した後、希釈分散液の濁度を測定した。結果を表２に示す。
Comparative 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 polymer dispersant having no structure and 400 g of ammonium sulfate were dissolved in 1037.14 g of ion-exchanged water. To this, 270.13 g (84.998 mol%) of acrylamide, 162.32 g of 80% by weight aqueous solution of acryloyloxyethyltrimethylammonium chloride (pure content: 129.856 g; 15 mol%), 0.0138 g of methylenebisacrylamide (0. 002 mol%) was added, and nitrogen substitution was performed while heating to 30 ° C. To this was added 20 g of a 2% by weight aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, polymerized for 24 hours with stirring, and a dispersion of a water-soluble polymer dispersed in the aqueous salt solution. Got. After measuring the average particle size and viscosity of the obtained dispersion, and further diluted with water so that the total content of the component (A) and the component (B) in the dispersion is 0.2 wt%, The turbidity of the diluted dispersion was measured. The results are shown in Table 2.
（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３で得られた分岐構造を有する高分子分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水１０３７．１４ｇに溶解した。これに、アクリルアミド２７０．１３ｇ（８４．９９８モル％）、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リドの８０重量％水溶液１６２．３２ｇ（純分１２９．８５６ｇ；１５モル％）、メチレンビスアクリルアミド０．０１３８ｇ（０．００２モル％）を加え３０℃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重量％水溶液２０ｇを加え、攪拌下で２４時間重合を行い、塩水溶液に分散した水溶性重合体の分散液を得た。得られた分散液の平均粒子径と粘度を測定し、さらに、分散液中の（Ａ）成分および（Ｂ）成分の合計含有量を０．２重量％となるように水で希釈した後、希釈分散液の濁度を測定した。結果を表２に示す。
Comparative Example 4 Production Method of Water-Soluble Polymer Dispersion Branched in Production Example 3 in a 2 liter five-necked separable flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube 110 g of the polymer dispersant having a structure and 400 g of ammonium sulfate were dissolved in 1037.14 g of ion-exchanged water. To this, 270.13 g (84.998 mol%) of acrylamide, 162.32 g (pure content: 129.856 g; 15 mol%) of an 80 wt% aqueous solution of acryloyloxyethyltrimethylammonium chloride, 0.0138 g (0. 002 mol%) was added, and nitrogen substitution was performed while heating to 30 ° C. To this was added 20 g of a 2% by weight aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, polymerized for 24 hours with stirring, and a dispersion of a water-soluble polymer dispersed in the aqueous salt solution. Got. After measuring the average particle size and viscosity of the obtained dispersion, and further diluted with water so that the total content of the component (A) and the component (B) in the dispersion is 0.2 wt%, The turbidity of the diluted dispersion was measured. The results are shown in Table 2.
（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１で得られた分岐構造を有する高分子分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水１０３９．５２ｇに溶解した。これに、アクリルアミド２１５ｇ（７３モル％）、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リドの８０重量％水溶液１５０．４２ｇ（純分１２０．３３６ｇ；１５モル％）、イタコン酸６４．６７ｇ（１２モル％）を加え３０℃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重量％水溶液２０ｇを加え、攪拌下で２４時間重合を行い、塩水溶液に分散した水溶性重合体の分散液を得た。得られた分散液の平均粒子径と粘度を測定し、さらに、分散液中の（Ａ）成分および（Ｂ）成分の合計含有量を０．２重量％となるように水で希釈した後、希釈分散液の濁度を測定した。結果を表２に示す。
Comparative Example 5 Production Method of Water-Soluble Polymer Dispersion Branch obtained in Production Example 1 in a 2 liter five-necked separable flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube 110 g of the polymer dispersant having a structure and 400 g of ammonium sulfate were dissolved in 1039.52 g of ion-exchanged water. To this was added 215 g (73 mol%) of acrylamide, 150.42 g of 80% by weight aqueous solution of acryloyloxyethyltrimethylammonium chloride (120.336 g pure; 15 mol%), and 64.67 g (12 mol%) itaconic acid. While warming to 0 ° C., nitrogen substitution was performed. To this was added 20 g of a 2% by weight aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, polymerized for 24 hours with stirring, and a dispersion of a water-soluble polymer dispersed in the aqueous salt solution. Got. After measuring the average particle size and viscosity of the obtained dispersion, and further diluted with water so that the total content of the component (A) and the component (B) in the dispersion is 0.2 wt%, The turbidity of the diluted dispersion was measured. The results are shown in Table 2.
（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３で得られた分岐構造を有する高分子分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水１０３９．５２ｇに溶解した。これに、アクリルアミド２１５ｇ（７３モル％）、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リドの８０重量％水溶液１５０．４２ｇ（純分１２０．３３６ｇ；１５モル％）、イタコン酸６４．６７ｇ（１２モル％）を加え３０℃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重量％水溶液２０ｇを加え、攪拌下で２４時間重合を行い、塩水溶液に分散した水溶性重合体の分散液を得た。得られた分散液の平均粒子径と粘度を測定し、さらに、分散液中の（Ａ）成分および（Ｂ）成分の合計含有量を０．２重量％となるように水で希釈した後、希釈分散液の濁度を測定した。結果を表２に示す。
Comparative Example 6 Production Method of Water-Soluble Polymer Dispersion Branched in Production Example 3 in a 2 liter five-necked separable flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube 110 g of the polymer dispersant having a structure and 400 g of ammonium sulfate were dissolved in 1039.52 g of ion-exchanged water. To this was added 215 g (73 mol%) of acrylamide, 150.42 g of 80% by weight aqueous solution of acryloyloxyethyltrimethylammonium chloride (120.336 g pure; 15 mol%), and 64.67 g (12 mol%) itaconic acid. While warming to 0 ° C., nitrogen substitution was performed. To this was added 20 g of a 2% by weight aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, polymerized for 24 hours with stirring, and a dispersion of a water-soluble polymer dispersed in the aqueous salt solution. Got. After measuring the average particle size and viscosity of the obtained dispersion, and further diluted with water so that the total content of the component (A) and the component (B) in the dispersion is 0.2 wt%, The turbidity of the diluted dispersion was measured. The results are shown in Table 2.
（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１で得られた分岐構造を有する高分子分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水１０４１．７３ｇに溶解した。これに、アクリルアミド１６３．７１ｇ（６０モル％）、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リドの８０重量％水溶液１３９．３５ｇ（純分１１１．４８ｇ；１５モル％）、イタコン酸１２４．８１ｇ（２５モル％）を加え３０℃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重量％水溶液２０ｇを加え、攪拌下で２４時間重合を行い、塩水溶液に分散した水溶性重合体の分散液を得た。得られた分散液の平均粒子径と粘度を測定し、さらに、分散液中の（Ａ）成分および（Ｂ）成分の合計含有量を０．２重量％となるように水で希釈した後、希釈分散液の濁度を測定した。結果を表２に示す。
Comparative Example 7 Production Method of Water-Soluble Polymer Dispersion Branch obtained in Production Example 1 in a 2 liter five-necked separable flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube 110 g of the polymer dispersant having a structure and 400 g of ammonium sulfate were dissolved in 1041.73 g of ion-exchanged water. To this, 163.71 g (60 mol%) of acrylamide, 139.35 g of an 80 wt% aqueous solution of acryloyloxyethyltrimethylammonium chloride (111.48 g of pure matter; 15 mol%), and 124.81 g (25 mol%) of itaconic acid were added. In addition, nitrogen was substituted while heating to 30 ° C. To this was added 20 g of a 2% by weight aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, polymerized for 24 hours with stirring, and a dispersion of a water-soluble polymer dispersed in the aqueous salt solution. Got. After measuring the average particle size and viscosity of the obtained dispersion, and further diluted with water so that the total content of the component (A) and the component (B) in the dispersion is 0.2 wt%, The turbidity of the diluted dispersion was measured. The results are shown in Table 2.
（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３で得られた分岐構造を有する高分子分散剤を１１０ｇ、硫酸アンモニウム４００ｇをイオン交換水１０４１．７３ｇに溶解した。これに、アクリルアミド１６３．７１ｇ（６０モル％）、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リドの８０重量％水溶液１３９．３５ｇ（純分１１１．４８ｇ；１５モル％）、イタコン酸１２４．８１ｇ（２５モル％）を加え３０℃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重量％水溶液２０ｇを加え、攪拌下で２４時間重合を行い、塩水溶液に分散した水溶性重合体の分散液を得た。得られた分散液の平均粒子径と粘度を測定し、さらに、分散液中の（Ａ）成分および（Ｂ）成分の合計含有量を０．２重量％となるように水で希釈した後、希釈分散液の濁度を測定した。結果を表２に示す。
Comparative Example 8 Production Method of Water-Soluble Polymer Dispersion Branched in Production Example 3 in a 2 liter five-necked separable flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube 110 g of the polymer dispersant having a structure and 400 g of ammonium sulfate were dissolved in 1041.73 g of ion-exchanged water. To this, 163.71 g (60 mol%) of acrylamide, 139.35 g of an 80 wt% aqueous solution of acryloyloxyethyltrimethylammonium chloride (111.48 g of pure matter; 15 mol%), and 124.81 g (25 mol%) of itaconic acid were added. In addition, nitrogen was substituted while heating to 30 ° C. To this was added 20 g of a 2% by weight aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, polymerized for 24 hours with stirring, and a dispersion of a water-soluble polymer dispersed in the aqueous salt solution. Got. After measuring the average particle size and viscosity of the obtained dispersion, and further diluted with water so that the total content of the component (A) and the component (B) in the dispersion is 0.2 wt%, The turbidity of the diluted dispersion was measured. The results are shown in Table 2.
実施例および比較例で得られた水溶性重合体分散液について、平均粒子径、粘度を測定した結果を表２および表３に示す。なお、各測定方法は、以下のとおりである。
（平均粒子径）
光学顕微鏡で観察（顕微鏡視野中の分散粒子を、任意に１００個測定した平均値）することにより行った。
（粘度）
B型粘度を使用してJIS
K7117-1に従い、２５℃における粘度を測定した。
（濁度）
脱イオン水で分散液中の（Ａ）成分と前記（Ｂ）成分の合計含有量を０．２重量％に希釈後、希釈分散液が示したｐＨ（２５℃）から、１重量％の水酸化ナトリウム水溶液を滴下し、希釈分散液のｐＨを８まで変化させ、そのｐＨが５〜８に変化する過程で、希釈分散液が示した濁度の最小値と最大値を測定し、濁度の範囲を求めた。
Tables 2 and 3 show the results of measuring the average particle diameter and the viscosity of the water-soluble polymer dispersions obtained in Examples and Comparative Examples. Each measurement method is as follows.
(Average particle size)
This was performed by observing with an optical microscope (an average value obtained by arbitrarily measuring 100 dispersed particles in the microscope field).
(viscosity)
JIS using B-type viscosity
The viscosity at 25 ° C. was measured according to K7117-1.
(Turbidity)
After diluting the total content of component (A) and component (B) in the dispersion with deionized water to 0.2% by weight, 1% by weight of water from the pH (25 ° C.) indicated by the diluted dispersion A sodium oxide aqueous solution is dropped, and the pH of the diluted dispersion is changed to 8. In the process of changing the pH from 5 to 8, the minimum and maximum turbidity values indicated by the diluted dispersion are measured. The range of was calculated.
表中の数字はモル％。粘度は不揮発分を２０重量％に調整した場合の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。
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リド
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
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
The numbers in the table are mol%. The viscosity is a value measured at 25 ° C. when the nonvolatile content is adjusted to 20% by weight.
In addition, about description of each compound (monomer etc.) abbreviation in Table 2, it shall represent the following compound.
DMAEA-Q: acryloyloxyethyltrimethylammonium chloride DMAEA-BQ: benzyl chloride quaternized product of N, N-dimethylaminoethyl acrylate IA: itaconic acid MBAA: methylenebisacrylamide AM: acrylamide
評価方法：
（評価例１〜１７及び比較評価例１〜４）
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）３００ｍｌに調整し、固形分濃度１．０重量％の紙料を得た。つぎに、紙料の固形分量に対し１．０重量％の硫酸バンドを添加してｐＨ７．０のパルプスラリーを調製した。そして、実施例１から１７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、水溶性重合体分散液の希釈液を調製した。つぎに、パルプスラリーに水溶性重合体分散液の希釈液を、パルプスラリー中の紙料の固形分量に対し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１５０ｇ／ｍ２
の紙を得た。次いで、得られた紙を回転型乾燥機で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:
(Evaluation Examples 1 to 17 and Comparative Evaluation Examples 1 to 4)
Corrugated cardboard paper was beaten with a Niagara-type beater and adjusted to 300 ml of Canadian Standard Freeness (CSF) to obtain a paper stock having a solid content concentration of 1.0% by weight. Next, a 1.0% by weight sulfuric acid band was added to the solid content of the stock to prepare a pH 7.0 pulp slurry. The water-soluble polymer dispersions obtained in Examples 1 to 17 and Comparative Examples 1 to 8 were diluted with tap water to a solid content concentration of the polymer ((A) + (B)) to 0.05% by weight. Then, a diluted solution of the water-soluble polymer dispersion was prepared. Next, a dilution of the water-soluble polymer dispersion is added to the pulp slurry in an amount of 0.05% by weight based on the solid content of the paper stock in the pulp slurry, dehydrated with a tapi sheet machine, and 5 kg / cm 2 . Press for 2 minutes, basis weight 150g / m 2
I got the paper. The resulting paper was then dried for 4 minutes at 105 ° C. with a rotary drier, 23 ° C., 50% R.D. 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、地合変動係数は、数値が小さいほど地合が良好であることを示す。 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. In addition, a formation variation coefficient shows that formation is so favorable that a numerical value is small.
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.
Claims (9)
A paper production yield improver comprising the water-soluble polymer dispersion according to any one of claims 1 to 6.
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