JP2021011540A - Method for producing paper-strengthening agent for paper-making - Google Patents
Method for producing paper-strengthening agent for paper-making Download PDFInfo
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- JP2021011540A JP2021011540A JP2019126406A JP2019126406A JP2021011540A JP 2021011540 A JP2021011540 A JP 2021011540A JP 2019126406 A JP2019126406 A JP 2019126406A JP 2019126406 A JP2019126406 A JP 2019126406A JP 2021011540 A JP2021011540 A JP 2021011540A
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- mass
- paper
- polymer
- monomer
- surfactant
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Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- 238000005728 strengthening Methods 0.000 title abstract 2
- 239000000178 monomer Substances 0.000 claims abstract description 71
- 229920000642 polymer Polymers 0.000 claims abstract description 62
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000004094 surface-active agent Substances 0.000 claims abstract description 26
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 19
- 125000002091 cationic group Chemical group 0.000 claims abstract description 14
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims description 32
- 239000013054 paper strength agent Substances 0.000 claims description 21
- 239000000126 substance Substances 0.000 abstract description 22
- 230000002708 enhancing effect Effects 0.000 abstract description 13
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 32
- -1 2-ethylhexyl Chemical group 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 19
- LBSPZZSGTIBOFG-UHFFFAOYSA-N bis[2-(4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene;dihydrochloride Chemical compound Cl.Cl.N=1CCNC=1C(C)(C)N=NC(C)(C)C1=NCCN1 LBSPZZSGTIBOFG-UHFFFAOYSA-N 0.000 description 18
- 238000003756 stirring Methods 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 229910001873 dinitrogen Inorganic materials 0.000 description 17
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 16
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 14
- 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 13
- 239000011734 sodium Substances 0.000 description 13
- 229910052708 sodium Inorganic materials 0.000 description 13
- 150000005215 alkyl ethers Chemical class 0.000 description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 9
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 9
- 125000000129 anionic group Chemical group 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229920003169 water-soluble polymer Polymers 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- 239000004147 Sorbitan trioleate Substances 0.000 description 4
- 238000010009 beating Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 4
- 235000019333 sodium laurylsulphate Nutrition 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
- 235000019337 sorbitan trioleate Nutrition 0.000 description 4
- 229960000391 sorbitan trioleate Drugs 0.000 description 4
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 229920001214 Polysorbate 60 Polymers 0.000 description 3
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229920000831 ionic polymer Polymers 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N alpha-Methyl-n-butyl acrylate Natural products CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003623 enhancer Substances 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 1
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 1
- IOSXLUZXMXORMX-UHFFFAOYSA-N 1-ethenoxypentane Chemical group CCCCCOC=C IOSXLUZXMXORMX-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- WHNPOQXWAMXPTA-UHFFFAOYSA-N 3-methylbut-2-enamide Chemical compound CC(C)=CC(N)=O WHNPOQXWAMXPTA-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 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
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- PZXSLFQJOZPCJG-UHFFFAOYSA-N bis[2-(5-methyl-4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene;dihydrochloride Chemical compound Cl.Cl.N1C(C)CN=C1C(C)(C)N=NC(C)(C)C1=NCC(C)N1 PZXSLFQJOZPCJG-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-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
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229940079826 hydrogen sulfite Drugs 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- 229940075566 naphthalene Drugs 0.000 description 1
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Chemical compound CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 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
- 239000013055 pulp slurry Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940083575 sodium dodecyl sulfate Drugs 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000001593 sorbitan monooleate Substances 0.000 description 1
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- 229940035049 sorbitan monooleate Drugs 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paper (AREA)
Abstract
Description
本発明は紙の製造に使用される製紙用紙力剤の製造方法に関する。 The present invention relates to a method for producing a paper-making paper strength agent used for producing paper.
従来から紙に強度を付与する紙力剤として、ポリアクリルアミド系紙力剤がある。ポリアクリルアミド系紙力剤はイオン性によりアニオンタイプ、カチオンタイプ、及び両性タイプに分類される。現在では性能の面から、両性タイプの紙力剤が主流となっている。両性タイプのポリアクリルアミド系紙力剤は、アクリルアミドにカチオン性モノマーとアニオン性モノマー等の各種重合成分を共重合して得られる両性アクリルアミド系水溶性ポリマーよりなる（特許文献１）。両性アクリルアミド系水溶性ポリマーは、ポリイオンコンプレックスを形成する。ポリイオンコンプレックスは、カチオン基とアニオン基の間の静電相互作用により形成される。ポリイオンコンプレックスを形成することで、両性アクリルアミド系水溶性ポリマーは紙力増強効果を発揮することが知られている。 Conventionally, there is a polyacrylamide-based paper strength agent as a paper strength agent that imparts strength to paper. Polyacrylamide-based paper strength agents are classified into anionic type, cationic type, and amphoteric type according to ionicity. At present, amphoteric type paper strength agents are the mainstream in terms of performance. An amphoteric type polyacrylamide-based paper strength agent comprises an amphoteric acrylamide-based water-soluble polymer obtained by copolymerizing acrylamide with various polymerization components such as a cationic monomer and an anionic monomer (Patent Document 1). Amphoteric acrylamide-based water-soluble polymers form a polyion complex. The polyion complex is formed by electrostatic interaction between cation and anion groups. It is known that an amphoteric acrylamide-based water-soluble polymer exerts a paper strength enhancing effect by forming a polyion complex.
近年古紙のリサイクル化やクローズド化が進むことで、抄紙系内には微細繊維や溶存電解質物質が蓄積され、抄紙系の電気伝導度は上昇傾向にある。このため、特に両性タイプの紙力剤はイオンコンプレックスの形成が阻害され、十分な効果が発揮できない状況となっている。 In recent years, with the progress of recycling and closing of used paper, fine fibers and dissolved electrolyte substances are accumulated in the papermaking system, and the electric conductivity of the papermaking system tends to increase. For this reason, especially amphoteric type paper strength agents are in a situation where the formation of an ion complex is inhibited and a sufficient effect cannot be exhibited.
一方、分子内に疎水性基を有する水溶性高分子は水中で会合体を形成することが知られている（非特許文献１）。疎水性会合体は疎水性相互作用により形成されるため、溶存電解質の存在によりその形成が阻害されることは無い。 On the other hand, it is known that a water-soluble polymer having a hydrophobic group in the molecule forms an aggregate in water (Non-Patent Document 1). Since the hydrophobic aggregate is formed by hydrophobic interaction, the presence of the dissolved electrolyte does not inhibit its formation.
カチオン性モノマー、アニオン性モノマー、架橋性ビニル系モノマー、疎水性ビニル系モノマー及び（メタ）アクリルアミドを共重合した共重合体を含有してなる紙力増強剤が知られている（特許文献２）。当該技術における疎水性モノマーとは、水に対する溶解度が小さい難溶性を有するビニル系モノマーであり、（メタ）アクリロニトリル、メタクリル酸メチル、メタクリル酸グリシジル、メタクリル酸ベンジルの群から選ばれた１種又は２種以上の混合物が挙げられている。これらのモノマーを水に添加し、重合開始剤を投入して重合し、目的の重合体を得ている。しかし、水に難溶性のモノマーは水に添加し撹拌した場合、疎水性モノマー液滴を形成し、他の水溶性モノマーとの共重合が均一に起こりにくいという問題がある。 A paper strength enhancer containing a copolymer of a cationic monomer, an anionic monomer, a crosslinkable vinyl monomer, a hydrophobic vinyl monomer, and (meth) acrylamide is known (Patent Document 2). .. The hydrophobic monomer in the present technology is a vinyl-based monomer having low solubility in water and having low solubility in water, and is one or 2 selected from the group of (meth) acrylonitrile, methyl methacrylate, glycidyl methacrylate, and benzyl methacrylate. Mixtures of seeds and above are listed. These monomers are added to water, and a polymerization initiator is added to polymerize the polymer to obtain the desired polymer. However, when a monomer sparingly soluble in water is added to water and stirred, there is a problem that hydrophobic monomer droplets are formed and copolymerization with other water-soluble monomers is unlikely to occur uniformly.
溶解パラメーターが２０．５（ＭＰａ）１／２以下で非イオン性のモノマーの一種以上に由来する構成単位と、アニオン性又はカチオン性モノマーの一種以上に由来する構成単位とを有する共重合体（Ａ）と界面活性剤（Ｂ）とを（Ａ）／（Ｂ）＝９９／１〜１／９９（重量比）の範囲で含有する紙質向上剤が開示されている（特許文献３）。当該技術における紙質向上剤は、予め共重合体を得た後に、界面活性剤を混合することにより得られるものである。 A copolymer having a structural unit derived from one or more nonionic monomers and a structural unit derived from one or more anionic or cationic monomers having a dissolution parameter of 20.5 (MPa) 1/2 or less. A paper quality improver containing A) and a surfactant (B) in the range of (A) / (B) = 99/1 to 1/99 (weight ratio) is disclosed (Patent Document 3). The paper quality improver in the present technology is obtained by obtaining a copolymer in advance and then mixing the surfactant.
本発明の目的は、一般に使用されている両性タイプの紙力剤の問題点を解決し、イオン性夾雑物の影響を受けにくく紙力増強効果に優れた新しいタイプの紙力剤を提供することにある。また、疎水性モノマーと親水性モノマーを共重合して紙力増強剤を得る場合に、その性能を向上させることにある。 An object of the present invention is to solve a problem of a commonly used amphoteric type paper strength agent and to provide a new type of paper strength agent which is not easily affected by ionic impurities and has an excellent paper strength enhancing effect. It is in. Another object of the present invention is to improve the performance of a paper strength enhancer obtained by copolymerizing a hydrophobic monomer and a hydrophilic monomer.
本発明者は鋭意検討を重ねた結果、疎水性単量体、（メタ）アクリルアミド、カチオン性単量体を必須成分とし、反応性界面活性剤を含まない単量体を界面活性剤存在下重合することにより得られる高分子が、優れた紙力増強効果を発揮することを見出した。 As a result of diligent studies, the present inventor polymerizes a monomer containing a hydrophobic monomer, (meth) acrylamide, and a cationic monomer as essential components and containing no reactive surfactant in the presence of a surfactant. It was found that the polymer obtained by the above exerts an excellent effect of enhancing the paper strength.
本発明によれば、優れた紙力増強効果を有する紙力剤を得ることができる。 According to the present invention, it is possible to obtain a paper strength agent having an excellent paper strength enhancing effect.
以下本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明によれば、疎水性単量体、（メタ）アクリルアミド、カチオン性単量体を必須成分とし、反応性界面活性剤を含まない単量体を界面活性剤存在下重合することにより優れた紙力増強効果を有する高分子が得られる。重合は水溶液重合、懸濁重合、塩水中分散重合等の従来公知の方法により行うことができる。例えば、所定の反応容器に単量体混合物、水、界面活性剤、ラジカル重合開始剤を添加し、窒素ガス等の不活性ガス雰囲気下、撹拌、加温することにより目的の高分子を得ることができる。 According to the present invention, it is excellent to polymerize a monomer containing a hydrophobic monomer, (meth) acrylamide, and a cationic monomer as essential components and not containing a reactive surfactant in the presence of a surfactant. A polymer having a paper strength enhancing effect can be obtained. The polymerization can be carried out by conventionally known methods such as aqueous solution polymerization, suspension polymerization, and dispersion polymerization in salt water. For example, a monomer mixture, water, a surfactant, and a radical polymerization initiator are added to a predetermined reaction vessel, and the desired polymer is obtained by stirring and heating in an atmosphere of an inert gas such as nitrogen gas. Can be done.
疎水性単量体としては、ブチル（メタ）アクリレート、オクチル（メタ）アクリレート、２−エチルへキシル（メタ）アクリレート、ドデシル（メタ）アクリレート、オクタデシル（メタ）アクリレート、スチレン等が挙げられる。これらを二種以上組み合わせることも可能である。疎水性単量体は全単量体に対し、０．０５〜１５質量％が好ましく、さらに好ましくは０．１〜１０質量％である。疎水性単量体の量が少ないと疎水性会合体の形成が不十分となり紙力増強効果が低下する。疎水性単量体の量が多いとアクリルアミドの量が少なくなり、パルプとの水素結合による結合力が低下し紙力増強効果が低下する。 Examples of the hydrophobic monomer include butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, and styrene. It is also possible to combine two or more of these. The hydrophobic monomer is preferably 0.05 to 15% by mass, more preferably 0.1 to 10% by mass, based on all the monomers. If the amount of the hydrophobic monomer is small, the formation of the hydrophobic aggregate is insufficient and the paper strength enhancing effect is lowered. When the amount of the hydrophobic monomer is large, the amount of acrylamide is small, the bonding force due to hydrogen bonding with pulp is reduced, and the paper strength enhancing effect is reduced.
カチオン性単量体としては、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、ジメチルアミノプロピル（メタ）アクリルアミド、ジエチルアミノプロピル（メタ）アクリルアミドなどの無機酸若しくは有機酸の塩類、またはこれら第３級アミノ基含有単量体とメチルクロライド、ベンジルクロライド、ジメチル硫酸、エピクロロヒドリン等の四級化剤との反応によって得られる第四級アンモニウム塩を有する単量体などが挙げられる。これらを二種以上組み合わせることも可能である。カチオン性単量体は全単量体に対し、３〜３０質量％が好ましく、更に好ましくは５〜２５質量％である。カチオン性単量体の量が少ないとパルプへの吸着性が低下し紙力増強効果が低下する。またカチオン性単量体の量が多すぎるとアクリルアミドの量が少なくなり、パルプとの水素結合による結合力が低下し紙力増強効果が低下する。 Examples of the cationic monomer include salts of inorganic or organic acids such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, and diethylaminopropyl (meth) acrylamide, or salts thereof. Examples thereof include a monomer having a quaternary ammonium salt obtained by reacting a tertiary amino group-containing monomer with a quaternary agent such as methyl chloride, benzyl chloride, dimethyl sulfate, and epichlorohydrin. It is also possible to combine two or more of these. The cationic monomer is preferably 3 to 30% by mass, more preferably 5 to 25% by mass, based on all the monomers. If the amount of the cationic monomer is small, the adsorptivity to pulp is lowered and the paper strength enhancing effect is lowered. On the other hand, if the amount of the cationic monomer is too large, the amount of acrylamide decreases, the binding force due to hydrogen bonding with pulp decreases, and the paper strength enhancing effect decreases.
本発明の紙力剤に係る高分子は重合成分としてさらにアクリルアミド以外のノニオン性単量体、アニオン性単量体、架橋性単量体等を含むことができる。これらの合計量は全単量体の２０質量％以下が好ましい。尚、本発明の紙力剤に係る高分子は重合成分として反応性界面活性は含まない。ここで反応性界面活性剤とは、一分子中にラジカル重合可能なエチレン性二重結合を持つ置換基を有し界面活性剤として機能する単量体である。 The polymer according to the paper strength agent of the present invention can further contain a nonionic monomer, an anionic monomer, a crosslinkable monomer and the like other than acrylamide as a polymerization component. The total amount of these is preferably 20% by mass or less of the total monomer. The polymer according to the paper strength agent of the present invention does not contain reactive surfactant as a polymerization component. Here, the reactive surfactant is a monomer having a substituent having a radically polymerizable ethylenic double bond in one molecule and functioning as a surfactant.
アクリルアミド以外のノニオン性単量体としては、ジメチルアクリルアミド、ビニルホルムアミド、ヒドロキシエチル（メタ）アクリレート等がある。これらを二種以上組み合わせることも可能である。 Nonionic monomers other than acrylamide include dimethylacrylamide, vinylformamide, hydroxyethyl (meth) acrylate and the like. It is also possible to combine two or more of these.
アニオン性単量体としては、（メタ）アクリル酸、クロトン酸等のモノカルボン酸単量体、マレイン酸、イタコン酸等のジカルボン酸単量体、２−アクリルアミド−２−メチルプロパンスルホン酸等の有機スルホン酸単量体、またはこれらのナトリウム塩等のアルカリ金属塩、アンモニウム塩等が挙げられる。これらを二種以上組み合わせることも可能である。 Examples of the anionic monomer include monocarboxylic acid monomers such as (meth) acrylic acid and crotonic acid, dicarboxylic acid monomers such as maleic acid and itaconic acid, and 2-acrylamide-2-methylpropanesulfonic acid. Examples thereof include organic sulfonic acid monomers, alkali metal salts such as sodium salts thereof, ammonium salts and the like. It is also possible to combine two or more of these.
架橋性単量体としては、メチレンビスアクリルアミド、エチレングリコールジ（メタ）アクリレート、Ｎ−メチロールアクリルアミド、トリアリルイソシアネート、ジビニルベンゼン等が挙げられる。これらを二種以上組み合わせることも可能である。添加量は全単量体に対し１質量％以下が好ましい。 Examples of the crosslinkable monomer include methylenebisacrylamide, ethylene glycol di (meth) acrylate, N-methylolacrylamide, triallylisocyanate, and divinylbenzene. It is also possible to combine two or more of these. The amount added is preferably 1% by mass or less based on all the monomers.
重合の際使用する界面活性剤は、分子内に親水性基と疎水性基を有する物質であり、ポリオキシアルキレンアルキルエーテル、ポリオキシエチレンソルビタンモノオレエート、ポリオキシエチレンソルビタントリオレエート等のポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンセチルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンラウリルエーテル等のポリオキシエチレンアルキルエーテル、ソルビタンモノオレエート、ソルビタンモノステアレート等のソルビタン脂肪酸エステル、ドデシル硫酸ナトリウム、ナフタレンスルホネート・ホルマリン縮合物、ペンタオキシエチレンオレイルアルコールエーテル等のポリオキシエチレン高級アルコールエーテル等が挙げられる。これらを二種以上組み合わせることも可能である。界面活性剤存在下、水中で重合することで単量体を微細分散させる効果が作用し、共重合が促進されるため本発明における紙力剤の紙力増強効果を発揮すると考えられる。界面活性剤の量が少ないと単量体を微細分散させる効果が小さく、多すぎると溶解時、使用時に発泡の原因となる。界面活性剤の添加量は全単量体に対して０．０１質量％〜５質量％であり、好ましくは０．０５質量％〜３質量％、更に好ましくは０．１質量％〜１質量％である。 The surfactant used in the polymerization is a substance having a hydrophilic group and a hydrophobic group in the molecule, and is a polyoxy such as polyoxyalkylene alkyl ether, polyoxyethylene sorbitan monooleate, and polyoxyethylene sorbitan trioleate. Polyoxyethylene alkyl ethers such as ethylene sorbitan fatty acid esters, polyoxyethylene cetyl ethers, polyoxyethylene oleyl ethers, and polyoxyethylene lauryl ethers, sorbitan fatty acid esters such as sorbitan monooleate and sorbitan monostearate, sodium dodecyl sulfate, naphthalene. Examples thereof include sulfonate-formalin condensate, polyoxyethylene higher alcohol ether such as pentaoxyethylene oleyl alcohol ether, and the like. It is also possible to combine two or more of these. It is considered that the effect of finely dispersing the monomers by polymerizing in water in the presence of a surfactant acts and the copolymerization is promoted, so that the paper strength enhancing effect of the paper strength agent in the present invention is exhibited. If the amount of the surfactant is small, the effect of finely dispersing the monomer is small, and if it is too large, it causes foaming during dissolution and use. The amount of the surfactant added is 0.01% by mass to 5% by mass, preferably 0.05% by mass to 3% by mass, and more preferably 0.1% by mass to 1% by mass with respect to all the monomers. Is.
本発明においては連鎖移動剤を使用することが好ましい。連鎖移動剤としては、アルキルメルカプタン類、チオグリコール酸及びそのエステル類、イソプロピルアルコール、アリルアルコール、アリルアミン、ジ亜リン酸ナトリウム等が挙げられる。また、メタリルスルホン酸ナトリウム、メタリルスルホン酸カリウム、メタリルスルホン酸アンモニウム等のメタリルスルホン酸塩等の単量体が挙げられる。 In the present invention, it is preferable to use a chain transfer agent. Examples of the chain transfer agent include alkyl mercaptans, thioglycolic acid and its esters, isopropyl alcohol, allyl alcohol, allylamine, sodium diphosphate and the like. In addition, monomers such as methallyl sulfonates such as sodium methallyl sulfonate, potassium metharyl sulfonate, and ammonium metharyl sulfonate can be mentioned.
重合開始剤としては、例えば過硫酸ナトリウム、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩、過酸化水素、過酸化ベンゾイル等の過酸化物等が挙げられる。これらは単独でも使用できるが、亜硫酸塩、亜硫酸水素塩等の還元剤と組合せてレドックス系重合開始剤としても使用できる。２、２’−アゾビス［２−（５−メチル−イミダゾリン−２−イル）プロパン］二塩酸塩、２、２’−アゾビス［２−（２−イミダゾリン−２−イル）プロパン］二塩酸塩、２、２’−アゾビス−２−アミジノプロパン二塩酸塩等のアゾ系の重合開始剤も使用可能である。重合開始剤の量は全単量体に対し０．０５質量％〜２質量％、好ましくは０．１〜１質量％である。 Examples of the polymerization initiator include persulfates such as sodium persulfate, potassium persulfate and ammonium persulfate, and peroxides such as hydrogen peroxide and benzoyl peroxide. These can be used alone, but can also be used as a redox-based polymerization initiator in combination with a reducing agent such as sulfite or hydrogen sulfite. 2,2'-Azobis [2- (5-methyl-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, Azo-based polymerization initiators such as 2,2'-azobis-2-amidinopropane dihydrochloride can also be used. The amount of the polymerization initiator is 0.05% by mass to 2% by mass, preferably 0.1 to 1% by mass, based on all the monomers.
重合反応は、通常温度３０℃〜１００℃、時間は０．５時間〜２０時間で行う。得られる高分子の濃度は通常５〜５０質量％である。 The polymerization reaction is usually carried out at a temperature of 30 ° C. to 100 ° C. and a time of 0.5 to 20 hours. The concentration of the obtained polymer is usually 5 to 50% by mass.
得られた高分子は、高分子１質量％水溶液の粘度が５〜５０ｍＰａ・ｓであることが好ましい。粘度はＢ型粘度計で回転数６０ｒｐｍ、２５℃で測定したものである。粘度がこれより小さいと紙力増強効果が不十分となる。また、粘度がこれより大きいと溶解性が低下し取扱いが困難となる。Ｂ型粘度計として、東機産業株式会社製Ｂ８Ｍ型、ＴＶＢ−１０Ｍ型等の汎用品が適宜に使用される。粘度が１００ｍＰａ・ｓ以下の場合は、１号ローターを用いる。 The obtained polymer preferably has a viscosity of a 1% by mass aqueous solution of the polymer of 5 to 50 mPa · s. The viscosity was measured with a B-type viscometer at a rotation speed of 60 rpm and 25 ° C. If the viscosity is smaller than this, the paper strength enhancing effect becomes insufficient. Further, if the viscosity is larger than this, the solubility is lowered and handling becomes difficult. As the B-type viscometer, general-purpose products such as B8M type and TVB-10M type manufactured by Toki Sangyo Co., Ltd. are appropriately used. When the viscosity is 100 mPa · s or less, the No. 1 rotor is used.
本発明における紙力剤を使用する紙の種類としては、新聞用紙、上質印刷用紙、中質印刷用紙、グラビア印刷用紙、ＰＰＣ用紙、塗工原紙、微塗工紙、包装用紙、ライナーや中芯原紙の板紙等が挙げられる。添加する場所としては、抄紙工程におけるパルプスラリー中あるいは湿紙上などのウエットエンド部に添加される。添加率としては、パルプ乾燥固形分に対して、固形分で０．０５〜１０質量％であり、好ましくは０．１〜５質量％である。又、その他の紙力剤やサイズ剤、硫酸バンド、凝結剤、歩留向上剤、濾水性向上剤等の製紙用薬品と併用することができる。 The types of paper that use the paper strength agent in the present invention include newspaper paper, high-quality printing paper, medium-quality printing paper, gravure printing paper, PPC paper, coated base paper, finely coated paper, wrapping paper, liner and core. Examples include board paper for base paper. As a place to add, it is added to a wet end portion such as in a pulp slurry or on wet paper in a papermaking process. The addition rate is 0.05 to 10% by mass, preferably 0.1 to 5% by mass, based on the dry pulp content. Further, it can be used in combination with other paper chemicals such as a paper strength agent, a sizing agent, a sulfuric acid band, a coagulant, a yield improver, and a drainage improver.
以下、実施例によって本発明をさらに詳しく説明するが、本発明はその要旨を超えない限り、以下の実施例に制約されるものではない。なお、粘度はＢ型粘度計を使用し、回転数６０ｒｐｍ、２５℃で測定した。 Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded. The viscosity was measured using a B-type viscometer at a rotation speed of 60 rpm and 25 ° C.
（実施例１）
５００ｍＬの４つ口フラスコに、ドデシルアクリレート０．５ｇ、ジメチルアミノエチルメタクリレート７．５ｇ、３５質量％塩酸５．０ｇ、５０質量％アクリルアミド８４．３ｇ、脱塩水１５３．０ｇ、ドデシル硫酸ナトリウム０．０５ｇ、メタリルスルホン酸ナトリウム０．３０ｇ、２、２’−アゾビス［２−（２−イミダゾリン−２−イル）プロパン］二塩酸塩（和光純薬工業製ＶＡ−０４４）０．１ｇを仕込み２００ｒｐｍで撹拌しながら窒素ガスを通じた。３０分後、５０℃まで昇温し、３時間保持した。その後７０℃で２時間保持した。その後冷却し、高分子水溶液を得た。得られた高分子の１質量％水溶液の粘度は、２５．５ｍＰａ・ｓであった。この結果を表１に示す。
(Example 1)
Dodecyl acrylate 0.5 g, dimethylaminoethyl methacrylate 7.5 g, 35 mass% hydrochloric acid 5.0 g, 50 mass% acrylamide 84.3 g, desalted water 153.0 g, sodium dodecyl sulfate 0.05 g in a 500 mL four-necked flask. , Sodium methallyl sulfonate 0.30 g, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (VA-044 manufactured by Wako Pure Chemical Industries, Ltd.) 0.1 g was charged at 200 rpm. Nitrogen gas was passed through with stirring. After 30 minutes, the temperature was raised to 50 ° C. and held for 3 hours. Then, it was kept at 70 degreeC for 2 hours. Then, it cooled and obtained the polymer aqueous solution. The viscosity of the 1% by mass aqueous solution of the obtained polymer was 25.5 mPa · s. The results are shown in Table 1.
（実施例２）
５００ｍＬの４つ口フラスコに、ドデシルアクリレート１．０ｇ、ジメチルアミノエチルメタクリレート７．５ｇ、３５質量％塩酸５．０ｇ、５０質量％アクリルアミド８３．３ｇ、脱塩水１５３．５ｇ、ナフタレンスルホネート・ホルマリン縮合物（センカ製ＷＳ−１００）０．１ｇ、メタリルスルホン酸ナトリウム０．３０ｇ、ＶＡ−０４４（和光純薬工業製）０．１ｇを仕込み２００ｒｐｍで撹拌しながら窒素ガスを通じた。３０分後、５０℃まで昇温し、３時間保持した。その後７０℃で２時間保持した。その後冷却し、高分子水溶液を得た。得られた高分子の１質量％水溶液の粘度は、１７．５ｍＰａ・ｓであった。この結果を表１に示す。
(Example 2)
Dodecyl acrylate 1.0 g, dimethylaminoethyl methacrylate 7.5 g, 35 mass% hydrochloric acid 5.0 g, 50 mass% acrylamide 83.3 g, desalted water 153.5 g, naphthalene sulfonate formalin condensate in a 500 mL four-necked flask. 0.1 g of (WS-100 manufactured by Senka), 0.30 g of sodium metalylsulfonate, and 0.1 g of VA-044 (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and passed through nitrogen gas while stirring at 200 rpm. After 30 minutes, the temperature was raised to 50 ° C. and held for 3 hours. Then, it was kept at 70 degreeC for 2 hours. Then, it cooled and obtained the polymer aqueous solution. The viscosity of the 1% by mass aqueous solution of the obtained polymer was 17.5 mPa · s. The results are shown in Table 1.
（実施例３）
５００ｍＬの４つ口フラスコに、ドデシルアクリレート１．０ｇ、ジメチルアミノエチルメタクリレート７．５ｇ、３５質量％塩酸５．０ｇ、５０質量％アクリルアミド８３．０ｇ、脱塩水１５３．５ｇ、ポリオキシアルキレンアルキルエーテル（三洋化成工業製ＣＬ−１００）０．１ｇ、メタリルスルホン酸ナトリウム０．３０ｇ、ＶＡ−０４４（和光純薬工業製）０．１ｇを仕込み２００ｒｐｍで撹拌しながら窒素ガスを通じた。３０分後、５０℃まで昇温し、３時間保持した。その後７０℃で２時間保持した。その後冷却し、高分子水溶液を得た。得られた高分子の１質量％水溶液の粘度は、２４．０ｍＰａ・ｓであった。この結果を表１に示す。
(Example 3)
In a 500 mL four-necked flask, 1.0 g of dodecyl acrylate, 7.5 g of dimethylaminoethyl methacrylate, 5.0 g of 35 mass% hydrochloric acid, 83.0 g of 50 mass% acrylamide, 153.5 g of desalted water, and polyoxyalkylene alkyl ether ( 0.1 g of CL-100 manufactured by Sanyo Kasei Kogyo, 0.30 g of sodium metallyl sulfonate, and 0.1 g of VA-044 (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and passed through nitrogen gas while stirring at 200 rpm. After 30 minutes, the temperature was raised to 50 ° C. and held for 3 hours. Then, it was kept at 70 degreeC for 2 hours. Then, it cooled and obtained the polymer aqueous solution. The viscosity of the 1% by mass aqueous solution of the obtained polymer was 24.0 mPa · s. The results are shown in Table 1.
（実施例４）
５００ｍＬの４つ口フラスコに、ドデシルアクリレート１．０ｇ、スチレン１．０ｇ、ジメチルアミノエチルメタクリレート７．５ｇ、３５質量％塩酸５．０ｇ、５０質量％アクリルアミド８１．０ｇ、脱塩水１５４．５ｇ、ポリオキシアルキレンアルキルエーテル（三洋化成工業製ＣＬ−１００）０．１０ｇ、メタリルスルホン酸ナトリウム０．３０ｇ、ＶＡ−０４４（和光純薬工業製）０．１ｇを仕込み２００ｒｐｍで撹拌しながら窒素ガスを通じた。３０分後、５０℃まで昇温し、３時間保持した。その後７０℃で２時間保持した。その後冷却し、高分子水溶液を得た。得られた高分子の１質量％水溶液の粘度は、２８．０ｍＰａ・ｓであった。この結果を表１に示す。
(Example 4)
Dodecyl acrylate 1.0 g, styrene 1.0 g, dimethylaminoethyl methacrylate 7.5 g, 35 mass% hydrochloric acid 5.0 g, 50 mass% acrylamide 81.0 g, desalted water 154.5 g, poly in a 500 mL four-necked flask. 0.10 g of oxyalkylene alkyl ether (CL-100 manufactured by Sanyo Kasei Kogyo), 0.30 g of sodium metalylsulfonate, and 0.1 g of VA-044 (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and passed through nitrogen gas while stirring at 200 rpm. .. After 30 minutes, the temperature was raised to 50 ° C. and held for 3 hours. Then, it was kept at 70 degreeC for 2 hours. Then, it cooled and obtained the polymer aqueous solution. The viscosity of the 1% by mass aqueous solution of the obtained polymer was 28.0 mPa · s. The results are shown in Table 1.
（実施例５）
５００ｍＬの４つ口フラスコに、ドデシルアクリレート１．０ｇ、２−エチルへキシルアクリレート１．０ｇ、ジメチルアミノエチルメタクリレート７．５ｇ、３５質量％塩酸５．０ｇ、５０質量％アクリルアミド８１．２ｇ、脱塩水１５４．５ｇ、ポリオキシアルキレンアルキルエーテル（三洋化成工業製ＣＬ−１００）０．１０ｇ、メタリルスルホン酸ナトリウム０．３０ｇ、ＶＡ−０４４（和光純薬工業製）０．１ｇを仕込み２００ｒｐｍで撹拌しながら窒素ガスを通じた。３０分後、５０℃まで昇温し、３時間保持した。その後７０℃で２時間保持した。その後冷却し、高分子水溶液を得た。得られた高分子の１質量％水溶液の粘度は、１８．０ｍＰａ・ｓであった。この結果を表１に示す。
(Example 5)
Dodecyl acrylate 1.0 g, 2-ethylhexyl acrylate 1.0 g, dimethylaminoethyl methacrylate 7.5 g, 35 mass% hydrochloric acid 5.0 g, 50 mass% acrylamide 81.2 g, desalted water in a 500 mL four-necked flask. 154.5 g, 0.10 g of polyoxyalkylene alkyl ether (CL-100 manufactured by Sanyo Kasei Kogyo), 0.30 g of sodium metalylsulfonate, 0.1 g of VA-044 (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and stirred at 200 rpm. While passing through nitrogen gas. After 30 minutes, the temperature was raised to 50 ° C. and held for 3 hours. Then, it was kept at 70 degreeC for 2 hours. Then, it cooled and obtained the polymer aqueous solution. The viscosity of the 1% by mass aqueous solution of the obtained polymer was 18.0 mPa · s. The results are shown in Table 1.
（実施例６）
５００ｍＬの４つ口フラスコに、ドデシルアクリレート１．０ｇ、２−エチルへキシルアクリレート１．０ｇ、ジメチルアミノエチルメタクリレート７．５ｇ、３５質量％塩酸５．０ｇ、５０質量％アクリルアミド８１．２ｇ、脱塩水１５４．５ｇ、ポリオキシアルキレンアルキルエーテル（三洋化成工業製ＣＬ−１００）０．５０ｇ、メタリルスルホン酸ナトリウム０．３０ｇ、ＶＡ−０４４（和光純薬工業製）０．１ｇを仕込み２００ｒｐｍで撹拌しながら窒素ガスを通じた。３０分後、５０℃まで昇温し、３時間保持した。その後７０℃で２時間保持した。その後冷却し、高分子水溶液を得た。得られた高分子の１質量％水溶液の粘度は、１６．０ｍＰａ・ｓであった。この結果を表１に示す。
(Example 6)
Dodecyl acrylate 1.0 g, 2-ethylhexyl acrylate 1.0 g, dimethylaminoethyl methacrylate 7.5 g, 35 mass% hydrochloric acid 5.0 g, 50 mass% acrylamide 81.2 g, desalted water in a 500 mL four-necked flask. 154.5 g, 0.50 g of polyoxyalkylene alkyl ether (CL-100 manufactured by Sanyo Kasei Kogyo), 0.30 g of sodium metalylsulfonate, 0.1 g of VA-044 (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and stirred at 200 rpm. While passing through nitrogen gas. After 30 minutes, the temperature was raised to 50 ° C. and held for 3 hours. Then, it was kept at 70 degreeC for 2 hours. Then, it cooled and obtained the polymer aqueous solution. The viscosity of the 1% by mass aqueous solution of the obtained polymer was 16.0 mPa · s. The results are shown in Table 1.
（実施例７）
５００ｍＬの４つ口フラスコに、ドデシルアクリレート１．０ｇ、ジメチルアミノエチルメタクリレート７．５ｇ、３５質量％塩酸５．０ｇ、５０質量％アクリルアミド８３．１ｇ、８０質量％アクリル酸１．３ｇ、脱塩水１５３．５ｇ、ポリオキシアルキレンアルキルエーテル（三洋化成工業製ＣＬ−１００）０．１０ｇ、メタリルスルホン酸ナトリウム０．３０ｇ、ＶＡ−０４４（和光純薬工業製）０．１ｇを仕込み２００ｒｐｍで撹拌しながら窒素ガスを通じた。３０分後、５０℃まで昇温し、３時間保持した。その後７０℃で２時間保持した。その後冷却し、高分子水溶液を得た。得られた高分子の１質量％水溶液の粘度は、１６．０ｍＰａ・ｓであった。この結果を表１に示す。
(Example 7)
Dodecyl acrylate 1.0 g, dimethylaminoethyl methacrylate 7.5 g, 35 mass% hydrochloric acid 5.0 g, 50 mass% acrylamide 83.1 g, 80 mass% acrylic acid 1.3 g, desalted water 153 in a 500 mL four-necked flask. .5 g, polyoxyalkylene alkyl ether (CL-100 manufactured by Sanyo Kasei Kogyo) 0.10 g, sodium metalylsulfonate 0.30 g, VA-044 (manufactured by Wako Pure Chemical Industries, Ltd.) 0.1 g were charged and stirred at 200 rpm. Through nitrogen gas. After 30 minutes, the temperature was raised to 50 ° C. and held for 3 hours. Then, it was kept at 70 degreeC for 2 hours. Then, it cooled and obtained the polymer aqueous solution. The viscosity of the 1% by mass aqueous solution of the obtained polymer was 16.0 mPa · s. The results are shown in Table 1.
（実施例８）
５００ｍＬの４つ口フラスコに、ドデシルアクリレート０．２ｇ、ジメチルアミノエチルメタクリレート７．５ｇ、３５質量％塩酸５．０ｇ、５０質量％アクリルアミド８４．５ｇ、脱塩水１５２．８ｇ、ポリオキシアルキレンアルキルエーテル（三洋化成工業製ＣＬ−１００）０．１０ｇ、メタリルスルホン酸ナトリウム０．３０ｇ、ＶＡ−０４４（和光純薬工業製）０．１ｇを仕込み２００ｒｐｍで撹拌しながら窒素ガスを通じた。３０分後、５０℃まで昇温し、３時間保持した。その後７０℃で２時間保持した。その後冷却し、高分子水溶液を得た。得られた高分子の１質量％水溶液の粘度は、１９．５ｍＰａ・ｓであった。この結果を表１に示す。
(Example 8)
In a 500 mL four-necked flask, 0.2 g of dodecyl acrylate, 7.5 g of dimethylaminoethyl methacrylate, 5.0 g of 35 mass% hydrochloric acid, 84.5 g of 50 mass% acrylamide, 152.8 g of desalted water, and polyoxyalkylene alkyl ether ( 0.10 g of CL-100 manufactured by Sanyo Kasei Kogyo, 0.30 g of sodium metallyl sulfonate, and 0.1 g of VA-044 (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and passed through nitrogen gas while stirring at 200 rpm. After 30 minutes, the temperature was raised to 50 ° C. and held for 3 hours. Then, it was kept at 70 degreeC for 2 hours. Then, it cooled and obtained the polymer aqueous solution. The viscosity of the 1% by mass aqueous solution of the obtained polymer was 19.5 mPa · s. The results are shown in Table 1.
（実施例９）
５００ｍＬの４つ口フラスコに、オクダデシルメタクリレート０．０５ｇ、ジメチルアミノエチルメタクリレート７．５ｇ、３５質量％塩酸５．０ｇ、５０質量％アクリルアミド８４．９ｇ、脱塩水１５２．６ｇ、ポリオキシアルキレンアルキルエーテル（三洋化成工業製ＣＬ−１００）０．１０ｇ、メタリルスルホン酸ナトリウム０．３０ｇ、ＶＡ−０４４（和光純薬工業製）０．１ｇを仕込み２００ｒｐｍで撹拌しながら窒素ガスを通じた。３０分後、５０℃まで昇温し、３時間保持した。その後７０℃で２時間保持した。その後冷却し、高分子水溶液を得た。得られた高分子の１質量％水溶液の粘度は、２２．５ｍＰａ・ｓであった。この結果を表１に示す。
(Example 9)
In a 500 mL four-necked flask, 0.05 g of octadecil methacrylate, 7.5 g of dimethylaminoethyl methacrylate, 5.0 g of 35 mass% hydrochloric acid, 84.9 g of 50 mass% acrylamide, 152.6 g of desalted water, and polyoxyalkylene alkyl ether. (CL-100 manufactured by Sanyo Kasei Kogyo Co., Ltd.) 0.10 g, sodium metallyl sulfonate 0.30 g, and VA-044 (manufactured by Wako Pure Chemical Industries, Ltd.) 0.1 g were charged and passed through nitrogen gas while stirring at 200 rpm. After 30 minutes, the temperature was raised to 50 ° C. and held for 3 hours. Then, it was kept at 70 degreeC for 2 hours. Then, it cooled and obtained the polymer aqueous solution. The viscosity of the 1% by mass aqueous solution of the obtained polymer was 22.5 mPa · s. The results are shown in Table 1.
（実施例１０）
５００ｍＬの４つ口フラスコに、ドデシルアクリレート１．０ｇ、ジメチルアミノエチルメタクリレート７．５ｇ、３５質量％塩酸５．０ｇ、５０質量％アクリルアミド８３．１ｇ、メチレンビスアクリルアミド０．０５１ｇ、脱塩水１５３．５ｇ、ポリオキシアルキレンアルキルエーテル（三洋化成工業製ＣＬ−１００）０．１０ｇ、メタリルスルホン酸ナトリウム０．７５ｇ、ＶＡ−０４４（和光純薬工業製）０．１ｇを仕込み２００ｒｐｍで撹拌しながら窒素ガスを通じた。３０分後、５０℃まで昇温し、３時間保持した。その後７０℃で２時間保持した。その後冷却し、高分子水溶液を得た。得られた高分子の１質量％水溶液の粘度は、３０．５ｍＰａ・ｓであった。この結果を表１に示す。
(Example 10)
Dodecyl acrylate 1.0 g, dimethylaminoethyl methacrylate 7.5 g, 35 mass% hydrochloric acid 5.0 g, 50 mass% acrylamide 83.1 g, methylenebis acrylamide 0.051 g, desalted water 153.5 g in a 500 mL four-necked flask. , Polyoxyalkylene alkyl ether (CL-100 manufactured by Sanyo Kasei Kogyo Co., Ltd.) 0.10 g, sodium metallyl sulfonate 0.75 g, VA-044 (manufactured by Wako Pure Chemical Industries, Ltd.) 0.1 g, and nitrogen gas while stirring at 200 rpm. Through. After 30 minutes, the temperature was raised to 50 ° C. and held for 3 hours. Then, it was kept at 70 degreeC for 2 hours. Then, it cooled and obtained the polymer aqueous solution. The viscosity of the 1% by mass aqueous solution of the obtained polymer was 30.5 mPa · s. The results are shown in Table 1.
（実施例１１）
５００ｍＬの４つ口フラスコに、ブチルアクリレート５．０ｇ、ジメチルアミノエチルメタクリレート７．５ｇ、３５質量％塩酸５．０ｇ、５０質量％アクリルアミド７５．１ｇ、脱塩水１５７．５ｇ、ポリオキシアルキレンアルキルエーテル（三洋化成工業製ＣＬ−１００）０．１０ｇ、メタリルスルホン酸ナトリウム０．３０ｇ、ＶＡ−０４４（和光純薬工業製）０．１ｇを仕込み２００ｒｐｍで撹拌しながら窒素ガスを通じた。３０分後、５０℃まで昇温し、３時間保持した。その後７０℃で２時間保持した。その後冷却し、高分子水溶液を得た。得られた高分子の１質量％水溶液の粘度は、２６．０ｍＰａ・ｓであった。この結果を表１に示す。
(Example 11)
Butyl acrylate 5.0 g, dimethylaminoethyl methacrylate 7.5 g, 35 mass% hydrochloric acid 5.0 g, 50 mass% acrylamide 75.1 g, desalted water 157.5 g, polyoxyalkylene alkyl ether (in a 500 mL four-necked flask) 0.10 g of CL-100 manufactured by Sanyo Kasei Kogyo, 0.30 g of sodium metallyl sulfonate, and 0.1 g of VA-044 (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and passed through nitrogen gas while stirring at 200 rpm. After 30 minutes, the temperature was raised to 50 ° C. and held for 3 hours. Then, it was kept at 70 degreeC for 2 hours. Then, it cooled and obtained the polymer aqueous solution. The viscosity of the 1% by mass aqueous solution of the obtained polymer was 26.0 mPa · s. The results are shown in Table 1.
（実施例１２）
５００ｍＬの４つ口フラスコに、ドデシルアクリレート１．０ｇ、スチレン１．０ｇ、ジメチルアミノエチルメタクリレート７．５ｇ、３５質量％塩酸５．０ｇ、５０質量％アクリルアミド８１．０ｇ、脱塩水１５４．５ｇ、ポリオキシエチレンソルビタントリオレエート（和光純薬工業製ＴＷ−８５）０．１０ｇ、メタリルスルホン酸ナトリウム０．３０ｇ、ＶＡ−０４４（和光純薬工業製）０．１ｇを仕込み２００ｒｐｍで撹拌しながら窒素ガスを通じた。３０分後、５０℃まで昇温し、３時間保持した。その後７０℃で２時間保持した。その後冷却し、高分子水溶液を得た。得られた高分子の１質量％水溶液の粘度は、１７．５ｍＰａ・ｓであった。この結果を表１に示す。
(Example 12)
Dodecyl acrylate 1.0 g, styrene 1.0 g, dimethylaminoethyl methacrylate 7.5 g, 35 mass% hydrochloric acid 5.0 g, 50 mass% acrylamide 81.0 g, desalted water 154.5 g, poly in a 500 mL four-necked flask. Oxyethylene sorbitan trioleate (TW-85 manufactured by Wako Pure Chemical Industries, Ltd.) 0.10 g, sodium metallyl sulfonate 0.30 g, VA-044 (manufactured by Wako Pure Chemical Industries, Ltd.) 0.1 g were charged and nitrogen gas was stirred at 200 rpm. Through. After 30 minutes, the temperature was raised to 50 ° C. and held for 3 hours. Then, it was kept at 70 degreeC for 2 hours. Then, it cooled and obtained the polymer aqueous solution. The viscosity of the 1% by mass aqueous solution of the obtained polymer was 17.5 mPa · s. The results are shown in Table 1.
（比較例１）
５００ｍＬの４つ口フラスコに、ジメチルアミノエチルメタクリレート７．５ｇ、３５質量％塩酸５．０ｇ、５０質量％アクリルアミド８５．０ｇ、脱塩水１５２．５ｇ、メタリルスルホン酸ナトリウム０．２５ｇ、ＶＡ−０４４（和光純薬工業製）０．１ｇを仕込み２００ｒｐｍで撹拌しながら窒素ガスを通じた。３０分後、５０℃まで昇温し、３時間保持した。その後７０℃で２時間保持した。その後冷却し、透明の高分子水溶液を得た。得られた高分子の１質量％水溶液の粘度は、２２．５ｍＰａ・ｓであった。この結果を表１に示す。
(Comparative Example 1)
In a 500 mL four-necked flask, 7.5 g of dimethylaminoethyl methacrylate, 5.0 g of 35 mass% hydrochloric acid, 85.0 g of 50 mass% acrylamide, 152.5 g of desalted water, 0.25 g of sodium metalylsulfonate, VA-044. 0.1 g (manufactured by Wako Pure Chemical Industries, Ltd.) was charged and passed through nitrogen gas while stirring at 200 rpm. After 30 minutes, the temperature was raised to 50 ° C. and held for 3 hours. Then, it was kept at 70 degreeC for 2 hours. After that, it was cooled to obtain a transparent aqueous polymer solution. The viscosity of the 1% by mass aqueous solution of the obtained polymer was 22.5 mPa · s. The results are shown in Table 1.
（比較例２）
５００ｍＬの４つ口フラスコに、ドデシルアクリレート０．５０ｇ、ジメチルアミノエチルメタクリレート７．５ｇ、３５質量％塩酸５．０ｇ、５０質量％アクリルアミド８４．０ｇ、脱塩水１５３．０ｇ、メタリルスルホン酸ナトリウム０．３０ｇ、ＶＡ−０４４（和光純薬工業製）０．１ｇを仕込み２００ｒｐｍで撹拌しながら窒素ガスを通じた。３０分後、５０℃まで昇温し、３時間保持した。その後７０℃で２時間保持した。その後冷却し、透明の高分子水溶液を得た。得られた高分子の１質量％水溶液の粘度は、２２．５ｍＰａ・ｓであった。この結果を表１に示す。
(Comparative Example 2)
In a 500 mL four-necked flask, 0.50 g of dodecyl acrylate, 7.5 g of dimethylaminoethyl methacrylate, 5.0 g of 35 mass% hydrochloric acid, 84.0 g of 50 mass% acrylamide, 153.0 g of desalted water, and 0 sodium methallyl sulfonate. .30 g and 0.1 g of VA-044 (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and passed through nitrogen gas while stirring at 200 rpm. After 30 minutes, the temperature was raised to 50 ° C. and held for 3 hours. Then, it was kept at 70 degreeC for 2 hours. After that, it was cooled to obtain a transparent aqueous polymer solution. The viscosity of the 1% by mass aqueous solution of the obtained polymer was 22.5 mPa · s. The results are shown in Table 1.
（比較例３）
５００ｍＬの４つ口フラスコに、ドデシルアクリレート１．０ｇ、ジメチルアミノエチルメタクリレート７．５ｇ、３５質量％塩酸５．０ｇ、５０質量％アクリルアミド８３．０ｇ、脱塩水１５３．５ｇ、メタリルスルホン酸ナトリウム０．３０ｇ、ＶＡ−０４４（和光純薬工業製）０．１ｇを仕込み２００ｒｐｍで撹拌しながら窒素ガスを通じた。３０分後、５０℃まで昇温し、３時間保持した。その後７０℃で２時間保持した。その後冷却し、透明の高分子水溶液を得た。得られた高分子の１質量％水溶液の粘度は、１８．５ｍＰａ・ｓであった。この結果を表１に示す。
(Comparative Example 3)
In a 500 mL four-necked flask, 1.0 g of dodecyl acrylate, 7.5 g of dimethylaminoethyl methacrylate, 5.0 g of 35 mass% hydrochloric acid, 83.0 g of 50 mass% acrylamide, 153.5 g of desalted water, and 0 sodium methallyl sulfonate. .30 g and 0.1 g of VA-044 (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and passed through nitrogen gas while stirring at 200 rpm. After 30 minutes, the temperature was raised to 50 ° C. and held for 3 hours. Then, it was kept at 70 degreeC for 2 hours. After that, it was cooled to obtain a transparent aqueous polymer solution. The viscosity of the 1% by mass aqueous solution of the obtained polymer was 18.5 mPa · s. The results are shown in Table 1.
（比較例４）
５００ｍＬの４つ口フラスコに、ドデシルアクリレート１．０ｇ、スチレン１．０ｇ、ジメチルアミノエチルメタクリレート７．５ｇ、３５質量％塩酸５．０ｇ、５０質量％アクリルアミド８１．０ｇ、脱塩水１５４．５ｇ、メタリルスルホン酸ナトリウム０．３０ｇ、ＶＡ−０４４（和光純薬工業製）０．１ｇを仕込み２００ｒｐｍで撹拌しながら窒素ガスを通じた。３０分後、５０℃まで昇温し、３時間保持した。その後７０℃で２時間保持した。その後冷却し、高分子水溶液を得た。得られた高分子にポリオキシエチレンソルビタントリオレエート（和光純薬工業製ＴＷ−８５）０．１０ｇを混合した。得られた高分子の１質量％水溶液の粘度は、１７．５ｍＰａ・ｓであった。この結果を表１に示す。
(Comparative Example 4)
Dodecyl acrylate 1.0 g, styrene 1.0 g, dimethylaminoethyl methacrylate 7.5 g, 35 mass% hydrochloric acid 5.0 g, 50 mass% acrylamide 81.0 g, desalted water 154.5 g, meta in a 500 mL four-necked flask. 0.30 g of sodium lyl sulfonate and 0.1 g of VA-044 (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and passed through nitrogen gas while stirring at 200 rpm. After 30 minutes, the temperature was raised to 50 ° C. and held for 3 hours. Then, it was kept at 70 degreeC for 2 hours. Then, it cooled and obtained the polymer aqueous solution. 0.10 g of polyoxyethylene sorbitan trioleate (TW-85 manufactured by Wako Pure Chemical Industries, Ltd.) was mixed with the obtained polymer. The viscosity of the 1% by mass aqueous solution of the obtained polymer was 17.5 mPa · s. The results are shown in Table 1.
（表１）
疎水性単量体；ＤＤＡ：ドデシルアクリレート、Ｓｔ：スチレン、２ＥＨＡ：２−エチルへキシルアクリレート、ＯＤＭＡ：オクダデシルメタクリレート、ＢＭＡ：ブチルメタクリレート
カチオン性単量体；ＤＭＭ：ジメチルアミノエチルメタクリレート
ＡＡＭ；アクリルアミド
その他の単量体；ＡＡＣ：アクリル酸、ＭＢＡＡ：メチレンビスアクリルアミド
界面活性剤；ＳＤＳ：ドデシル硫酸ナトリウム、ＷＳ−１００：ナフタレンスルホネート・ホルマリン縮合物、ＣＬ−１００：ポリオキシアルキレンアルキルエーテル、ＴＷ−８５：ポリオキシエチレンソルビタントリオレエート
(Table 1)
Hydrophobic Monomer; DDA: Dodecyl Acrylate, St: Styrene, 2EHA: 2-Ethylhexyl Acrylate, ODMA: Okudadecyl Methacrylate, BMA: Butyl Methacrylate Cationic Monomer; Monomer; AAC: Acrylic acid, MBAA: Methylenebisacrylamide surfactant; SDS: Sodium dodecyl sulfate, WS-100: Naphthalene sulfonate formalin condensate, CL-100: Polyoxyalkylene alkyl ether, TW-85: Polyoxyethylene sorbitan trioleate
（試験例１）
本発明における紙力剤の紙質測定試験を実施した。先ず、ＬＢＫＰをナイアガラ式ビーターで叩解し、カナディアンスタンダードフリーネス３４５ｍＬに調整した。パルプ濃度１質量％のスラリー（ｐＨ６．４、ＥＣ１７．１ｍＳ／ｍ）５００ｍＬに対し、パルプ固形分に対し０．５質量％あるいは１質量％となるように表１の実施例の高分子試料あるいは比較例の高分子試料、比較試料として市販の紙力剤（両性アクリルアミド系水溶性高分子、濃度２０質量％）を添加し、８００ｒｐｍで１分間撹拌後、タッピシートマシンにて抄紙（８０メッシュワイヤー）し、続いて圧力４１０ｋＰａで５分間プレスし、さらに回転型乾燥機を使用し１０５℃で乾燥した。温度２３℃、湿度５０％の条件下で２４時間調湿して、坪量８０ｇ／ｃｍ２の紙を得た。得られた紙の内部結合強さ（熊谷理機工業製インターナルボンドテスター）、ＪＩＳ Ｐ８１１２に準じて破裂強度を測定し、表２の結果を得た。実施試験例では比較試験例の紙に比較して紙力の向上を示した。
(Test Example 1)
The paper quality measurement test of the paper strength agent in the present invention was carried out. First, LBKP was beaten with a Niagara beater to adjust to Canadian Standard Freeness 345 mL. The polymer sample of the example in Table 1 or 1% by mass with respect to 500 mL of a slurry (pH 6.4, EC17.1 mS / m) having a pulp concentration of 1% by mass, so as to be 0.5% by mass or 1% by mass with respect to the pulp solid content. A polymer sample of a comparative example and a commercially available paper strength agent (amphoteric acrylamide-based water-soluble polymer, concentration 20% by mass) were added as a comparative sample, and after stirring at 800 rpm for 1 minute, papermaking (80 mesh wire) was performed using a tappi sheet machine. ), Then pressed at a pressure of 410 kPa for 5 minutes, and further dried at 105 ° C. using a rotary dryer. The humidity was adjusted for 24 hours under the conditions of a temperature of 23 ° C. and a humidity of 50% to obtain a paper having a basis weight of 80 g / cm 2 . The internal bond strength of the obtained paper (internal bond tester manufactured by Kumagai Riki Kogyo) and the burst strength were measured according to JIS P8112, and the results shown in Table 2 were obtained. In the test example, the paper strength was improved as compared with the paper in the comparative test example.
（表２）
(Table 2)
（試験例２）
試験例１と同様に調製（叩解度３６０ｍＬ）したパルプ濃度１質量％のスラリー５００ｍＬに対し、パルプ固形分に対し０．５質量％あるいは１質量％となるように表１の実施例の高分子試料あるいは比較例の高分子試料、比較試料を添加し、８００ｒｐｍで１分間撹拌後、タッピシートマシンにて抄紙（８０メッシュワイヤー）し、続いて圧力４１０ｋＰａで５分間プレスし、さらに回転型乾燥機を使用し１０５℃で乾燥した。温度２３℃、湿度５０％の条件下で２４時間調湿して、坪量８０ｇ／ｃｍ２の紙を得た。得られた紙の内部結合強さ（熊谷理機工業製インターナルボンドテスター）、ＪＩＳ Ｐ８１１２に準じて破裂強度を測定し、表３の結果を得た。実施試験例では比較試験例の紙に比較して紙力の向上を示した。
(Test Example 2)
The polymer of the example of Table 1 was prepared in the same manner as in Test Example 1 (beating degree 360 mL) so that the content was 0.5% by mass or 1% by mass with respect to the pulp solid content with respect to 500 mL of the slurry having a pulp concentration of 1% by mass. A sample or a polymer sample of a comparative example or a comparative sample is added, and after stirring at 800 rpm for 1 minute, papermaking (80 mesh wire) is performed with a tappy sheet machine, and then pressed at a pressure of 410 kPa for 5 minutes, and then a rotary dryer. Was dried at 105 ° C. The humidity was adjusted for 24 hours under the conditions of a temperature of 23 ° C. and a humidity of 50% to obtain a paper having a basis weight of 80 g / cm 2 . The internal bond strength of the obtained paper (internal bond tester manufactured by Kumagai Riki Kogyo) and the burst strength were measured according to JIS P8112, and the results shown in Table 3 were obtained. In the test example, the paper strength was improved as compared with the paper in the comparative test example.
（表３）
(Table 3)
（試験例３）
試験例１と同様に調製（叩解度３６０ｍＬ）したパルプ濃度１質量％のスラリー５００ｍＬに対し、パルプ固形分に対し０．５質量％あるいは１質量％となるように表１の実施例の高分子試料あるいは比較例の高分子試料、比較試料を添加し、８００ｒｐｍで１分間撹拌後、タッピシートマシンにて抄紙（８０メッシュワイヤー）し、続いて圧力４１０ｋＰａで５分間プレスし、さらに回転型乾燥機を使用し１０５℃で乾燥した。温度２３℃、湿度５０％の条件下で２４時間調湿して、坪量８０ｇ／ｃｍ２の紙を得た。得られた紙の内部結合強さ（熊谷理機工業製インターナルボンドテスター）、ＪＩＳ Ｐ８１１２に準じて破裂強度を測定し、表４の結果を得た。実施試験例では比較試験例の紙に比較して紙力の向上を示した。
(Test Example 3)
The polymer of the example of Table 1 was prepared in the same manner as in Test Example 1 (beating degree 360 mL) so that the content was 0.5% by mass or 1% by mass with respect to the pulp solid content with respect to 500 mL of the slurry having a pulp concentration of 1% by mass. A sample or a polymer sample of a comparative example or a comparative sample is added, and after stirring at 800 rpm for 1 minute, papermaking (80 mesh wire) is performed with a tappy sheet machine, and then pressed at a pressure of 410 kPa for 5 minutes, and then a rotary dryer. Was dried at 105 ° C. The humidity was adjusted for 24 hours under the conditions of a temperature of 23 ° C. and a humidity of 50% to obtain a paper having a basis weight of 80 g / cm 2 . The internal bond strength of the obtained paper (internal bond tester manufactured by Kumagai Riki Kogyo) and the burst strength were measured according to JIS P8112, and the results shown in Table 4 were obtained. In the test example, the paper strength was improved as compared with the paper in the comparative test example.
（表４）
(Table 4)
（試験例４）
試験例１と同様に調製（叩解度３６０ｍＬ）したパルプ濃度１質量％のスラリー５００ｍＬに対し、パルプ固形分に対し１質量％となるように表１の実施例の高分子試料あるいは比較例の高分子試料、比較試料を添加し、８００ｒｐｍで１分間撹拌後、タッピシートマシンにて抄紙（８０メッシュワイヤー）し、続いて圧力４１０ｋＰａで５分間プレスし、さらに回転型乾燥機を使用し１０５℃で乾燥した。温度２３℃、湿度５０％の条件下で２４時間調湿して、坪量８０ｇ／ｃｍ２の紙を得た。得られた紙の内部結合強さ（熊谷理機工業製インターナルボンドテスター）、ＪＩＳ Ｐ８１１２に準じて破裂強度を測定し、表５の結果を得た。実施試験例では比較試験例の紙に比較して紙力の向上を示した。
(Test Example 4)
The polymer sample of Example in Table 1 or the height of Comparative Example so as to be 1% by mass with respect to the solid pulp content with respect to 500 mL of the slurry having a pulp concentration of 1% by mass prepared in the same manner as in Test Example 1 (beating degree 360 mL). A molecular sample and a comparative sample are added, and after stirring at 800 rpm for 1 minute, papermaking (80 mesh wire) is performed with a tappi sheet machine, then pressed at a pressure of 410 kPa for 5 minutes, and further at 105 ° C. using a rotary dryer. It was dry. The humidity was adjusted for 24 hours under the conditions of a temperature of 23 ° C. and a humidity of 50% to obtain a paper having a basis weight of 80 g / cm 2 . The internal bond strength of the obtained paper (internal bond tester manufactured by Kumagai Riki Kogyo) and the burst strength were measured according to JIS P8112, and the results shown in Table 5 were obtained. In the test example, the paper strength was improved as compared with the paper in the comparative test example.
（表５）
(Table 5)
（試験例５）
試験例１と同様に調製（叩解度３６０ｍＬ）したパルプ濃度１質量％のスラリー５００ｍＬに対し、パルプ固形分に対し１質量％となるように表１の実施例の高分子試料あるいは比較例の高分子試料、比較試料を添加し、８００ｒｐｍで１分間撹拌後、タッピシートマシンにて抄紙（８０メッシュワイヤー）し、続いて圧力４１０ｋＰａで５分間プレスし、さらに回転型乾燥機を使用し１０５℃で乾燥した。温度２３℃、湿度５０％の条件下で２４時間調湿して、坪量８０ｇ／ｃｍ２の紙を得た。得られた紙の内部結合強さ（熊谷理機工業製インターナルボンドテスター）、ＪＩＳ Ｐ８１１２に準じて破裂強度を測定し、表６の結果を得た。実施試験例では比較試験例の紙に比較して紙力の向上を示した。
(Test Example 5)
The polymer sample of Example in Table 1 or the height of Comparative Example so as to be 1% by mass with respect to the solid pulp content with respect to 500 mL of the slurry having a pulp concentration of 1% by mass prepared in the same manner as in Test Example 1 (beating degree 360 mL). A molecular sample and a comparative sample are added, and after stirring at 800 rpm for 1 minute, papermaking (80 mesh wire) is performed with a tappi sheet machine, then pressed at a pressure of 410 kPa for 5 minutes, and further at 105 ° C. using a rotary dryer. It was dry. The humidity was adjusted for 24 hours under the conditions of a temperature of 23 ° C. and a humidity of 50% to obtain a paper having a basis weight of 80 g / cm 2 . The internal bond strength of the obtained paper (internal bond tester manufactured by Kumagai Riki Kogyo) and the burst strength were measured according to JIS P8112, and the results shown in Table 6 were obtained. In the test example, the paper strength was improved as compared with the paper in the comparative test example.
（表６）
(Table 6)
Claims (4)
The paper strength agent according to any one of claims 1 to 3, wherein the viscosity of a 1% by mass aqueous solution of the polymer at a rotation speed of 60 rpm and a temperature of 25 ° C. by a B-type viscometer is 5 to 50 mPa · s. Manufacturing method.
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| JPS5865097A (en) * | 1981-10-08 | 1983-04-18 | 三井東圧化学株式会社 | Paper strength increasing composition with good penetrating property of size liquid |
| JP2002115199A (en) * | 2000-10-12 | 2002-04-19 | Kao Corp | Additive for making paper |
| JP2006299429A (en) * | 2005-04-15 | 2006-11-02 | Kao Corp | Paper quality-improving agent for papermaking |
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| JPS5865097A (en) * | 1981-10-08 | 1983-04-18 | 三井東圧化学株式会社 | Paper strength increasing composition with good penetrating property of size liquid |
| JP2002115199A (en) * | 2000-10-12 | 2002-04-19 | Kao Corp | Additive for making paper |
| JP2006299429A (en) * | 2005-04-15 | 2006-11-02 | Kao Corp | Paper quality-improving agent for papermaking |
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