JP4817109B2 - Paper manufacturing method - Google Patents
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- JP4817109B2 JP4817109B2 JP2005319270A JP2005319270A JP4817109B2 JP 4817109 B2 JP4817109 B2 JP 4817109B2 JP 2005319270 A JP2005319270 A JP 2005319270A JP 2005319270 A JP2005319270 A JP 2005319270A JP 4817109 B2 JP4817109 B2 JP 4817109B2
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- paper strength
- parts
- polyacrylamide
- strength enhancer
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- 238000004519 manufacturing process Methods 0.000 title claims description 101
- 229920002401 polyacrylamide Polymers 0.000 claims description 68
- 239000003623 enhancer Substances 0.000 claims description 64
- 239000000178 monomer Substances 0.000 claims description 62
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 47
- 239000007864 aqueous solution Substances 0.000 claims description 31
- 229920000642 polymer Polymers 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- 229920002554 vinyl polymer Polymers 0.000 claims description 21
- 125000002091 cationic group Chemical group 0.000 claims description 16
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 125000000129 anionic group Chemical group 0.000 claims description 9
- -1 allyl sulfonate Chemical compound 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 5
- 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 claims description 3
- 239000013054 paper strength agent Substances 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims 1
- 239000000123 paper Substances 0.000 description 123
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 78
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 58
- 230000000694 effects Effects 0.000 description 38
- 229920001577 copolymer Polymers 0.000 description 32
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 29
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 26
- 239000000243 solution Substances 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 229910001873 dinitrogen Inorganic materials 0.000 description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 16
- 238000005342 ion exchange Methods 0.000 description 16
- 239000001301 oxygen Substances 0.000 description 16
- 229910052760 oxygen Inorganic materials 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 15
- 239000003505 polymerization initiator Substances 0.000 description 14
- 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 13
- WHNPOQXWAMXPTA-UHFFFAOYSA-N 3-methylbut-2-enamide Chemical compound CC(C)=CC(N)=O WHNPOQXWAMXPTA-UHFFFAOYSA-N 0.000 description 13
- 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 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 9
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 9
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 9
- 230000007423 decrease Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000002708 enhancing effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 150000003926 acrylamides Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-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
- 238000006683 Mannich reaction Methods 0.000 description 3
- 238000000149 argon plasma sintering Methods 0.000 description 3
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 3
- 229940073608 benzyl chloride Drugs 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-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
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 239000008351 acetate buffer Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- TXXHDPDFNKHHGW-UHFFFAOYSA-N muconic acid Chemical compound OC(=O)C=CC=CC(O)=O TXXHDPDFNKHHGW-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001374 small-angle light scattering Methods 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001302 tertiary amino group Chemical group 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- GNWBLLYJQXKPIP-ZOGIJGBBSA-N (1s,3as,3bs,5ar,9ar,9bs,11as)-n,n-diethyl-6,9a,11a-trimethyl-7-oxo-2,3,3a,3b,4,5,5a,8,9,9b,10,11-dodecahydro-1h-indeno[5,4-f]quinoline-1-carboxamide Chemical compound CN([C@@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H](C(=O)N(CC)CC)[C@@]2(C)CC1 GNWBLLYJQXKPIP-ZOGIJGBBSA-N 0.000 description 1
- 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
- FYBFGAFWCBMEDG-UHFFFAOYSA-N 1-[3,5-di(prop-2-enoyl)-1,3,5-triazinan-1-yl]prop-2-en-1-one Chemical group C=CC(=O)N1CN(C(=O)C=C)CN(C(=O)C=C)C1 FYBFGAFWCBMEDG-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 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
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 1
- QENRKQYUEGJNNZ-UHFFFAOYSA-N 2-methyl-1-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound CC(C)C(S(O)(=O)=O)NC(=O)C=C QENRKQYUEGJNNZ-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- 101100108891 Arabidopsis thaliana PRMT11 gene Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000019743 Choline chloride Nutrition 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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 101000987090 Homo sapiens MORF4 family-associated protein 1 Proteins 0.000 description 1
- 101000831175 Homo sapiens Mitochondrial import inner membrane translocase subunit TIM16 Proteins 0.000 description 1
- 240000001931 Ludwigia octovalvis Species 0.000 description 1
- 102100027862 MORF4 family-associated protein 1 Human genes 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 102100024285 Mitochondrial import inner membrane translocase subunit TIM16 Human genes 0.000 description 1
- TXXHDPDFNKHHGW-CCAGOZQPSA-N Muconic acid Natural products OC(=O)\C=C/C=C\C(O)=O TXXHDPDFNKHHGW-CCAGOZQPSA-N 0.000 description 1
- 108700038250 PAM2-CSK4 Proteins 0.000 description 1
- 101100484946 Petunia hybrida VPY gene Proteins 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 101100206155 Schizosaccharomyces pombe (strain 972 / ATCC 24843) tbp1 gene Proteins 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 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
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000001588 bifunctional effect Effects 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
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 230000000739 chaotic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 1
- 229960003178 choline chloride Drugs 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 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
- 125000005394 methallyl group Chemical group 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Chemical compound CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 1
- 101150091418 pam1 gene Proteins 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
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- Paper (AREA)
Description
本発明は、紙の製造方法に関する。更に詳しくは、ポリアクリルアミド系紙力増強剤を用いた紙の製造方法に関する。 The present invention relates to a paper manufacturing method. More specifically, the present invention relates to a paper manufacturing method using a polyacrylamide type paper strength enhancer.
従来、紙を製造する際には、紙に強度を付与すべく紙力増強剤が用いられており、性能等の点からポリアクリルアミド系紙力増強剤が広く用いられている。通常、紙力増強剤を用いる場合には、一種の紙力増強剤を一度にまたは分割して紙料に添加される。しかしながら、紙力増強剤を一種類しか用いない場合には、地合いと濾水性のバランスを取ることが困難であり、紙力増強剤を多く使用しなければならなかった。 Conventionally, when producing paper, a paper strength enhancer is used to impart strength to the paper, and polyacrylamide type paper strength enhancers are widely used from the viewpoint of performance and the like. Usually, when a paper strength enhancer is used, a kind of paper strength enhancer is added to the paper stock at one time or dividedly. However, when only one type of paper strength enhancer is used, it is difficult to balance the texture and drainage, and a large amount of paper strength enhancer must be used.
このような問題を解決すべく、数種の紙力増強剤を用いる紙の製造方法が提案されている。例えば、ポリアクリルアミド系重合体とカチオン性基を有し前記ポリアクリルアミド系重合体とは異なるポリマーを含有する添加剤を用いる紙の製造法（特許文献１参照）が提案されており、さらに、ポリアクリルアミド系重合体と、カチオン性基を有し前記ポリアクリルアミド系重合体とは異なるポリマーと、アルミニウム化合物とを用いて抄紙する紙の製造法（特許文献２参照）などが提案されている。しかしながら、いずれの方法においても、地合いと濾水性のバランスを取ることが困難であった。そこで、本出願人は、地合いと濾水性のバランスを容易にとることができる紙の製造方法を提案した（特許文献３参照）。当該方法により、地合いと濾水性のバランスを容易に取れるようになったが、地合いが良好となると、抄紙時の水切れ性が悪くなり、水切れ性が悪くなると断紙等が生じ易くなり、操業性に悪影響を及ぼす場合があった。 In order to solve the problems such as this, process for manufacturing paper using several paper strength agent has been proposed. For example, a paper manufacturing method (see Patent Document 1) using an additive containing a polyacrylamide polymer and a cationic group and a polymer different from the polyacrylamide polymer has been proposed. A method for producing paper using an acrylamide polymer, a polymer having a cationic group and different from the polyacrylamide polymer, and an aluminum compound (see Patent Document 2) has been proposed. However, in any method, it is difficult to balance the texture and the drainage. Therefore, the present applicant has proposed a paper manufacturing method that can easily balance the texture and drainage (see Patent Document 3). With this method, the balance between the texture and the drainage can be easily taken.However, when the texture becomes good, the water drainability at the time of papermaking deteriorates, and when the water drainability deteriorates, the paper breakage is likely to occur, and the operability. May have an adverse effect.
本発明は、地合いと濾水性のバランスを容易にとることができ、このため紙力を向上させ、結果として紙の製造に用いる紙力増強剤の使用量を減少させることができ、さらには抄紙時の水切れ性を向上させることにより、操業性を向上させることができる紙の製造方法を提供することを目的とする。 The present invention can easily balance the texture and drainage, thereby improving the paper strength, and as a result, reducing the amount of paper strength enhancer used for paper production, and further papermaking. It aims at providing the manufacturing method of the paper which can improve operativity by improving the water drainability at the time.
本発明者らは、前記課題を解決すべく、検討を重ねたところ、異種の特定のポリアクリルアミド系紙力増強剤を併用することにより、前記課題を解決し得ることを見出し、さらにはこれら異種のポリアクリルアミド系紙力増強剤をそれぞれ特定の場所で添加することにより、著しい紙力増強効果が得られることを見出した。 As a result of repeated studies to solve the above problems, the present inventors have found that the above problems can be solved by using a combination of different specific polyacrylamide-based paper strength enhancers. It was found that a remarkable paper strength enhancing effect can be obtained by adding each of the polyacrylamide type paper strength enhancing agents at specific locations.
すなわち、本発明は、ノニオン性ポリアクリルアミド系紙力増強剤（Ａ）と紙力増強剤の添加前後におけるＪＩＳ Ｐ ８１２１により測定される濾水度の差がノニオン性ポリアクリルアミド系紙力増強剤（Ａ）よりも大きいカチオン性ポリアクリルアミド系紙力増強剤（Ｂ−１）またはアニオン性ポリアクリルアミド系紙力増強剤（Ｂ−２）とを用い抄紙することを特徴とする紙の製造方法に関する。 That is, the present invention is a nonionic polyacrylamide type paper strength enhancer (nonionic polyacrylamide type paper strength enhancer (A) and the difference in the freeness measured by JIS P 8121 before and after the addition of the paper strength enhancer. The present invention relates to a paper production method comprising making paper using a cationic polyacrylamide type paper strength enhancer (B-1) or an anionic polyacrylamide type paper strength enhancer (B-2) larger than A).
本発明によれば、地合いと濾水性のバランスを容易に保つことができるため、紙力向上効果を増幅させることができ、その結果、抄紙時の紙力増強剤の使用量を減少させることができる。 According to the present invention, the balance between the texture and the drainage can be easily maintained, so that the paper strength improvement effect can be amplified, and as a result, the amount of the paper strength enhancer used during papermaking can be reduced. it can.
本発明の紙の製造方法には、ノニオン性ポリアクリルアミド系紙力増強剤（Ａ）（以後、（Ａ）成分という）および紙力増強剤の添加前後におけるＪＩＳ Ｐ ８１２１により測定される濾水度の差が（Ａ）成分よりも大きいカチオン性ポリアクリルアミド系紙力増強剤（Ｂ−１）（以後、（Ｂ−１）成分という。）またはアニオン性ポリアクリルアミド系紙力増強剤（Ｂ−２）（以後、（Ｂ−２）成分という）を用いる。（なお、以後、（Ｂ−１）成分または（Ｂ−２）成分を（Ｂ）成分ということがある）なお、本願明細書でいう濾水度の差とは、濾水度４００ｍｌ程度まで叩解した抄紙しようとする紙料に硫酸アルミニウムを１．０％添加してから３０秒後に紙力増強剤を０．５重量％添加し、３０秒攪拌したときの、ＪＩＳ Ｐ ８１２１に記載されるカナディアンフリーネステスターを使用した濾水量と、紙力増強剤を添加する前の抄紙しようとする紙料の、カナディアンフリーネステスターを使用した濾水量との差である。紙力増強剤の添加は、紙料固形分の濃度が約１．０％である紙料３００ｇをステンレス製１リットルビーカーに取り、紙料の温度を２５℃として、４枚平羽根の攪拌羽根（２ｃｍ×３ｃｍの平羽根４枚の付いた攪拌羽根）を用いて３００ｒｐｍで攪拌することにより行う。なお、本発明で言うノニオン性とは、アニオン性ビニルモノマー（（ｃ）成分のモル％）／カチオン性ビニルモノマー（（ｂ）成分のモル％））比を０．８５〜１．１の範囲となるように配合（ただし、（ｃ）成分が２価の酸の場合、（ｃ）成分のモル％を２倍した値を用いる。）することを言う。 In the method for producing paper of the present invention, the freeness measured by JIS P 8121 before and after the addition of the nonionic polyacrylamide-based paper strength enhancer (A) (hereinafter referred to as component (A)) and the paper strength enhancer. A cationic polyacrylamide type paper strength enhancer (B-1) (hereinafter referred to as (B-1) component) or an anionic polyacrylamide type paper strength enhancer (B-2) having a larger difference ) (Hereinafter referred to as component (B-2)). (Hereinafter, the component (B-1) or the component (B-2) may be referred to as the component (B).) The difference in the freeness as used in the present specification is a refining up to a freeness of about 400 ml. Canadian described in JIS P 8121 when 0.5% by weight of a paper strength enhancer is added 30 seconds after adding 1.0% of aluminum sulfate to a paper to be made, and stirred for 30 seconds This is the difference between the amount of drainage using the freeness tester and the amount of drainage using the Canadian freeness tester of the paper to be made before adding the paper strength enhancer. The paper strength enhancer is added by taking 300 g of paper stock having a stock solid concentration of about 1.0% into a stainless steel 1 liter beaker, setting the temperature of the stock to 25 ° C., and stirring blades of 4 flat blades. This is carried out by stirring at 300 rpm using a stirring blade with 4 flat blades of 2 cm × 3 cm. In addition, the nonionic property said by this invention is the range whose anionic vinyl monomer (mol% of (c) component) / cationic vinyl monomer (mol% of (b) component)) ratio is 0.85-1.1. (However, when the component (c) is a divalent acid, a value obtained by doubling the mol% of the component (c) is used).
本発明に用いられる（Ａ）成分としては、ポリアクリルアミド系紙力増強剤でありアニオン性およびカチオン性を示さない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が、特に紙力増強効果の点から、分岐構造を有するものが好ましい。 The component (A) used in the present invention is not particularly limited as long as it is a polyacrylamide-based paper strength enhancer and does not exhibit anionicity and cationicity. From the viewpoint of the force enhancing effect, those having a branched structure are preferred.
（Ａ）成分は、（ａ）（メタ）アクリルアミド（以下、（ａ）成分という）、（ｂ）カチオン性ビニルモノマー（以下、（ｂ）成分という）および（ｃ）アニオン性ビニルモノマー（以下、（ｃ）成分という）を必須成分とし、必要に応じて、（ｄ）Ｎ−置換（メタ）アクリルアミド（以下、（ｄ）成分という）、（ｅ）（メタ）アリルスルホン酸ナトリウム（以下、（ｅ）成分という）および（ｆ）ビニルモノマーであって（ｃ）〜（ｅ）成分以外のもの（以下、（ｆ）成分という）を共重合して得られるポリアクリルアミド系共重合体を含有するものであるが、（ａ）〜（ｅ）成分を必須成分として用いて得られたポリアクリルアミド系樹脂を用いる場合には、ポリアクリルアミド系樹脂中に分岐構造を導入することが容易であるため好ましい。また、濾水度の差が５０ｍｌ以下となる（Ａ）成分を用いることにより、紙力強度をさらに向上させることができるため好ましい。 (A) component includes (a) (meth) acrylamide (hereinafter referred to as (a) component), (b) cationic vinyl monomer (hereinafter referred to as (b) component) and (c) anionic vinyl monomer (hereinafter referred to as “component”). (C) component) as an essential component, and if necessary, (d) N-substituted (meth) acrylamide (hereinafter referred to as (d) component), (e) sodium (meth) allylsulfonate (hereinafter referred to as ( e) a component) and (f) a vinyl monomer, which is a polyacrylamide copolymer obtained by copolymerizing a monomer other than components (c) to (e) (hereinafter referred to as component (f)) However, when a polyacrylamide resin obtained by using the components (a) to (e) as essential components is used, it is preferable because it is easy to introduce a branched structure into the polyacrylamide resin. Arbitrariness. Further, it is preferable to use the component (A) having a freeness difference of 50 ml or less because the paper strength can be further improved.
（ｂ）成分としては、少なくとも１つのカチオン性官能基及び１つのビニル基を有するものであれば特に制限されず公知のものを用いることができる。具体的には、例えば、アリルアミンの他、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）アクリルアミドなどの第三級アミノ基を有するビニルモノマーまたはそれらの塩酸、硫酸、酢酸などの無機酸もしくは有機酸の塩類、または該第三級アミノ基含有ビニルモノマ−とメチルクロライド、ベンジルクロライド、ジメチル硫酸、エピクロルヒドリンなど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含有するビニルモノマ−等が挙げられる。 The component (b) is not particularly limited as long as it has at least one cationic functional group and one vinyl group, and known components can be used. Specifically, for example, in addition to allylamine, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, N, N- Vinyl monomers having a tertiary amino group such as diethylaminopropyl (meth) acrylamide or salts of inorganic or organic acids such as hydrochloric acid, sulfuric acid or acetic acid, or vinyl monomers and methyl chloride containing such tertiary amino groups, benzyl And vinyl monomers containing a quaternary ammonium salt obtained by reaction with a quaternizing agent such as chloride, dimethyl sulfate, epichlorohydrin and the like.
（ｃ）成分としては、（ｅ）成分以外の少なくとも１つのアニオン性官能基及び１つのビニル基を有する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、例えば、（メタ）アクリル酸、クロトン酸等のモノカルボン酸；マレイン酸、フマル酸、イタコン酸、ムコン酸、シトラコン酸等のジカルボン酸；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の有機スルホン酸；またはこれら各種有機酸のナトリウム塩、カリウム塩等が挙げられる。 The component (c) is not particularly limited as long as it has at least one anionic functional group other than the component (e) and one vinyl group, and known components can be used. Specifically, for example, monocarboxylic acids such as (meth) acrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, muconic acid and citraconic acid; vinyl sulfonic acid, styrene sulfonic acid, 2- Examples thereof include organic sulfonic acids such as acrylamido-2-methylpropanesulfonic acid; and sodium salts and potassium salts of these various organic acids.
（ｄ）成分としては、（ｂ）成分以外のＮ−置換（メタ）アクリルアミド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、例えば、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、Ｎ，Ｎ−ジエチル（メタ）アクリルアミド、Ｎ，Ｎ−ジイソプロピル（メタ）アクリルアミド、Ｎ−メチル（メタ）アクリルアミド、Ｎ−エチル（メタ）アクリルアミド、Ｎ−イソプロピル（メタ）アクリルアミド、Ｎ−ｔ−ブチル（メタ）アクリルアミド等が挙げられる。 The component (d) is not particularly limited as long as it is N-substituted (meth) acrylamide other than the component (b), and a known component can be used. Specifically, for example, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-diisopropyl (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meta) ) Acrylamide, N-isopropyl (meth) acrylamide, Nt-butyl (meth) acrylamide and the like.
（ｆ）成分としては、（ａ）〜（ｅ）成分以外のビニルモノマー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）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル等のアクリル酸アルキルエステル類、アリルアルコール等のアリル基を含有するアリル系モノマー類、イソプロピルアクリルアミド等のＮ−置換アクリルアミド系モノマー類、（メタ）アクリロニトリルなどの他、２官能ビニルモノマー系としてメチレンビス（メタ）アクリルアミド、エチレンビス（メタ）アクリルアミド等のビスアクリルアミド系モノマー類やエチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート等のジアクリレート系モノマー類、ジアリルアミン、ジビニルベンゼン等であり、３以上のビニル基を有する多官能ビニルモノマー類としては、１，３，５-トリアクロイルヘキサヒドロ−Ｓ−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などを単独または複数種を混合して使用することができる。 (F) As a component, if it is vinyl monomers other than (a)-(e) component, it will not specifically limit, A well-known thing can be used. Specifically, for example, alkyl methacrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate, allyl monomers containing an allyl group such as allyl alcohol, isopropyl In addition to N-substituted acrylamide monomers such as acrylamide, (meth) acrylonitrile and the like, bifunctional vinyl monomers such as bisacrylamide monomers such as methylene bis (meth) acrylamide and ethylene bis (meth) acrylamide, and ethylene glycol di (meth) ) Diacrylate monomers such as acrylate and diethylene glycol di (meth) acrylate, diallylamine, divinylbenzene and the like, and polyfunctional vinyl monomers having three or more vinyl groups include 1,3,5-triacroyl hexa Hydro-S-triazine, triallyl isocyanurate, triallylamine, tetramethylolmethane tetraacrylate and the like can be used alone or in combination.
これら（ａ）〜（ｅ）成分のうち、（ｅ）成分を用いることにより、ラジカルの移動（連鎖移動）が生じやすくなり、分子量の調整が容易となるため好ましく、また、（ｄ）成分や、（ｆ）成分としてビスアクリルアミド系モノマー、ジアクリレート系モノマー、ジビニルベンゼン、多官能ビニルモノマーを用いることにより、得られるポリマーを架橋により高分子量化させることができるため好ましい。 Among these components (a) to (e), the use of the component (e) is preferable because radical transfer (chain transfer) is likely to occur and the molecular weight can be easily adjusted. It is preferable to use a bisacrylamide monomer, a diacrylate monomer, divinylbenzene, or a polyfunctional vinyl monomer as the component (f) because the resulting polymer can be made high molecular weight by crosslinking.
前記モノマーを重合させる方法としては特に限定されず、公知の方法を採用することができる。具体的には、前記モノマー類を混合したものに、公知のラジカル重合開始剤を加えることにより行われる。具体的には、例えば、所定の反応容器に溶媒として水を仕込み所定温度まで加温し、上記各種モノマーおよび水を仕込んだ滴下ロートと、重合開始剤と水を仕込んだ滴下ロートから、それぞれの成分を撹拌下に、反応容器中に滴下しながら重合する方法や所定の反応容器に上記各種モノマーを仕込み、所定の重合温度に調整し、重合開始剤を添加し、重合する方法などが挙げられる。なお、必要に応じて、イソプロピルアルコール、ペンタノール等のアリル基を有さないアルコール類を連鎖移動剤として用い、得られるアクリルアミド系樹脂の分子量を調整してもよい。 The method for polymerizing the monomer is not particularly limited, and a known method can be employed. Specifically, it is carried out by adding a known radical polymerization initiator to a mixture of the monomers. Specifically, for example, water is charged in a predetermined reaction vessel as a solvent and heated to a predetermined temperature, and a dropping funnel charged with the above various monomers and water, and a dropping funnel charged with a polymerization initiator and water, A method of polymerizing components while dropping them into a reaction vessel under stirring, a method of charging the above various monomers in a predetermined reaction vessel, adjusting to a predetermined polymerization temperature, adding a polymerization initiator, and polymerizing, etc. . If necessary, alcohols having no allyl group such as isopropyl alcohol and pentanol may be used as a chain transfer agent to adjust the molecular weight of the resulting acrylamide resin.
（Ａ）成分を得るために用いられる（ａ）〜（ｅ）成分の使用量は、（ａ）成分を５７〜９９．７８モル％程度、より好ましくは６３〜９７．８モル％、（ｂ）成分を０.１〜１５モル％程度、より好ましくは１〜１５モル％、（ｃ）成分を０.１〜１５モル％程度、より好ましくは１〜１５モル％用い、（ｄ）成分を用いる場合には、（ｄ）成分を０．０１〜２モル％程度、より好ましくは０．１〜１モル％、（ｅ）成分を用いる場合には、（ｅ）成分を０．０１〜１０モル％程度、より好ましくは０．１〜５モル％用いることが好ましい。なお、（ｂ）成分を０.１モル％未満しか用いない場合には定着効果が低く、紙力効果が低くなる傾向があり、１５モル％を越えるとポリマー中のアクリルアミド分が減少することにより紙力効果が低くなる傾向があり、さらには、高価となるため好ましくない。なお、（ｃ）成分を０.１モル％未満しか使用しない場合には定着効果が低く、紙力効果が低くなる傾向があり、１５モル％を越えるとポリマー中のアクリルアミド分が減少することにより紙力効果が低くなる傾向があり、さらには、高価となるため好ましくない。なお、（ｄ）成分を０．０１モル％未満しか用いない場合には高分子量化効果は小さくなり、２．０モル％を超えて用いるとゲル化するおそれがある。なお、（ｅ）成分を０．０５モル％未満しか使用しない場合には連鎖移動効果が弱く、また分岐点の生成も少ないために、分岐構造が不十分となる傾向がある。１０モル％を超える場合は連鎖移動効果が強すぎるため、ポリマー鎖が短くなり、高分子量ポリマーが生成しにくくなる。なお、（ｆ）成分を用いる場合には、１モル％以下とすることが好ましい。 The amount of the components (a) to (e) used to obtain the component (A) is about 57 to 99.78 mol% of the component (a), more preferably 63 to 97.8 mol%, (b ) Component is about 0.1 to 15 mol%, more preferably 1 to 15 mol%, (c) component is about 0.1 to 15 mol%, more preferably 1 to 15 mol%, and (d) component is used. When used, the component (d) is about 0.01 to 2 mol%, more preferably 0.1 to 1 mol%, and when the component (e) is used, the component (e) is 0.01 to 10 mol%. It is preferable to use about mol%, more preferably 0.1 to 5 mol%. When component (b) is used in an amount of less than 0.1 mol%, the fixing effect tends to be low and the paper strength effect tends to be low. When the component exceeds 15 mol%, the acrylamide content in the polymer decreases. The paper strength effect tends to be low, and further, it is not preferable because it becomes expensive. When component (c) is used in an amount of less than 0.1 mol%, the fixing effect tends to be low and the paper strength effect tends to be low. When the component exceeds 15 mol%, the acrylamide content in the polymer decreases. The paper strength effect tends to be low, and further, it is not preferable because it becomes expensive. In addition, when the component (d) is used in an amount of less than 0.01 mol%, the effect of increasing the molecular weight is reduced, and when it is used in an amount exceeding 2.0 mol%, there is a risk of gelation. When the component (e) is used in an amount of less than 0.05 mol%, the chain transfer effect is weak and the number of branch points is small, so that the branch structure tends to be insufficient. When it exceeds 10 mol%, the chain transfer effect is too strong, so that the polymer chain is shortened and it is difficult to produce a high molecular weight polymer. In addition, when using (f) component, it is preferable to set it as 1 mol% or less.
このようにして得られた（Ａ）成分の重量平均分子量は１００万程度以上が好ましい。ここでいう重量平均分子量は、ＧＰＣ−ＬＡＬＬＳ法あるいはＧＰＣ−ＲＡＬＬＳ法によるポリエチレンオキシド換算した重量平均分子量をいい、０．５ｍｏｌ／ｌ酢酸緩衝液（０．５ｍｏｌ／ｌ酢酸＋０．５ｍｏｌ／ｌ酢酸ナトリウム水溶液、ｐＨ約４．２）を溶媒（溶離液）として、ポリマー濃度０．０２５％で、光散乱角角５°あるいは９０°で測定した値（温度４０℃）をいう。（Ａ）成分の重量平均分子量が１００万未満では充分な紙力効果が得られない場合がある。（Ａ）成分は、通常５重量％以上の不揮発物を含有するように調整する。なお、（Ａ）成分の不揮発物を５重量％水溶液に調整した場合の粘度は、２０，０００ｍＰａ・ｓ程度以下とすることが好ましい。粘度が２０，０００ｍＰａ・ｓを超える場合は地合を乱しやすくなり、紙力向上効果が著しく低下する場合がある。 The weight average molecular weight of the component (A) thus obtained is preferably about 1 million or more. The weight average molecular weight here refers to the weight average molecular weight converted to polyethylene oxide by the GPC-LALLS method or GPC-RALLS method, and is 0.5 mol / l acetate buffer (0.5 mol / l acetic acid + 0.5 mol / l sodium acetate). A value (temperature: 40 ° C.) measured at a light scattering angle of 5 ° or 90 ° at a polymer concentration of 0.025% using an aqueous solution, pH of about 4.2) as a solvent (eluent). When the weight average molecular weight of the component (A) is less than 1 million, sufficient paper strength effect may not be obtained. The component (A) is usually adjusted to contain 5% by weight or more of non-volatile materials. In addition, it is preferable that the viscosity at the time of adjusting the non-volatile substance of (A) component to 5 weight% aqueous solution shall be about 20,000 mPa * s or less. When the viscosity exceeds 20,000 mPa · s, the formation tends to be disturbed, and the paper strength improvement effect may be significantly reduced.
本発明に用いられる（Ｂ−１）成分としては、紙力増強剤の添加前後におけるＪＩＳ Ｐ ８１２１により測定される濾水度の差が（Ａ）成分よりも大きいポリアクリルアミド系紙力増強剤であり、カチオン性を示す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が、特に紙力増強効果の点から、分岐構造を有するものが好ましい。なお、濾水度の差が５０ｍｌを超えるポリアクリルアミド系紙力増強剤を用いることにより、操業性をさらに改善させることができるためより好ましい。なお、ここで言うカチオン性とは、アニオン性ビニルモノマー（（ｃ）成分のモル％）／カチオン性ビニルモノマー（（ｂ）成分のモル％）比が、０．８５未満となるように配合（ただし、（ｃ）成分がジカルボン酸の場合、（ｃ）成分のモル％を２倍した値を用いる。）することを言う。（Ｂ−１）成分を調製する際に用いられるモノマーとしては、具体的には、前記（Ａ）成分の調製に用いたモノマーと同種のモノマーを使用することができる。 The component (B-1) used in the present invention is a polyacrylamide type paper strength enhancer in which the difference in freeness measured by JIS P 8121 before and after the addition of the paper strength enhancer is larger than that of the component (A). Yes, any known one can be used as long as it exhibits a cationic property, and those having a branched structure are preferred from the viewpoint of the paper strength enhancing effect. In addition, since the operativity can be further improved by using the polyacrylamide type paper strength enhancer in which the difference of freeness exceeds 50 ml, it is more preferable. The term “cationic” as used herein means that the ratio of anionic vinyl monomer (mol% of component (c)) / cationic vinyl monomer (mol% of component (b)) is less than 0.85 ( However, when the component (c) is a dicarboxylic acid, a value obtained by doubling the mol% of the component (c) is used. As the monomer used when preparing the component (B-1), specifically, the same type of monomer as the monomer used for preparing the component (A) can be used.
（Ｂ−１）成分は、（ａ）成分、（ｂ）成分および（ｃ）成分を必須成分とし、必要に応じて（ｄ）成分、（ｅ）成分および（ｆ）成分を共重合して得られるポリアクリルアミド系共重合体が挙げられるが、（ａ）〜（ｅ）成分を必須成分として用いて得られたポリアクリルアミド系樹脂を用いる場合には、ポリアクリルアミド系樹脂中に分岐構造を導入することが容易であるため好ましい。 The component (B-1) comprises the components (a), (b) and (c) as essential components, and if necessary, the components (d), (e) and (f) are copolymerized. The resulting polyacrylamide copolymer can be mentioned, but when using a polyacrylamide resin obtained using components (a) to (e) as essential components, a branched structure is introduced into the polyacrylamide resin. It is preferable because it is easy to do.
（Ｂ−１）成分を得るために用いられる（ａ）〜（ｅ）成分の使用量は、（ａ）成分を５１〜９９．６８モル％程度、より好ましくは６６〜９６．８モル％、（ｂ）成分を０.２〜２０モル％程度、より好ましくは２〜１５モル％、（ｃ）成分を０.１〜１６．５モル％程度、より好ましくは１〜１２．５モル％用い、（ｄ）成分を用いる場合には、（ｄ）成分を０．０１〜２モル％程度、より好ましくは０．１〜１モル％、（ｅ）成分を用いる場合には、（ｅ）成分を０．０１〜１０モル％程度、より好ましくは０．１〜５モル％用いることが好ましい。なお、（ｂ）成分を０.１モル％未満しか用いない場合には定着効果が低く、紙力効果が低くなる傾向があり、１７．５モル％を越えるとポリマー中のアクリルアミド分が減少することにより紙力効果が低くなる傾向があり、さらには、高価となるため好ましくない。なお、（ｃ）成分を０.２モル％未満しか用いない場合には定着効果が低く、紙力効果が低くなる傾向があり、２０モル％を越えるとポリマー中のアクリルアミド分が減少することにより紙力効果が低くなる傾向があり、さらには、高価となるため好ましくない。（Ｂ−１）成分は、（Ａ）成分と同様の重合法により重合を行えば良く、通常５重量％以上の不揮発物を含有するように調整する。なお、（ｆ）成分を用いる場合には、０．５モル％以下とすることが好ましい。 The amount of the components (a) to (e) used to obtain the component (B-1) is about 51 to 99.68 mol%, more preferably 66 to 96.8 mol% of the component (a). The component (b) is used in an amount of about 0.2 to 20 mol%, more preferably 2 to 15 mol%, and the component (c) is used in an amount of about 0.1 to 16.5 mol%, more preferably 1 to 12.5 mol%. When the component (d) is used, the component (d) is about 0.01 to 2 mol%, more preferably 0.1 to 1 mol%. When the component (e) is used, the component (e) Is preferably about 0.01 to 10 mol%, more preferably 0.1 to 5 mol%. When the component (b) is used in an amount of less than 0.1 mol%, the fixing effect tends to be low and the paper strength effect tends to be low. When the component exceeds 17.5 mol%, the acrylamide content in the polymer decreases. As a result, the paper strength effect tends to be low, and further, it is not preferable because it becomes expensive. When the component (c) is used in an amount of less than 0.2 mol%, the fixing effect tends to be low and the paper strength effect tends to be low. When the component exceeds 20 mol%, the acrylamide content in the polymer decreases. The paper strength effect tends to be low, and further, it is not preferable because it becomes expensive. (B-1) A component should just superpose | polymerize by the polymerization method similar to (A) component, and it adjusts so that normally 5 weight% or more of non-volatile matters may be contained. In addition, when using (f) component, it is preferable to set it as 0.5 mol% or less.
これら（Ｂ−１）成分の重量平均分子量は、特に限定されないが、通常、１００万程度である。また、不揮発物を５重量％に調整した場合の粘度は、２０，０００ｍＰａ・ｓ程度以下とすることが好ましい。粘度が２０，０００ｍＰａ・ｓを超える場合は地合を乱しやすくなり、紙力向上効果が著しく低下する場合がある。 Although the weight average molecular weight of these (B-1) components is not specifically limited, Usually, it is about 1 million. Further, the viscosity when the nonvolatile matter is adjusted to 5% by weight is preferably about 20,000 mPa · s or less. When the viscosity exceeds 20,000 mPa · s, the formation tends to be disturbed, and the paper strength improvement effect may be significantly reduced.
なお、本発明では、前記（ａ）〜（ｆ）成分（なお、（ｄ）〜（ｆ）成分は任意使用である。）を前記方法により重合して、ポリアクリルアミド共重合体を製造した後に、変性させたカチオン変性ポリアクリルアミド系重合体を用いてもよい。カチオン変性ポリアクリルアミド系重合体としては、例えば、ホフマン分解法、マンニッヒ反応法によるものが挙げられる。 In addition, in this invention, after polymerizing the said (a)-(f) component (In addition, (d)-(f) component is arbitrary use) by the said method, and manufacturing a polyacrylamide copolymer. Alternatively, a modified cation-modified polyacrylamide polymer may be used. Examples of the cation-modified polyacrylamide polymer include those obtained by the Hofmann decomposition method and the Mannich reaction method.
ホフマン分解法によるカチオン変性アクリルアミド系重合体の調製法は、従来と同様の方法を採用すればよい。例えば、アクリルアミド系重合体の水溶液に次亜ハロゲン酸塩とアルカリ触媒とを添加することにより、アルカリ性領域においてアクリルアミド系重合体と次亜ハロゲン酸塩とを反応させた後に酸を添加し、ｐＨ３．５〜５．５に調整すればよい。本発明において、前記ホフマン分解反応により調製したカオチン変性アクリルアミド系重合体以外に、以下のものを例示することができる。即ち、塩化コリンの存在下にポリアクリルアミドをホフマン分解反応して調製したカチオン変性物（特開昭５３−１０９５９４号）、ホフマン分解反応において水酸基を有する第３級アミンと塩化ベンジルあるいはその誘導体との４級化反応物を添加して調製したカチオン変性物（特公昭５８−８６８２号）、ホフマン分解反応において安定剤として有機多価アミンを添加して調製したカチオン変性物（特公昭６０−１７３２２号）、またホフマン分解反応において安定剤として特定のカチオン性化合物を添加して調製したカチオン変性物（特公昭６２−４５８８４号）等を使用することができる。前記ホフマン分解反応により調製される重合体は、カチオン性単量体単位を５〜５０モル％程度、アクリルアミド単位を６０〜９５モル％程度、含有することができる。また、ホフマン分解反応により調製されるカチオン変性アクリルアミド系重合体の平均分子量は、５〜３００万程度が好ましい。 As a method for preparing the cation-modified acrylamide polymer by the Hofmann decomposition method, a method similar to the conventional method may be employed. For example, by adding a hypohalite and an alkali catalyst to an aqueous solution of an acrylamide polymer, an acid is added after reacting the acrylamide polymer and the hypohalite in an alkaline region, and pH 3. What is necessary is just to adjust to 5-5.5. In the present invention, the following can be exemplified in addition to the chaotic modified acrylamide polymer prepared by the Hofmann decomposition reaction. That is, a cation-modified product prepared by subjecting polyacrylamide to Hofmann decomposition reaction in the presence of choline chloride (Japanese Patent Laid-Open No. 53-109594), a tertiary amine having a hydroxyl group and benzyl chloride or a derivative thereof in Hofmann decomposition reaction Cation-modified product prepared by adding a quaternized reaction product (Japanese Patent Publication No. 58-8682), and cation-modified product prepared by adding an organic polyvalent amine as a stabilizer in the Hofmann decomposition reaction (Japanese Patent Publication No. 60-17322) In addition, a cation-modified product (Japanese Examined Patent Publication No. 62-45884) prepared by adding a specific cationic compound as a stabilizer in the Hofmann decomposition reaction can be used. The polymer prepared by the Hofmann decomposition reaction may contain about 5 to 50 mol% of cationic monomer units and about 60 to 95 mol% of acrylamide units. The average molecular weight of the cation-modified acrylamide polymer prepared by the Hofmann decomposition reaction is preferably about 5 to 3 million.
本発明のマンニッヒ反応によるカチオン変性アクリルアミド系重合体の調製法は、従来と同様の方法を採用すればよい。例えば、アクリルアミド系重合体の水溶液中にホルマリン及びジメチルアミン等の２級アミンを加え、温度４０〜６０℃程度、１〜５時間程度反応させるという条件を採用すればよい。前記マンニッヒ反応により調製される重合体は、カチオン性単量体単位を１０〜６０モル％程度、アクリルアミド単位を４０〜９０モル％程度、含有することができる。 The preparation method of the cation-modified acrylamide polymer by the Mannich reaction of the present invention may be the same as the conventional method. For example, a condition in which a secondary amine such as formalin and dimethylamine is added to an aqueous solution of an acrylamide polymer and the reaction is performed at a temperature of about 40 to 60 ° C. for about 1 to 5 hours may be employed. The polymer prepared by the Mannich reaction can contain about 10 to 60 mol% of cationic monomer units and about 40 to 90 mol% of acrylamide units.
本発明に用いられる（Ｂ−２）成分としては、紙力増強剤の添加前後におけるＪＩＳ Ｐ ８１２１により測定される濾水度の差が（Ａ）成分よりも大きいポリアクリルアミド系紙力増強剤であり、アニオン性を示す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が、特に紙力増強効果の点から、分岐構造を有するものが好ましい。なお、濾水度の差が５０ｍｌを超えるポリアクリルアミド系紙力増強剤を用いることにより、操業性をさらに改善させることができるためより好ましい。ここで言うアニオン性とは、アニオン性ビニルモノマー（（ｃ）成分のモル％）／カチオン性ビニルモノマー（（ｂ）成分のモル％）比が、１．１を越えるように配合（ただし、（ｃ）成分がジカルボン酸の場合、（ｃ）成分のモル％を２倍した値を用いる。）することを言う。（Ｂ−２）成分を調製する際に用いられるモノマーとしては、具体的には、前記（Ａ）成分の調製に用いたモノマーと同種のモノマーを使用することができる。 The component (B-2) used in the present invention is a polyacrylamide type paper strength enhancer in which the difference in the freeness measured by JIS P 8121 before and after the addition of the paper strength enhancer is larger than the component (A). Yes, any known anionic property can be used without particular limitation, but those having a branched structure are particularly preferred from the viewpoint of enhancing paper strength. In addition, since the operativity can be further improved by using the polyacrylamide type paper strength enhancer in which the difference of freeness exceeds 50 ml, it is more preferable. The anionicity mentioned here is formulated so that the ratio of anionic vinyl monomer (mol% of component (c)) / cationic vinyl monomer (mol% of component (b)) exceeds 1.1 (however, ( c) When the component is a dicarboxylic acid, the value obtained by doubling the mol% of the component (c) is used. As the monomer used when preparing the component (B-2), specifically, the same type of monomer as the monomer used for preparing the component (A) can be used.
（Ｂ−２）成分は、（ａ）成分、（ｂ）成分および（ｃ）成分を必須成分とし、必要に応じて（ｄ）成分、（ｅ）成分および（ｆ）成分を共重合して得られるポリアクリルアミド系共重合体が挙げられるが、（ａ）〜（ｅ）成分を必須成分として用いて得られたポリアクリルアミド系樹脂を用いる場合には、ポリアクリルアミド系樹脂中に分岐構造を導入することが容易であるため好ましい。なお、 The component (B-2) includes the component (a), the component (b), and the component (c) as essential components, and copolymerizes the component (d), the component (e), and the component (f) as necessary. The resulting polyacrylamide copolymer can be mentioned, but when using a polyacrylamide resin obtained using components (a) to (e) as essential components, a branched structure is introduced into the polyacrylamide resin. It is preferable because it is easy to do. In addition,
（Ｂ−２）成分を得るために用いられる（ａ）〜（ｅ）成分の使用量は、（ａ）成分を５０〜９９．６８モル％程度、より好ましくは６５〜９６．８モル％、（ｂ）成分を０.１〜１７．５モル％程度、より好ましくは１〜１３．５モル％、（ｃ）成分を０.２〜２０モル％程度、より好ましくは２〜１５モル％用い、（ｄ）成分を用いる場合には、（ｄ）成分を０．０１〜２モル％程度、より好ましくは０．１〜１モル％、（ｅ）成分を用いる場合には、（ｅ）成分を０．０１〜１０モル％程度、より好ましくは０．１〜５モル％用いることが好ましい。なお、（ｂ）成分を０.１モル％未満しか用いない場合には定着効果が低く、紙力効果が低くなる傾向があり、１７．５モル％を越えるとポリマー中のアクリルアミド分が減少することにより紙力効果が低くなる傾向があり、さらには、高価となるため好ましくない。なお、（ｃ）成分を０.２モル％未満しか用いない場合には定着効果が低く、紙力効果が低くなる傾向があり、２０モル％を越えるとポリマー中のアクリルアミド分が減少することにより紙力効果が低くなる傾向があり、さらには、高価となるため好ましくない。（Ｂ−２）成分は、（Ａ）成分と同様の重合法により重合を行えば良く、通常５重量％以上の不揮発物を含有するように調整する。なお、（ｆ）成分を用いる場合には、０．５モル％以下とすることが好ましい。 The amount of the components (a) to (e) used to obtain the component (B-2) is about 50 to 99.68 mol% of the component (a), more preferably 65 to 96.8 mol%, (B) About 0.1-17.5 mol% of a component, More preferably, 1-13.5 mol%, (c) About 0.2-20 mol% of a component, More preferably, 2-15 mol% is used. When the component (d) is used, the component (d) is about 0.01 to 2 mol%, more preferably 0.1 to 1 mol%. When the component (e) is used, the component (e) Is preferably about 0.01 to 10 mol%, more preferably 0.1 to 5 mol%. When the component (b) is used in an amount of less than 0.1 mol%, the fixing effect tends to be low and the paper strength effect tends to be low. When the component exceeds 17.5 mol%, the acrylamide content in the polymer decreases. As a result, the paper strength effect tends to be low, and further, it is not preferable because it becomes expensive. When the component (c) is used in an amount of less than 0.2 mol%, the fixing effect tends to be low and the paper strength effect tends to be low. When the component exceeds 20 mol%, the acrylamide content in the polymer decreases. The paper strength effect tends to be low, and further, it is not preferable because it becomes expensive. (B-2) A component should just superpose | polymerize by the polymerization method similar to (A) component, and it adjusts so that normally 5 weight% or more of non-volatile matters may be contained. In addition, when using (f) component, it is preferable to set it as 0.5 mol% or less.
これら（Ｂ−２）成分の重量平均分子量は、特に限定されないが、通常、１００万程度である。また、不揮発物を５重量％に調整した場合の粘度は、２０，０００ｍＰａ・ｓ程度以下とすることが好ましい。粘度が２０，０００ｍＰａ・ｓを超える場合は地合を乱しやすくなり、紙力向上効果が著しく低下する場合がある。 Although the weight average molecular weight of these (B-2) components is not specifically limited, Usually, it is about 1 million. Further, the viscosity when the nonvolatile matter is adjusted to 5% by weight is preferably about 20,000 mPa · s or less. When the viscosity exceeds 20,000 mPa · s, the formation tends to be disturbed, and the paper strength improvement effect may be significantly reduced.
前記（Ａ）成分および（Ｂ）成分を添加する際の量は特に制限されないが、通常（Ａ）成分を固形分重量換算で、紙料に対して、０．１〜１．５重量％程度、より好ましくは０．３〜１．０重量％、（Ｂ）成分を固形分重量換算で、紙料に対して、０．０５〜０．７５重量％程度、好ましくは０．１〜０．５重量％添加する。（Ａ）成分の使用量は固形分重量換算で、紙料に対して、０．１重量％未満の場合には紙力効果が十分でない場合があり、１．５重量％を超える場合には定着性が低下し、汚れを誘発しやすくなる。（Ｂ）成分の使用量は固形分重量換算で、紙料に対して、０．０５重量％未満の場合には濾水性が十分でなく、０．７５重量％を超える場合には紙の地合が整いにくくなる。 The amount when the component (A) and the component (B) are added is not particularly limited, but the component (A) is usually about 0.1 to 1.5% by weight in terms of solid content, based on the stock. More preferably, it is 0.3 to 1.0% by weight, and the component (B) is about 0.05 to 0.75% by weight, preferably 0.1 to 0. Add 5% by weight. The amount of component (A) used in terms of solid content is less than 0.1% by weight, and the paper strength effect may not be sufficient if the amount is less than 0.1% by weight. Fixing property is lowered and stains are easily induced. The amount of component (B) used is calculated in terms of solid content, and if it is less than 0.05% by weight, the drainage is not sufficient, and if it exceeds 0.75% by weight, the paper ground is used. It becomes difficult to align.
なお、（Ａ）成分の使用量と（Ｂ）成分の使用量の固形分重量比（Ａ）／（Ｂ）が、０．２以上とすることにより、紙力向上効果が著しくなるため好ましい。（Ａ）成分と（Ｂ）成分の使用固形分重量比が０．２未満では地合乱れが起こりやすく、紙力効果が向上しにくくなる傾向がある。（Ａ）成分と（Ｂ）成分の使用固形分重量比の上限は制限されないが、２０を超える場合は抄速が低下する場合がある。なお、本発明の効果に影響を与えない範囲で、サイズ剤、ピッチコントロール剤、濾水剤等抄紙に必要な添加剤を添加できる。 In addition, it is preferable that the solid content weight ratio (A) / (B) of the usage amount of the component (A) and the usage amount of the component (B) is 0.2 or more because the effect of improving the paper strength becomes remarkable. If the weight ratio of the used solid content of the component (A) and the component (B) is less than 0.2, formation disturbance tends to occur, and the paper strength effect tends to be difficult to improve. The upper limit of the used solid content weight ratio of the component (A) and the component (B) is not limited, but when it exceeds 20, the paper making speed may be lowered. In addition, additives necessary for papermaking, such as a sizing agent, a pitch control agent, and a filtering agent, can be added as long as the effects of the present invention are not affected.
（Ａ）成分および（Ｂ）成分の添加場所としては特に制限されないが、（Ａ）成分を紙料濃度が２．０重量％以上の場所で、（Ｂ）成分を紙料濃度が２．０重量％未満の場所で添加することにより紙力強度を著しく向上させることができるため好ましい。なお、紙料濃度が２．０重量％以上の場所としては、例えば、ミキシングチェスト、マシンチェスト、種箱などが挙げられ、紙料濃度が２．０重量％未満の場所としては、例えば、ファンポンプ、白水ピット、スクリーンなどが挙げられる。これらのうち、（Ａ）成分の添加場所をマシンチェストで、（Ｂ）成分の添加場所をファンポンプとすることにより、特に著しい紙力効果が得られるため好ましい。 There are no particular restrictions on the location where the component (A) and the component (B) are added, but the component (A) is at a location where the stock concentration is 2.0% by weight or more, and the component (B) is at a stock concentration of 2.0. It is preferable to add it at a location of less than% by weight since the paper strength can be remarkably improved. Examples of the place where the paper material concentration is 2.0% by weight or more include a mixing chest, a machine chest, and a seed box. Examples of the place where the paper material concentration is less than 2.0% by weight include, for example, a fan. Examples include pumps, white water pits, and screens. Of these, it is preferable to use a machine chest for the component (A) and a fan pump for the component (B) because a particularly remarkable paper strength effect can be obtained.
以下、実施例により本発明を更に詳細に説明するが、本発明はこれに限定されるものではない。実施例中の部および％はそれぞれ重量部および重量％を示す。また、実施例中の試験法を下記に示す。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this. In the examples, parts and% represent parts by weight and% by weight, respectively. The test methods in the examples are shown below.
（１）濾水度
ＪＩＳ Ｐ ８１２１に準拠して前記の方法により測定した。測定に使用した紙料はＬ−ＵＫＰで、４００ｍｌまで叩解したものを用いた。
(1) Freeness measured in accordance with JIS P 8121 by the above method. The paper stock used for the measurement was L-UKP, which was beaten up to 400 ml.
（２）破裂強度
ＪＩＳ Ｐ ８１３１に準拠して測定し、比破裂強度（ｋＰａ・ｍ２／ｇ）で示した。
(2) Burst strength Measured according to JIS P 8131 and indicated as specific burst strength (kPa · m 2 / g).
（３）重量平均分子量
以下の測定条件にて測定した。
ＧＰＣ本体：東ソー（株）製
カラム：東ソー（株）製ガードカラムＰＷＸＬ１本およびＧＭＰＷＸＬ２本（温度４０℃）
溶離液：０．５ｍｏｌ／ｌ酢酸緩衝液（０．５ｍｏｌ／ｌ酢酸（和光純薬工業（株）製）＋０．５ｍｏｌ／ｌ酢酸ナトリウム（キシダ化学（株）製）水溶液、ｐＨ約４．２）
流速：０．８ｍｌ／分
検出器：東ソー（株）製濃度検出器（ＲＩ−８０１０）および光散乱検出器（ＬＳ−８０００）（室温）ＬＡＬＬＳ法
ビスコテック社製ＴＤＡ ＭＯＤＥＬ３０１（濃度検出器および９０°光散乱検出器および粘度検出器（温度４０℃））ＲＡＬＬＳ法
(3) It measured on the measurement conditions below a weight average molecular weight.
GPC body: Tosoh Co., Ltd. column: Tosoh Co., Ltd. guard column PWXL 1 and GMPWXL 2 (temperature 40 ° C.)
Eluent: 0.5 mol / l acetate buffer (0.5 mol / l acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.) + 0.5 mol / l sodium acetate (manufactured by Kishida Chemical Co., Ltd.), aqueous solution, pH about 4.2 )
Flow rate: 0.8 ml / min Detector: Tosoh Corporation concentration detector (RI-8010) and light scattering detector (LS-8000) (room temperature) LALLS method TDA MODEL 301 (concentration detector and 90) ° Light scattering detector and viscosity detector (temperature 40 ° C)) RALLS method
また、実施例中の略語の名称を以下に示す。
（ａ）ＡＡ：アクリル酸 ＩＡ：イタコン酸
（ｂ）ＤＭ：ジメチルアミノエチルメタクリレート ＤＭＡＥＡ−ＢＱ：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 ＤＭＬ：ＤＭのベンジルクロライド４級化物 Ｍｎ：マンニッヒ変性物 Ｈｆ：ホフマン変性物
（ｃ）ＤＭＡＡ：ジメチルアクリルアミド
（ｄ）ＳＭＡＳ：メタアリルスルホン酸ナトリウム
（ｅ）ＡＭ：アクリルアミド
（ｆ）ＭＢＡＡ：メチレンビスアクリルアミド ＡＮ：アクリロニトリル
Moreover, the name of the abbreviation in an Example is shown below.
(A) AA: acrylic acid IA: itaconic acid (b) DM: dimethylaminoethyl methacrylate DMAEA-BQ: benzyl chloride quaternized product of dimethylaminoethyl acrylate DML: benzyl chloride quaternized product of DM Mn: Mannich modified product Hf: Hoffman modified product (c) DMAA: dimethylacrylamide (d) SMAS: sodium methallylsulfonate (e) AM: acrylamide (f) MBAA: methylenebisacrylamide AN: acrylonitrile
製造例１（ＰＡＭ１の製造法）
撹拌機、温度計、還流冷却管、窒素ガス導入管および２つの滴下ロートを備えた反応装置に、イオン交換水３３８部を入れ、窒素ガスを通じて反応系内の酸素を除去した後、９０℃まで加熱した。一方の滴下ロートにアクリルアミド１６６部、６２．５％硫酸１０部、８０％アクリル酸水溶液１０．９部、メタアリルスルホン酸ナトリウム２．１部、ジメチルアミノエチルメタクリレ−ト２０．６部、ジメチルアクリルアミド２．６部、メチレンビスアクリルアミド０．０４部およびイオン交換水１７９部を仕込み、硫酸によりｐＨを３に調整した。また、他方の滴下ロートに過硫酸アンモニウム０．３部とイオン交換水１８０部を入れた。次に、両方の滴下ロートより系内にモノマーおよび触媒を約３時間かけて滴下した。滴下終了後過硫酸アンモニウム０．４部とイオン交換水１０部を入れ１時間保温し、イオン交換水８０部を投入し、固形分２０．１％、粘度（２５℃）が８，０００ｍＰａ・ｓの共重合体水溶液を得た。各製造例で用いたモノマー成分と比率を表１に、また得られた共重合体水溶液の性状値を表２に示す。
Production Example 1 (PAM1 production method)
Into a reactor equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas inlet tube and two dropping funnels, 338 parts of ion-exchanged water was added and oxygen in the reaction system was removed through nitrogen gas, and then up to 90 ° C. Heated. In one dropping funnel, 166 parts of acrylamide, 10 parts of 62.5% sulfuric acid, 10.9 parts of 80% aqueous acrylic acid, 2.1 parts of sodium methallylsulfonate, 20.6 parts of dimethylaminoethyl methacrylate, dimethyl 2.6 parts of acrylamide, 0.04 part of methylenebisacrylamide and 179 parts of ion-exchanged water were charged, and the pH was adjusted to 3 with sulfuric acid. Moreover, 0.3 part of ammonium persulfate and 180 parts of ion-exchange water were put into the other dropping funnel. Next, a monomer and a catalyst were dropped into the system from both dropping funnels over about 3 hours. After completion of dropping, 0.4 part of ammonium persulfate and 10 parts of ion-exchanged water were added and kept for 1 hour, and 80 parts of ion-exchanged water were added. The solid content was 20.1% and the viscosity (25 ° C.) was 8,000 mPa · s. A copolymer aqueous solution was obtained. Table 1 shows the monomer components and ratios used in each production example, and Table 2 shows the property values of the aqueous copolymer solution obtained.
製造例２（ＰＡＭ２製造法）
製造例１と同様の反応装置に、イオン交換水３３８部を入れ、窒素ガスを通じて反応系内の酸素を除去した後、９０℃まで加熱した。一方の滴下ロートにアクリルアミド１６８部、６２．５％硫酸１０部、イタコン酸７．７部、メタアリルスルホン酸ナトリウム１．４部、ジメチルアミノエチルメタクリレ−ト２０部、ジメチルアクリルアミド２．６部、メチレンビスアクリルアミド０．０４部およびイオン交換水１７９部を仕込み、硫酸によりｐＨを３に調整した。また、他方の滴下ロートに過硫酸アンモニウム０．３部とイオン交換水１８０部を入れた。次に、両方の滴下ロートより系内にモノマーおよび触媒を約３時間かけて滴下した。滴下終了後過硫酸アンモニウム０．４部とイオン交換水１０部を入れ１時間保温し、イオン交換水８０部を投入し、固形分２０．３％、粘度（２５℃）が８，０００ｍＰａ・ｓの共重合体水溶液を得た。各製造例で用いたモノマー成分と比率を表１に、また得られた共重合体水溶液の性状値を表２に示す。
Production Example 2 (PAM2 production method)
In a reactor similar to Production Example 1, 338 parts of ion-exchanged water was added, oxygen in the reaction system was removed through nitrogen gas, and then heated to 90 ° C. In one dropping funnel, 168 parts of acrylamide, 10 parts of 62.5% sulfuric acid, 7.7 parts of itaconic acid, 1.4 parts of sodium methallylsulfonate, 20 parts of dimethylaminoethyl methacrylate, 2.6 parts of dimethylacrylamide Then, 0.04 part of methylenebisacrylamide and 179 parts of ion-exchanged water were charged, and the pH was adjusted to 3 with sulfuric acid. Moreover, 0.3 part of ammonium persulfate and 180 parts of ion-exchange water were put into the other dropping funnel. Next, a monomer and a catalyst were dropped into the system from both dropping funnels over about 3 hours. After completion of the dropping, 0.4 part of ammonium persulfate and 10 parts of ion exchange water were added and kept for 1 hour, 80 parts of ion exchange water were added, and the solid content was 20.3% and the viscosity (25 ° C.) was 8,000 mPa · s. A copolymer aqueous solution was obtained. Table 1 shows the monomer components and ratios used in each production example, and Table 2 shows the property values of the aqueous copolymer solution obtained.
製造例３（ＰＡＭ３製造法）
製造例１と同様の反応装置に、アクリルアミド１５５部、６０％ジメチルアミノエチルメタクリレートの４級化物水溶液５６．５部、イタコン酸７．２部、メタアリルスルホン酸ナトリウム１．５部、ジメチルアクリルアミド２．４部、メチレンビスアクリルアミド０．０４部およびイオン交換水６６６部を仕込み、窒素ガスを通じて反応系の酸素を除去した。系内を５５℃にし攪拌下に重合開始剤として過硫酸アンモニウム０．３部とイオン交換水１０部を投入した。９０℃まで昇温した後３０分保温し、過硫酸アンモニウム０．４部とイオン交換水１０部を投入して１時間保温した。重合終了後、イオン交換水８０部を投入し、固形分２０．１％、粘度（２５℃）が８，０００ｍＰａ・ｓの共重合体水溶液を得た。各製造例で用いたモノマー成分と比率を表１に、また得られた共重合体水溶液の性状値を表２に示す。
Production Example 3 (PAM3 production method)
In the same reactor as in Production Example 1, 155 parts of acrylamide, 56.5 parts of an aqueous solution of quaternized 60% dimethylaminoethyl methacrylate, 7.2 parts of itaconic acid, 1.5 parts of sodium methallylsulfonate, dimethylacrylamide 2 4 parts, 0.04 part of methylenebisacrylamide and 666 parts of ion-exchanged water were added, and oxygen in the reaction system was removed through nitrogen gas. The system was brought to 55 ° C., and 0.3 parts of ammonium persulfate and 10 parts of ion-exchanged water were added as a polymerization initiator with stirring. After raising the temperature to 90 ° C., the temperature was kept for 30 minutes, and 0.4 part of ammonium persulfate and 10 parts of ion-exchanged water were added and kept for 1 hour. After completion of the polymerization, 80 parts of ion exchange water was added to obtain a copolymer aqueous solution having a solid content of 20.1% and a viscosity (25 ° C.) of 8,000 mPa · s. Table 1 shows the monomer components and ratios used in each production example, and Table 2 shows the property values of the aqueous copolymer solution obtained.
製造例４（ＰＡＭ４製造法）
製造例１と同様の反応装置に、アクリルアミド８４．３部、６２．５％硫酸５部、ジメチルアミノエチルメタクリレ−ト１０．２部、イタコン酸３．９部、メタアリルスルホン酸ナトリウム０．３部、ジメチルアクリルアミド１．３部およびイオン交換水５４１部を仕込み、窒素ガスを通じて反応系の酸素を除去した。系内を５５℃にし攪拌下に重合開始剤として過硫酸アンモニウム０．１４部とイオン交換水２０部を投入した。９０℃まで昇温した後３０分保温し、過硫酸アンモニウム０．２部とイオン交換水１０部を投入して１時間保温した。重合終了後、イオン交換水３２０部を投入し、固形分１０．２％、粘度（２５℃）が１０，０００ｍＰａ・ｓの共重合体水溶液を得た。各製造例で用いたモノマー成分と比率を表１に、また得られた共重合体水溶液の性状値を表２に示す。
Production Example 4 (PAM4 production method)
In a reactor similar to Production Example 1, 84.3 parts of acrylamide, 5 parts of 62.5% sulfuric acid, 10.2 parts of dimethylaminoethyl methacrylate, 3.9 parts of itaconic acid, sodium methallylsulfonate, 0. 3 parts, 1.3 parts of dimethylacrylamide and 541 parts of ion-exchanged water were charged, and oxygen in the reaction system was removed through nitrogen gas. The system was brought to 55 ° C., and 0.14 part of ammonium persulfate and 20 parts of ion-exchanged water were added as a polymerization initiator with stirring. After raising the temperature to 90 ° C., the temperature was kept for 30 minutes, and 0.2 part of ammonium persulfate and 10 parts of ion-exchanged water were added and kept for 1 hour. After completion of the polymerization, 320 parts of ion-exchanged water was added to obtain a copolymer aqueous solution having a solid content of 10.2% and a viscosity (25 ° C.) of 10,000 mPa · s. Table 1 shows the monomer components and ratios used in each production example, and Table 2 shows the property values of the aqueous copolymer solution obtained.
製造例５（ＰＡＭ５の製造法）
製造例１と同様の反応装置に、イオン交換水１６７部を入れ、窒素ガスを通じて反応系内の酸素を除去した後、９０℃まで加熱した。一方の滴下ロートにアクリルアミド８５．４部、６２．５％硫酸５．１部、イタコン酸３．９部、ジメチルアミノエチルメタクリレ−ト１０．２部およびイオン交換水３００部を仕込み、硫酸によりｐＨを３に調整した。また、他方の滴下ロートに過硫酸アンモニウム０．１４部とイオン交換水１８０部を入れた。次に、両方の滴下ロートより系内にモノマーおよび触媒を約３時間かけて滴下した。滴下終了後過硫酸アンモニウム０．２部とイオン交換水１０部を入れ１時間保温し、イオン交換水３２０部を投入し、固形分１０．２％、粘度（２５℃）が１０，０００ｍＰａ・ｓの共重合体水溶液を得た。各製造例で用いたモノマー成分と比率を表１に、また得られた共重合体水溶液の性状値を表２に示す。
Production Example 5 (PAM5 production method)
In a reaction apparatus similar to Production Example 1, 167 parts of ion-exchanged water was added, oxygen in the reaction system was removed through nitrogen gas, and then heated to 90 ° C. One dropping funnel was charged with 85.4 parts of acrylamide, 5.1 parts of 62.5% sulfuric acid, 3.9 parts of itaconic acid, 10.2 parts of dimethylaminoethyl methacrylate, and 300 parts of ion-exchanged water. The pH was adjusted to 3. Moreover, 0.14 part of ammonium persulfate and 180 parts of ion-exchanged water were added to the other dropping funnel. Next, a monomer and a catalyst were dropped into the system from both dropping funnels over about 3 hours. After completion of the dropping, 0.2 part of ammonium persulfate and 10 parts of ion-exchanged water are added and kept warm for 1 hour, 320 parts of ion-exchanged water are added, and the solid content is 10.2% and the viscosity (25 ° C.) is 10,000 mPa · s. A copolymer aqueous solution was obtained. Table 1 shows the monomer components and ratios used in each production example, and Table 2 shows the property values of the aqueous copolymer solution obtained.
製造例６（ＰＡＭ６製造法）
製造例１と同様の反応装置に、アクリルアミド１４８．１部、７５％ジメチルアミノエチルアクリレ−トの４級化物水溶液５８．９部、８０％アクリル酸水溶液６．３部、メタアリルスルホン酸ナトリウム１．５部、ジメチルアクリルアミド１．２部、メチレンビスアクリルアミド０．０４部およびイオン交換水６７０部を仕込み、窒素ガスを通じて反応系の酸素を除去した。系内を５５℃にし攪拌下に重合開始剤として過硫酸アンモニウム０．２８部とイオン交換水２０部を投入した。９０℃まで昇温した後３０分保温し、過硫酸アンモニウム０．４部とイオン交換水１０部を投入して１時間保温した。重合終了後、イオン交換水４８部を投入し、固形分２０．２％、粘度（２５℃）が８，０００ｍＰａ・ｓの共重合体水溶液を得た。各製造例で用いたモノマー成分と比率を表１に、また得られた共重合体水溶液の性状値を表２に示す。
Production Example 6 (PAM6 production method)
In the same reactor as in Production Example 1, 148.1 parts of acrylamide, 58.9 parts of a quaternized aqueous solution of 75% dimethylaminoethyl acrylate, 6.3 parts of an 80% aqueous acrylic acid solution, sodium methallylsulfonate 1.5 parts, 1.2 parts of dimethylacrylamide, 0.04 parts of methylenebisacrylamide and 670 parts of ion-exchanged water were charged, and oxygen in the reaction system was removed through nitrogen gas. The system was brought to 55 ° C., and 0.28 parts of ammonium persulfate and 20 parts of ion-exchanged water were added as a polymerization initiator with stirring. After raising the temperature to 90 ° C., the temperature was kept for 30 minutes, and 0.4 part of ammonium persulfate and 10 parts of ion-exchanged water were added and kept for 1 hour. After completion of the polymerization, 48 parts of ion exchange water was added to obtain a copolymer aqueous solution having a solid content of 20.2% and a viscosity (25 ° C.) of 8,000 mPa · s. Table 1 shows the monomer components and ratios used in each production example, and Table 2 shows the property values of the aqueous copolymer solution obtained.
製造例７（ＰＡＭ７製造法）
製造例１と同様の反応装置に、アクリルアミド１４６．８部、６０％ジメチルアミノエチルメタクリレ−トの４級化物水溶液７６．６部、８０％アクリル酸水溶液６．３部、メタアリルスルホン酸ナトリウム１．１部、ジメチルアクリルアミド１．２部、メチレンビスアクリルアミド０．０４部およびイオン交換水６６０部を仕込み、窒素ガスを通じて反応系の酸素を除去した。過硫酸アンモニウム０．２８部とイオン交換水２０部を投入した。９０℃まで昇温した後３０分保温し、過硫酸アンモニウム０．４部とイオン交換水１０部を投入して１時間保温した。重合終了後、イオン交換水３８０部を投入し、固形分１５．２％、粘度（２５℃）が１０，０００ｍＰａ・ｓの共重合体水溶液を得た。各製造例で用いたモノマー成分と比率を表１に、また得られた共重合体水溶液の性状値を表２に示す。
Production Example 7 (PAM7 production method)
In the same reactor as in Production Example 1, 146.8 parts of acrylamide, 76.6 parts of an aqueous solution of quaternized 60% dimethylaminoethyl methacrylate, 6.3 parts of an aqueous 80% acrylic acid solution, sodium methallylsulfonate 1.1 parts, 1.2 parts of dimethylacrylamide, 0.04 parts of methylenebisacrylamide and 660 parts of ion-exchanged water were charged, and oxygen in the reaction system was removed through nitrogen gas. 0.28 part of ammonium persulfate and 20 parts of ion exchange water were added. After raising the temperature to 90 ° C., the temperature was kept for 30 minutes, and 0.4 part of ammonium persulfate and 10 parts of ion-exchanged water were added and kept for 1 hour. After completion of the polymerization, 380 parts of ion exchange water was added to obtain a copolymer aqueous solution having a solid content of 15.2% and a viscosity (25 ° C.) of 10,000 mPa · s. Table 1 shows the monomer components and ratios used in each production example, and Table 2 shows the property values of the aqueous copolymer solution obtained.
製造例８（ＰＡＭ８製造法）
製造例１と同様の反応装置に、アクリルアミド８２．６部、６２．５％硫酸７部、ジメチルアミノエチルメタクリレ−ト１４．１部、イタコン酸２．５部、メタアリルスルホン酸ナトリウム０．２部、ジメチルアクリルアミド０．６部、メチレンビスアクリルアミド０．０２部及びイオン交換水５４０部を仕込み、窒素ガスを通じて反応系の酸素を除去した。系内を５５℃にし攪拌下に重合開始剤として過硫酸アンモニウム０．１４部とイオン交換水２０部を投入した。９０℃まで昇温した後３０分保温し、過硫酸アンモニウム０．２部とイオン交換水１０部を投入して１時間保温した。重合終了後、イオン交換水３３０部を投入し、固形分１０．２％、粘度（２５℃）が１０，０００ｍＰａ・ｓの共重合体水溶液を得た。各製造例で用いたモノマー成分と比率を表１に、また得られた共重合体水溶液の性状値を表２に示す。
Production Example 8 (PAM8 production method)
In the same reactor as in Production Example 1, acrylamide 82.6 parts, 62.5% sulfuric acid 7 parts, dimethylaminoethyl methacrylate 14.1 parts, itaconic acid 2.5 parts, sodium methallylsulfonate 2 parts, 0.6 part of dimethylacrylamide, 0.02 part of methylenebisacrylamide and 540 parts of ion-exchanged water were charged, and oxygen in the reaction system was removed through nitrogen gas. The system was brought to 55 ° C., and 0.14 part of ammonium persulfate and 20 parts of ion-exchanged water were added as a polymerization initiator with stirring. After raising the temperature to 90 ° C., the temperature was kept for 30 minutes, and 0.2 part of ammonium persulfate and 10 parts of ion-exchanged water were added and kept for 1 hour. After completion of the polymerization, 330 parts of ion exchange water was added to obtain a copolymer aqueous solution having a solid content of 10.2% and a viscosity (25 ° C.) of 10,000 mPa · s. Table 1 shows the monomer components and ratios used in each production example, and Table 2 shows the property values of the aqueous copolymer solution obtained.
製造例９（ＰＡＭ９製造法）
製造例１と同様の反応装置に、アクリルアミド４１．３部、６２．５％硫酸３．５部、ジメチルアミノエチルメタクリレ−ト７部、イタコン酸１．３部、メタアリルスルホン酸ナトリウム０．０５部、ジメチルアクリルアミド０．３部、メチレンビスアクリルアミド０．０１部およびイオン交換水４３０部を仕込み、窒素ガスを通じて反応系の酸素を除去した。系内を５５℃にし攪拌下に重合開始剤として過硫酸アンモニウム０．０７部とイオン交換水１０部および亜硫酸水素ナトリウム０．０３部とイオン交換水１０部を投入した。９０℃まで昇温した後３０分保温し、過硫酸アンモニウム０．１部とイオン交換水１０部を投入して１時間保温した。重合終了後、イオン交換水４９０部を投入し、固形分５．２％、粘度（２５℃）が１５，０００ｍＰａ・ｓの共重合体水溶液を得た。各製造例で用いたモノマー成分と比率を表１に、また得られた共重合体水溶液の性状値を表２に示す。
Production Example 9 (PAM9 production method)
In a reaction apparatus similar to Production Example 1, 41.3 parts of acrylamide, 3.5 parts of 62.5% sulfuric acid, 7 parts of dimethylaminoethyl methacrylate, 1.3 parts of itaconic acid, sodium methallylsulfonate, 0. 05 parts, 0.3 part of dimethylacrylamide, 0.01 part of methylenebisacrylamide and 430 parts of ion-exchanged water were charged, and oxygen in the reaction system was removed through nitrogen gas. The system was brought to 55 ° C., and 0.07 part of ammonium persulfate, 10 parts of ion-exchanged water, 0.03 part of sodium hydrogen sulfite and 10 parts of ion-exchanged water were added as a polymerization initiator with stirring. After raising the temperature to 90 ° C., the temperature was kept for 30 minutes, and 0.1 part of ammonium persulfate and 10 parts of ion-exchanged water were added and kept for 1 hour. After completion of the polymerization, 490 parts of ion exchange water was added to obtain a copolymer aqueous solution having a solid content of 5.2% and a viscosity (25 ° C.) of 15,000 mPa · s. Table 1 shows the monomer components and ratios used in each production example, and Table 2 shows the property values of the aqueous copolymer solution obtained.
製造例１０（ＰＡＭ１０製造法）
製造例１と同様の反応装置に、アクリルアミド３３．１部、６２．５％硫酸２．８部、ジメチルアミノエチルメタクリレ−ト５．６部、イタコン酸１．０部、メタアリルスルホン酸ナトリウム０．０１部、ジメチルアクリルアミド０．３部、メチレンビスアクリルアミド０．０１部およびイオン交換水３４０部を仕込み、窒素ガスを通じて反応系の酸素を除去した。系内を５５℃にし攪拌下に重合開始剤として過硫酸アンモニウム０．０６部とイオン交換水１０部および亜硫酸水素ナトリウム０．０２部とイオン交換水１０部を投入した。９０℃まで昇温した後３０分保温し、過硫酸アンモニウム０．０８部とイオン交換水１０部を投入して１時間保温した。重合終了後、イオン交換水９１０部を投入し、固形分３．２％、粘度（２５℃）が１５，０００ｍＰａ・ｓの共重合体水溶液を得た。各製造例で用いたモノマー成分と比率を表１に、また得られた共重合体水溶液の性状値を表２に示す。
Production Example 10 (PAM10 production method)
In the same reactor as in Production Example 1, 33.1 parts of acrylamide, 2.8 parts of 62.5% sulfuric acid, 5.6 parts of dimethylaminoethyl methacrylate, 1.0 part of itaconic acid, sodium methallylsulfonate 0.01 part, 0.3 part of dimethylacrylamide, 0.01 part of methylenebisacrylamide and 340 parts of ion-exchanged water were charged, and oxygen in the reaction system was removed through nitrogen gas. The system was brought to 55 ° C., and 0.06 part of ammonium persulfate, 10 parts of ion-exchanged water, 0.02 part of sodium hydrogensulfite and 10 parts of ion-exchanged water were added as a polymerization initiator with stirring. After raising the temperature to 90 ° C., the temperature was kept for 30 minutes, and 0.08 part of ammonium persulfate and 10 parts of ion-exchanged water were added and kept for 1 hour. After the completion of the polymerization, 910 parts of ion exchange water was added to obtain a copolymer aqueous solution having a solid content of 3.2% and a viscosity (25 ° C.) of 15,000 mPa · s. Table 1 shows the monomer components and ratios used in each production example, and Table 2 shows the property values of the aqueous copolymer solution obtained.
製造例１１（ＰＡＭ１１製造法）
製造例１と同様の反応装置に、アクリルアミド１５０．５部、６２．５％硫酸１４．１部、ジメチルアミノエチルメタクリレ−ト２８．４部、８０％アクリル酸水溶液２３．２部、メタアリルスルホン酸ナトリウム１．２部、ジメチルアクリルアミド１．３部、メチレンビスアクリルアミド０．０４部およびイオン交換水７６０部を仕込み、窒素ガスを通じて反応系の酸素を除去した。系内を５５℃にし攪拌下に重合開始剤として過硫酸アンモニウム０．２８部とイオン交換水２０部を投入した。９０℃まで昇温した後３０分保温し、過硫酸アンモニウム０．４部とイオン交換水１０部を投入して１時間保温した。重合終了後、イオン交換水３５０部を投入し、固形分１５．２％、粘度（２５℃）が１０，０００ｍＰａ・ｓの共重合体水溶液を得た。各製造例で用いたモノマー成分と比率を表１に、また得られた共重合体水溶液の性状値を表２に示す。
Production Example 11 (PAM11 production method)
In the same reactor as in Production Example 1, 150.5 parts of acrylamide, 14.1 parts of 62.5% sulfuric acid, 28.4 parts of dimethylaminoethyl methacrylate, 23.2 parts of 80% aqueous acrylic acid solution, methallyl 1.2 parts of sodium sulfonate, 1.3 parts of dimethylacrylamide, 0.04 part of methylenebisacrylamide and 760 parts of ion-exchanged water were charged, and oxygen in the reaction system was removed through nitrogen gas. The system was brought to 55 ° C., and 0.28 parts of ammonium persulfate and 20 parts of ion-exchanged water were added as a polymerization initiator with stirring. After raising the temperature to 90 ° C., the temperature was kept for 30 minutes, and 0.4 part of ammonium persulfate and 10 parts of ion-exchanged water were added and kept for 1 hour. After completion of the polymerization, 350 parts of ion exchange water was added to obtain a copolymer aqueous solution having a solid content of 15.2% and a viscosity (25 ° C.) of 10,000 mPa · s. Table 1 shows the monomer components and ratios used in each production example, and Table 2 shows the property values of the aqueous copolymer solution obtained.
製造例１２（ＰＡＭ１２製造法）
製造例１と同様の反応装置に、アクリルアミド１３５．１部、６０％ジメチルアミノエチルメタクリレ−トの４級化物水溶液７６．５部、８０％アクリル酸水溶液２０．８部、メタアリルスルホン酸ナトリウム１．１部、ジメチルアクリルアミド１．２部、メチレンビスアクリルアミド０．０４部およびイオン交換水７４５部を仕込み、窒素ガスを通じて反応系の酸素を除去した。系内を５５℃にし攪拌下に重合開始剤として過硫酸アンモニウム０．２８部とイオン交換水２０部を投入した。９０℃まで昇温した後３０分保温し、過硫酸アンモニウム０．４部とイオン交換水１０部を投入して１時間保温した。重合終了後、イオン交換水２９０部を投入し、固形分１５．２％、粘度（２５℃）が１０，０００ｍＰａ・ｓの共重合体水溶液を得た。各製造例で用いたモノマー成分と比率を表１に、また得られた共重合体水溶液の性状値を表２に示す。
Production Example 12 (PAM12 production method)
In the same reactor as in Production Example 1, 135.1 parts of acrylamide, 76.5 parts of a quaternized aqueous solution of 60% dimethylaminoethyl methacrylate, 20.8 parts of an 80% aqueous acrylic acid solution, sodium methallylsulfonate 1.1 parts, 1.2 parts of dimethylacrylamide, 0.04 parts of methylenebisacrylamide and 745 parts of ion-exchanged water were charged, and oxygen in the reaction system was removed through nitrogen gas. The system was brought to 55 ° C., and 0.28 parts of ammonium persulfate and 20 parts of ion-exchanged water were added as a polymerization initiator with stirring. After raising the temperature to 90 ° C., the temperature was kept for 30 minutes, and 0.4 part of ammonium persulfate and 10 parts of ion-exchanged water were added and kept for 1 hour. After completion of the polymerization, 290 parts of ion exchange water was added to obtain a copolymer aqueous solution having a solid content of 15.2% and a viscosity (25 ° C.) of 10,000 mPa · s. Table 1 shows the monomer components and ratios used in each production example, and Table 2 shows the property values of the aqueous copolymer solution obtained.
製造例１３（ＰＡＭ１３製造法）
製造例１と同様の反応装置に、アクリルアミド１４０．１部、６０％ジメチルアミノエチルメタクリレ−トの４級化物水溶液７６．６部、８０％アクリル酸水溶液１４．６部、メタアリルスルホン酸ナトリウム１．１部、ジメチルアクリルアミド１．２部、メチレンビスアクリルアミド０．０４部およびイオン交換水７４５部を仕込み、窒素ガスを通じて反応系の酸素を除去した。系内を５５℃にし攪拌下に重合開始剤として過硫酸アンモニウム０．２８部とイオン交換水２０部を投入した。９０℃まで昇温した後３０分保温し、過硫酸アンモニウム０．４部とイオン交換水１０部を投入して１時間保温した。重合終了後、イオン交換水２９０部を投入し、固形分１５．２％、粘度（２５℃）が１０，０００ｍＰａ・ｓの共重合体水溶液を得た。各製造例で用いたモノマー成分と比率を表１に、また得られた共重合体水溶液の性状値を表２に示す。
Production Example 13 (PAM13 production method)
In the same reactor as in Production Example 1, acrylamide 140.1 parts, 60% dimethylaminoethyl methacrylate quaternized aqueous solution 76.6 parts, 80% acrylic acid aqueous solution 14.6 parts, sodium methallylsulfonate 1.1 parts, 1.2 parts of dimethylacrylamide, 0.04 parts of methylenebisacrylamide and 745 parts of ion-exchanged water were charged, and oxygen in the reaction system was removed through nitrogen gas. The system was brought to 55 ° C., and 0.28 parts of ammonium persulfate and 20 parts of ion-exchanged water were added as a polymerization initiator with stirring. After raising the temperature to 90 ° C., the temperature was kept for 30 minutes, and 0.4 part of ammonium persulfate and 10 parts of ion-exchanged water were added and kept for 1 hour. After completion of the polymerization, 290 parts of ion exchange water was added to obtain a copolymer aqueous solution having a solid content of 15.2% and a viscosity (25 ° C.) of 10,000 mPa · s. Table 1 shows the monomer components and ratios used in each production example, and Table 2 shows the property values of the aqueous copolymer solution obtained.
製造例１４（ＰＡＭ１４製造法）
製造例１と同様の反応装置に、アクリルアミド１２４部、８０％アクリル酸水溶液２２部、アクリロニトリル２６部及びイオン交換水６５０部を仕込み、窒素ガスを通じて反応系の酸素を除去した。系内を４０℃にし攪拌下に重合開始剤として過硫酸アンモニウム０．２３部とイオン交換水１０部および亜硫酸水素ナトリウム０．０９部とイオン交換水１０部を投入した。９０℃まで昇温した後、２時間保温した。重合終了後、イオン交換水２７０部を投入し、固形分１５．２％、粘度（２５℃）が５，０００ｍＰａ・ｓの共重合体水溶液を得た。各製造例で用いたモノマー成分と比率を表１に、また得られた共重合体水溶液の性状値を表２に示す。
Production Example 14 (PAM14 production method)
In a reactor similar to Production Example 1, 124 parts of acrylamide, 22 parts of 80% aqueous acrylic acid solution, 26 parts of acrylonitrile and 650 parts of ion-exchanged water were charged, and oxygen in the reaction system was removed through nitrogen gas. The system was heated to 40 ° C., and 0.23 parts of ammonium persulfate, 10 parts of ion-exchanged water, 0.09 part of sodium hydrogensulfite and 10 parts of ion-exchanged water were added as a polymerization initiator with stirring. After raising the temperature to 90 ° C., the temperature was kept for 2 hours. After completion of the polymerization, 270 parts of ion-exchanged water was added to obtain a copolymer aqueous solution having a solid content of 15.2% and a viscosity (25 ° C.) of 5,000 mPa · s. Table 1 shows the monomer components and ratios used in each production example, and Table 2 shows the property values of the aqueous copolymer solution obtained.
製造例１５（ＰＡＭ１５製造法）
製造例１と同様の反応装置に、アクリルアミド７３部、８０％アクリル酸水溶液１０部及びイオン交換水４４０部を仕込み、窒素ガスを通じて反応系の酸素を除去した。系内を４０℃にし攪拌下に重合開始剤として過硫酸アンモニウム０．１部とイオン交換水１０部および亜硫酸水素ナトリウム０．１部とイオン交換水１０部を投入した。９０℃まで昇温した後、１時間保温した。イオン交換水３６０部を投入後４０℃まで冷却し、４８％水酸化ナトリウム０．４部、５０％ジメチルアミン４９部、３７％ホルマリン３７部を投入して１時間保温した。重合終了後、イオン交換水１８０部を投入し、固形分１０．２％、粘度（２５℃）が１０，０００ｍＰａ・ｓの共重合体水溶液を得た。各製造例で用いたモノマー成分と比率を表１に、また得られた共重合体水溶液の性状値を表２に示す。
Production Example 15 (PAM15 production method)
A reaction apparatus similar to Production Example 1 was charged with 73 parts of acrylamide, 10 parts of an 80% aqueous acrylic acid solution, and 440 parts of ion-exchanged water, and oxygen in the reaction system was removed through nitrogen gas. The system was heated to 40 ° C., and 0.1 parts of ammonium persulfate, 10 parts of ion-exchanged water, 0.1 part of sodium bisulfite and 10 parts of ion-exchanged water were added as a polymerization initiator with stirring. After raising the temperature to 90 ° C., the temperature was kept for 1 hour. After adding 360 parts of ion exchange water, it was cooled to 40 ° C., 0.4 parts of 48% sodium hydroxide, 49 parts of 50% dimethylamine and 37 parts of 37% formalin were added and kept warm for 1 hour. After completion of the polymerization, 180 parts of ion-exchanged water was added to obtain a copolymer aqueous solution having a solid content of 10.2% and a viscosity (25 ° C.) of 10,000 mPa · s. Table 1 shows the monomer components and ratios used in each production example, and Table 2 shows the property values of the aqueous copolymer solution obtained.
製造例１６（ＰＡＭ１６製造法）
製造例１と同様の反応装置に、アクリルアミド７１．７部及びイオン交換水３９３部を仕込み、窒素ガスを通じて反応系の酸素を除去した。系内を４０℃にし攪拌下に重合開始剤として過硫酸アンモニウム０．１５部とイオン交換水１０部および亜硫酸水素ナトリウム０．１５部とイオン交換水１０部を投入した。９０℃まで昇温した後、１時間保温した。２０℃まで冷却後、１２％次亜塩素酸ナトリウム２５１．７部と４８％水酸化ナトリウム３３．８部を投入し、３０分保温した。重合終了後、イオン交換水３９５部を投入し、ｐＨ４．０、有効成分５．０％、粘度（２５℃）が２０ｍＰａ・ｓの共重合体水溶液を得た。各製造例で用いたモノマー成分と比率を表１に、また得られた共重合体水溶液の性状値を表２に示す。
Production Example 16 (PAM16 production method)
In a reactor similar to Production Example 1, 71.7 parts of acrylamide and 393 parts of ion-exchanged water were charged, and oxygen in the reaction system was removed through nitrogen gas. The system was brought to 40 ° C., and 0.15 parts of ammonium persulfate, 10 parts of ion-exchanged water, 0.15 part of sodium hydrogensulfite and 10 parts of ion-exchanged water were added as a polymerization initiator with stirring. After raising the temperature to 90 ° C., the temperature was kept for 1 hour. After cooling to 20 ° C., 251.7 parts of 12% sodium hypochlorite and 33.8 parts of 48% sodium hydroxide were added and kept warm for 30 minutes. After completion of the polymerization, 395 parts of ion exchange water was added to obtain a copolymer aqueous solution having a pH of 4.0, an active ingredient of 5.0%, and a viscosity (25 ° C.) of 20 mPa · s. Table 1 shows the monomer components and ratios used in each production example, and Table 2 shows the property values of the aqueous copolymer solution obtained.
表中の数字はいずれもモル％を表す。
All numbers in the table represent mol%.
製造例１６の不揮発物は有効成分を示し、重量平均分子量は変性前のポリマーの測定値。
なお、製１４＋製１５は製造例１４と製造例１５の混合物を示す。混合比は製造例１４／製造例１５＝２／１（重量比）。
The non-volatile material of Production Example 16 represents an active ingredient, and the weight average molecular weight is a measured value of the polymer before modification.
In addition, manufacture 14+ manufacture 15 shows the mixture of manufacture example 14 and manufacture example 15. The mixing ratio is Production Example 14 / Production Example 15 = 2/1 (weight ratio).
実施例１
段ボ−ル古紙をナイアガラ式ビーターにて叩解し、カナディアン・スタンダ−ド・フリ−ネス（Ｃ．Ｓ．Ｆ）３５０ｍｌに調整した紙料に硫酸バンドを１．０％添加してｐＨ６．５とした。当該紙料スラリーを抄紙するにおいて、紙料濃度３．０％として製造例１で得られた重合体水溶液を紙力増強剤として対紙料固形量０．３５％添加し、その後、紙料濃度１．５％として製造例７で得られた重合体水溶液を紙力増強剤として対紙料０．１５％添加し、タッピ・シートマシンにて脱水し、５ｋｇ／ｃｍ２
で２分間プレスして、坪量１５０ｇ／ｍ２ となるよう抄紙した。次いで回転型乾燥機で１０５℃において４分間乾燥し、２３℃、５０％Ｒ．Ｈ．の条件下に２４時間調湿したのち、比破裂強度を測定した。
Example 1
Corrugated cardboard paper is beaten with a Niagara beater and adjusted to 350 ml of Canadian Standard Freeness (C.S.F.) 1.0% sulfuric acid band is added to the stock to a pH of 6.5. It was. In making the paper slurry, the aqueous solution of the polymer obtained in Production Example 1 with a paper stock concentration of 3.0% was added as a paper strength enhancer at 0.35% solids to the paper stock. 1.5% of the aqueous polymer solution obtained in Production Example 7 as a paper strength enhancer was added at 0.15%, dehydrated with a tapi sheet machine, and 5 kg / cm 2.
And pressed for 2 minutes to make a paper having a basis weight of 150 g / m 2 . Subsequently, it dried for 4 minutes at 105 degreeC with a rotary dryer, and 23 degreeC and 50% R. H. After conditioned for 24 hours under the above conditions, the specific burst strength was measured.
実施例２〜９、比較例１〜６
使用紙力増強剤、紙力増強剤添加時の紙料濃度を表３のように変更した他は、実施例１と同様にして比破裂強度を測定した。結果を表３に示す。
Examples 2-9, Comparative Examples 1-6
The specific burst strength was measured in the same manner as in Example 1 except that the paper strength at the time of adding the paper strength enhancer and the strength enhancer was changed as shown in Table 3. The results are shown in Table 3.
なお、添加場所１での紙料濃度は３．０％、添加場所２での紙料濃度は１．５％である。
The stock concentration at the addition site 1 is 3.0%, and the stock concentration at the addition location 2 is 1.5%.
実施例１０
Ｌ−ＵＫＰ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）４５０ｍｌに調整した紙料に硫酸バンドを１．０％添加してｐＨ６．５とした。当該紙料スラリーを抄紙するにおいて、紙料濃度２．０％として製造例１で得られた重合体水溶液を紙力増強剤として対紙料１．０％添加し、その後、紙料濃度１．０％として製造例８で得られた重合体水溶液を紙力増強剤として対紙料０．２％添加し、タッピ・シートマシンにて脱水し、５ｋｇ／ｃｍ２ で２分間プレスして、坪量１５０ｇ／ｍ２ となるよう抄紙した。次いで回転型乾燥機で１０５℃において４分間乾燥し、２３℃、５０％Ｒ．Ｈ．の条件下に２４時間調湿したのち、比破裂強度を測定した。
Example 10
L-UKP was beaten with a Niagara-type beater, and 1.0% of a sulfuric acid band was added to the paper stock adjusted to 450 ml of Canadian Standard Freeness (C.S.F.) to adjust the pH to 6.5. . In making the paper slurry, the aqueous polymer solution obtained in Production Example 1 with a paper stock concentration of 2.0% was added as a paper strength enhancer to 1.0% of the paper stock, and then the paper stock concentration of 1. Add 0.2% of the aqueous polymer solution obtained in Production Example 8 as a paper strength enhancer to 0%, dehydrate with a tapi sheet machine, press at 5 kg / cm 2 for 2 minutes, Paper was made so that the amount was 150 g / m 2 . Subsequently, it dried for 4 minutes at 105 degreeC with a rotary dryer, and 23 degreeC and 50% R. H. After conditioned for 24 hours under the above conditions, the specific burst strength was measured.
実施例１１〜１８、比較例７〜１２
使用紙力増強剤、紙力増強剤添加時の紙料濃度を表４のように変更した他は、実施例１０と同様にして比破裂強度を測定した。結果を表４に示す。
Examples 11-18, Comparative Examples 7-12
The specific burst strength was measured in the same manner as in Example 10 except that the paper strength at the time of adding the paper strength enhancer and the paper strength enhancer was changed as shown in Table 4. The results are shown in Table 4.
なお、添加場所１での紙料濃度は２．０％、添加場所２での紙料濃度は１．０％である。
In addition, the paper material density | concentration in the addition place 1 is 2.0%, and the paper material density | concentration in the addition place 2 is 1.0%.
表３、４から明らかなように、本発明によれば、ノニオン性ポリアクリルアミド系紙力増強剤と紙力増強剤の添加前後におけるＪＩＳ Ｐ ８１２１により測定される濾水度の差がノニオン性ポリアクリルアミド系紙力増強剤よりも大きいノニオン性ポリアクリルアミド系紙力増強剤を添加する処方や、カチオン性ポリアクリルアミド系紙力増強剤と紙力増強剤の添加前後におけるＪＩＳ Ｐ ８１２１により測定される濾水度の差がカチオン性ポリアクリルアミド系紙力増強剤よりも大きいノニオン性ポリアクリルアミド系紙力増強剤を添加する処方対比強度が高い紙を容易に製造することが出来る（実施例１〜２０、比較例１、２、７、８）。なお、（Ａ）成分／（Ｂ）成分が０．２未満の場合は、若干紙力効果が低下する傾向にあるため、０．２以上とすることが好ましい（実施例１と６、１１と１６）。さらに、（Ａ）成分を紙料濃度２．０％未満として添加し、（Ｂ）成分を紙料濃度２．０％以上として添加すると若干紙力効果が低下する傾向にあるため、（Ａ）成分は紙料濃度２．０％以上として、（Ｂ）成分は紙料濃度２．０％未満として添加することが好ましい（実施例１と１０、１１と２０）。（Ａ）成分の重量平均分子量が１００万未満の場合、若干紙力効果が低下する傾向にあるため、（Ａ）成分の重量平均分子量は１００万以上とすることが好ましい（実施例３と５、１３と１５）。（Ｂ）成分の５重量％水溶液での粘度が２０，０００ｍＰａ・ｓを越える場合、地合乱れが起こることで若干紙力効果が低下する傾向にあるため、（Ｂ）成分の５重量％水溶液での粘度は２０，０００ｍＰａ・ｓ以下とすることが好ましい（実施例２と７、１２と１７）。異なる（Ａ）成分を紙料濃度２．０％以上として、紙料濃度２．０％未満として添加しても充分な紙力効果が得られない（実施例１〜２０、比較例３と５、９と１１）。また、異なる（Ｂ）成分を紙料濃度２．０％以上として、紙料濃度２．０％未満として添加しても充分な紙力効果が得られない（実施例１〜２０、比較例４と６、１０と１２）。
As is apparent from Tables 3 and 4, according to the present invention, the difference in the freeness measured by JIS P 8121 before and after the addition of the nonionic polyacrylamide-based paper strength enhancer and the paper strength enhancer is the nonionic polyacrylamide. A prescription in which a nonionic polyacrylamide type paper strength enhancer larger than an acrylamide type paper strength enhancer is added, or a filter measured by JIS P 8121 before and after the addition of a cationic polyacrylamide type paper strength enhancer and a paper strength enhancer. A paper having a high formulation contrast strength to which a nonionic polyacrylamide-based paper strength enhancer having a greater difference in water degree than that of a cationic polyacrylamide-based paper strength enhancer can be easily produced (Examples 1 to 20, Comparative Examples 1, 2, 7, 8). In addition, when the component (A) / component (B) is less than 0.2, the paper strength effect tends to be slightly lowered, and therefore, it is preferably 0.2 or more (Examples 1, 6, and 11). 16). Furthermore, when the component (A) is added at a paper stock concentration of less than 2.0% and the component (B) is added at a paper stock concentration of 2.0% or more, the paper strength effect tends to decrease slightly. The component is preferably added at a paper stock concentration of 2.0% or more, and the component (B) is preferably added at a paper stock concentration of less than 2.0% (Examples 1 and 10, 11 and 20). When the weight average molecular weight of the component (A) is less than 1,000,000, the paper strength effect tends to be slightly reduced. Therefore, the weight average molecular weight of the component (A) is preferably 1 million or more (Examples 3 and 5). 13 and 15). When the viscosity of the (B) component in a 5% by weight aqueous solution exceeds 20,000 mPa · s, the paper strength effect tends to decrease slightly due to the formation disturbance, so the 5% by weight aqueous solution of the (B) component The viscosity is preferably 20,000 mPa · s or less (Examples 2 and 7, 12 and 17). Even when the different component (A) is added at a stock concentration of 2.0% or more and less than 2.0%, a sufficient paper strength effect cannot be obtained (Examples 1 to 20, Comparative Examples 3 and 5). 9 and 11). Further, even when different component (B) is added at a paper stock concentration of 2.0% or more and less than a paper stock concentration of 2.0%, sufficient paper strength effect cannot be obtained (Examples 1 to 20, Comparative Example 4). And 6, 10 and 12).
Claims (7)
紙力増強剤の添加前後におけるＪＩＳ Ｐ ８１２１により測定される濾水度の差がノニオン性ポリアクリルアミド系紙力増強剤（Ａ）よりも大きい、（ａ）〜（ｃ）成分を必須成分とし、かつ、（ｃ）／（ｂ）比が０．８５未満となるように配合（ただし、（ｃ）成分が２価の酸の場合、（ｃ）成分のモル％を２倍した値を用いる。）したモノマー成分を共重合して得られるポリアクリルアミド系樹脂を含有するカチオン性ポリアクリルアミド系紙力増強剤（Ｂ−１）または（ａ）〜（ｃ）成分を必須成分とし、かつ、（ｃ）／（ｂ）比が１．１を越えるように配合（ただし、（ｃ）成分が２価の酸の場合、（ｃ）成分のモル％を２倍した値を用いる。）したモノマー成分を共重合して得られるポリアクリルアミド系樹脂を含有するアニオン性ポリアクリルアミド系紙力増強剤（Ｂ−２）とを用い抄紙することを特徴とする紙の製造方法。 (A) (Meth) acrylamide, (b) a cationic vinyl monomer, (c) an anionic vinyl monomer as an essential component, and a ratio (mol% of component (c) / mol% of component (b) ((c ) / (B) ratio) is in the range of 0.85 to 1.1 (however, when component (c) is a divalent acid, the value obtained by doubling mol% of component (c)) used.) and nonionic polyacrylamide strength agent to the monomer component containing a copolymerized polyacrylamide-based resin obtained was a (a),
Difference in freeness as measured by JIS P 8121 in addition before and after the paper strength agent is greater than nonionic polyacrylamide strength agent (A), an essential component of (a) ~ (c) component And blended so that the ratio (c) / (b) is less than 0.85 (however, when the component (c) is a divalent acid, a value obtained by doubling the mol% of the component (c)) is used. .) Cationic polyacrylamide-based paper strength enhancer (B-1) or (a) to (c) component containing a polyacrylamide-based resin obtained by copolymerizing the monomer component obtained as an essential component, and ( c) / (b) monomer component blended so that the ratio exceeds 1.1 (however, when component (c) is a divalent acid, a value obtained by doubling the mol% of component (c) is used). anions containing a copolymerized polyacrylamide-based resin obtained by Process for manufacturing paper, which comprises paper using a polyacrylamide-based paper strength agent (B-2).
The nonionic polyacrylamide type paper strength enhancer (A) and the cationic polyacrylamide type paper strength enhancer (B-1) or the anionic polyacrylamide type paper strength enhancer (B-2) are: (Meth) acrylamide, (b) cationic vinyl monomer, (c) anionic vinyl monomer, (d) N-substituted (meth) acrylamide, (e) sodium (meth) allyl sulfonate (F) The method for producing paper according to any one of claims 1 to 6, comprising a polymer obtained by copolymerizing a vinyl monomer other than the components (a) to (e).
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| CN104452455B (en) | 2013-09-12 | 2019-04-05 | 艺康美国股份有限公司 | The method that paper making auxiliary agent composition and increase are stayed at paper ash code insurance |
| CN104452463B (en) | 2013-09-12 | 2017-01-04 | 艺康美国股份有限公司 | Papermaking process and compositions |
| JP6268519B2 (en) * | 2013-12-12 | 2018-01-31 | 荒川化学工業株式会社 | Surface paper strength enhancer for papermaking and surface coated paper |
| FI126610B (en) | 2015-01-27 | 2017-03-15 | Kemira Oyj | Particulate polymer product and its use |
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| US4894119A (en) * | 1985-04-10 | 1990-01-16 | Drew Chemical Corporation | Retention and/or drainage and/or dewatering aid |
| US6168686B1 (en) * | 1998-08-19 | 2001-01-02 | Betzdearborn, Inc. | Papermaking aid |
| JP2001020198A (en) * | 1999-07-09 | 2001-01-23 | Seiko Kagaku Kogyo Co Ltd | Papermaking additive |
| JP4232189B2 (en) * | 2002-11-12 | 2009-03-04 | 荒川化学工業株式会社 | Paper manufacturing method |
| JP2004300629A (en) * | 2003-03-31 | 2004-10-28 | Arakawa Chem Ind Co Ltd | Additive for papermaking and paper using additive for papermaking |
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