JP4158145B2 - Papermaking additive and method for producing papermaking additive - Google Patents
Papermaking additive and method for producing papermaking additive Download PDFInfo
- Publication number
- JP4158145B2 JP4158145B2 JP2002554324A JP2002554324A JP4158145B2 JP 4158145 B2 JP4158145 B2 JP 4158145B2 JP 2002554324 A JP2002554324 A JP 2002554324A JP 2002554324 A JP2002554324 A JP 2002554324A JP 4158145 B2 JP4158145 B2 JP 4158145B2
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- JP
- Japan
- Prior art keywords
- monomers
- mol
- monomer
- paper
- acrylamide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000000654 additive Substances 0.000 title claims description 42
- 230000000996 additive effect Effects 0.000 title claims description 39
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 239000000178 monomer Substances 0.000 claims description 197
- 238000006243 chemical reaction Methods 0.000 claims description 49
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 47
- 238000006116 polymerization reaction Methods 0.000 claims description 36
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 33
- 229920002554 vinyl polymer Polymers 0.000 claims description 33
- -1 urea compound Chemical class 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 17
- 239000004202 carbamide Substances 0.000 claims description 16
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 15
- 125000001302 tertiary amino group Chemical group 0.000 claims description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 13
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 13
- 239000003505 polymerization initiator Substances 0.000 claims description 10
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 239000000123 paper Substances 0.000 description 99
- 229920002401 polyacrylamide Polymers 0.000 description 73
- 239000007864 aqueous solution Substances 0.000 description 59
- 239000000243 solution Substances 0.000 description 51
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 44
- 230000000052 comparative effect Effects 0.000 description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 30
- 229910001873 dinitrogen Inorganic materials 0.000 description 28
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 25
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 25
- 239000007787 solid Substances 0.000 description 25
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 24
- 229920000642 polymer Polymers 0.000 description 19
- 238000005259 measurement Methods 0.000 description 18
- 239000013055 pulp slurry Substances 0.000 description 18
- 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 18
- ZGCZDEVLEULNLJ-UHFFFAOYSA-M benzyl-dimethyl-(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C=CC(=O)OCC[N+](C)(C)CC1=CC=CC=C1 ZGCZDEVLEULNLJ-UHFFFAOYSA-M 0.000 description 16
- 238000010992 reflux Methods 0.000 description 16
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 238000001308 synthesis method Methods 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 239000012298 atmosphere Substances 0.000 description 13
- 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 12
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 description 12
- 150000003926 acrylamides Chemical class 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 12
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 11
- FYBFGAFWCBMEDG-UHFFFAOYSA-N 1-[3,5-di(prop-2-enoyl)-1,3,5-triazinan-1-yl]prop-2-en-1-one Chemical compound C=CC(=O)N1CN(C(=O)C=C)CN(C(=O)C=C)C1 FYBFGAFWCBMEDG-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 229920001131 Pulp (paper) Polymers 0.000 description 7
- 125000000129 anionic group Chemical group 0.000 description 7
- 230000002708 enhancing effect Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 6
- 230000001143 conditioned effect Effects 0.000 description 6
- 238000004513 sizing Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000002023 wood Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 4
- 239000012986 chain transfer agent Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- WFKDPJRCBCBQNT-UHFFFAOYSA-N n,2-dimethylprop-2-enamide Chemical compound CNC(=O)C(C)=C WFKDPJRCBCBQNT-UHFFFAOYSA-N 0.000 description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 238000010009 beating Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003377 silicon compounds Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical class OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 description 2
- 239000003623 enhancer Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 150000002500 ions Chemical class 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
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 2
- 239000010893 paper waste Substances 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000000346 sugar Nutrition 0.000 description 2
- 150000008163 sugars Chemical class 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 description 2
- 150000003672 ureas Chemical class 0.000 description 2
- JDCBWJCUHSVVMN-SCSAIBSYSA-N (2r)-but-3-en-2-amine Chemical class C[C@@H](N)C=C JDCBWJCUHSVVMN-SCSAIBSYSA-N 0.000 description 1
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 description 1
- HIACAHMKXQESOV-UHFFFAOYSA-N 1,2-bis(prop-1-en-2-yl)benzene Chemical compound CC(=C)C1=CC=CC=C1C(C)=C HIACAHMKXQESOV-UHFFFAOYSA-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
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- ZZHQUFIOKFFEAC-UHFFFAOYSA-N 18-triacetyloxysilyloctadecyl prop-2-enoate Chemical compound C(C=C)(=O)OCCCCCCCCCCCCCCCCCC[Si](OC(C)=O)(OC(C)=O)OC(C)=O ZZHQUFIOKFFEAC-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
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 1
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- HGJDNBZIDQOMEU-UHFFFAOYSA-N 2-methyl-n,n-bis(prop-2-enyl)prop-2-enamide Chemical compound CC(=C)C(=O)N(CC=C)CC=C HGJDNBZIDQOMEU-UHFFFAOYSA-N 0.000 description 1
- LDCWGVLBCJEQMT-UHFFFAOYSA-N 2-methyl-n-(2-methylprop-2-enyl)prop-2-en-1-amine Chemical class CC(=C)CNCC(C)=C LDCWGVLBCJEQMT-UHFFFAOYSA-N 0.000 description 1
- VXDHQYLFEYUMFY-UHFFFAOYSA-N 2-methylprop-2-en-1-amine Chemical compound CC(=C)CN VXDHQYLFEYUMFY-UHFFFAOYSA-N 0.000 description 1
- NRVQUYCYEAKQIF-UHFFFAOYSA-N 2-phenyl-2-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound C=CC(=O)NC(CS(O)(=O)=O)(C)C1=CC=CC=C1 NRVQUYCYEAKQIF-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
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- HHHPYRGQUSPESB-UHFFFAOYSA-N 3-(dimethoxymethylsilyl)propyl prop-2-enoate Chemical compound COC(OC)[SiH2]CCCOC(=O)C=C HHHPYRGQUSPESB-UHFFFAOYSA-N 0.000 description 1
- BXAAQNFGSQKPDZ-UHFFFAOYSA-N 3-[1,2,2-tris(prop-2-enoxy)ethoxy]prop-1-ene Chemical compound C=CCOC(OCC=C)C(OCC=C)OCC=C BXAAQNFGSQKPDZ-UHFFFAOYSA-N 0.000 description 1
- GBAQKTTVWCCNHH-UHFFFAOYSA-N 3-[dichloro(methyl)silyl]propyl prop-2-enoate Chemical compound C[Si](Cl)(Cl)CCCOC(=O)C=C GBAQKTTVWCCNHH-UHFFFAOYSA-N 0.000 description 1
- WOZHZOLFFPSEAM-UHFFFAOYSA-N 3-butene-1,2,3-tricarboxylic acid Chemical compound OC(=O)CC(C(O)=O)C(=C)C(O)=O WOZHZOLFFPSEAM-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- XWNSFEAWWGGSKJ-UHFFFAOYSA-N 4-acetyl-4-methylheptanedinitrile Chemical compound N#CCCC(C)(C(=O)C)CCC#N XWNSFEAWWGGSKJ-UHFFFAOYSA-N 0.000 description 1
- XRUKRHLZDVJJSX-UHFFFAOYSA-N 4-cyanopentanoic acid Chemical compound N#CC(C)CCC(O)=O XRUKRHLZDVJJSX-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- VVOPPFQHSWHFCD-UHFFFAOYSA-M Br(=O)(=O)[O-].[Br+] Chemical compound Br(=O)(=O)[O-].[Br+] VVOPPFQHSWHFCD-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 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
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004153 Potassium bromate Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- ONYIMLIZURYBQI-UHFFFAOYSA-N [diacetyloxymethyl(2,5-dimethylhexyl)silyl] prop-2-enoate Chemical compound C(C=C)(=O)O[SiH](C(OC(C)=O)OC(C)=O)CC(CCC(C)C)C ONYIMLIZURYBQI-UHFFFAOYSA-N 0.000 description 1
- KTVHXOHGRUQTPX-UHFFFAOYSA-N [ethenyl(dimethyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(C)C=C KTVHXOHGRUQTPX-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 229940091181 aconitic acid Drugs 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 150000001323 aldoses Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000008126 allyl sulfides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 125000004069 aziridinyl group Chemical group 0.000 description 1
- 239000007869 azo polymerization initiator Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- JZQAAQZDDMEFGZ-UHFFFAOYSA-N bis(ethenyl) hexanedioate Chemical compound C=COC(=O)CCCCC(=O)OC=C JZQAAQZDDMEFGZ-UHFFFAOYSA-N 0.000 description 1
- CJKWEXMFQPNNTL-UHFFFAOYSA-N bis(prop-2-enyl) 1,2,3,4,7,7-hexachlorobicyclo[2.2.1]hept-2-ene-5,6-dicarboxylate Chemical compound C=CCOC(=O)C1C(C(=O)OCC=C)C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl CJKWEXMFQPNNTL-UHFFFAOYSA-N 0.000 description 1
- YLTDNYQTDYMOBH-UHFFFAOYSA-N bis(prop-2-enyl) 2-hydroxybutanedioate Chemical compound C=CCOC(=O)C(O)CC(=O)OCC=C YLTDNYQTDYMOBH-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- HABAXTXIECRCKH-UHFFFAOYSA-N bis(prop-2-enyl) butanedioate Chemical compound C=CCOC(=O)CCC(=O)OCC=C HABAXTXIECRCKH-UHFFFAOYSA-N 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 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
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000011109 contamination 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
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- YIOJGTBNHQAVBO-UHFFFAOYSA-N dimethyl-bis(prop-2-enyl)azanium Chemical class C=CC[N+](C)(C)CC=C YIOJGTBNHQAVBO-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- BHDAXLOEFWJKTL-UHFFFAOYSA-L dipotassium;carboxylatooxy carbonate Chemical compound [K+].[K+].[O-]C(=O)OOC([O-])=O BHDAXLOEFWJKTL-UHFFFAOYSA-L 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- HJWBBBADPXPUPA-UHFFFAOYSA-N ethyl 3-(4-chlorophenyl)-5-methyl-1,2-oxazole-4-carboxylate Chemical compound CCOC(=O)C1=C(C)ON=C1C1=CC=C(Cl)C=C1 HJWBBBADPXPUPA-UHFFFAOYSA-N 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229960001031 glucose Drugs 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229960003151 mercaptamine Drugs 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 1
- WYRJQOPVEMCABI-UHFFFAOYSA-N n,n,n',n'-tetrakis(prop-2-enyl)butane-1,4-diamine Chemical compound C=CCN(CC=C)CCCCN(CC=C)CC=C WYRJQOPVEMCABI-UHFFFAOYSA-N 0.000 description 1
- BLYOHBPLFYXHQA-UHFFFAOYSA-N n,n-bis(prop-2-enyl)prop-2-enamide Chemical compound C=CCN(CC=C)C(=O)C=C BLYOHBPLFYXHQA-UHFFFAOYSA-N 0.000 description 1
- RIELFOQEDSWVGH-UHFFFAOYSA-N n-[(prop-2-enoylamino)methylidenecarbamoyliminomethyl]prop-2-enamide Chemical compound C=CC(=O)NC=NC(=O)N=CNC(=O)C=C RIELFOQEDSWVGH-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- QWFQZTFNZZNHLR-UHFFFAOYSA-N pent-4-ene-1,2,4-tricarboxylic acid Chemical compound OC(=O)CC(C(O)=O)CC(=C)C(O)=O QWFQZTFNZZNHLR-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000005342 perphosphate group Chemical group 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000012985 polymerization agent Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229940094037 potassium bromate Drugs 0.000 description 1
- 235000019396 potassium bromate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 229960004793 sucrose Drugs 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- HEKQWIORQJRILW-UHFFFAOYSA-N tetrakis(prop-2-enyl) benzene-1,2,4,5-tetracarboxylate Chemical compound C=CCOC(=O)C1=CC(C(=O)OCC=C)=C(C(=O)OCC=C)C=C1C(=O)OCC=C HEKQWIORQJRILW-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- GRPURDFRFHUDSP-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,2,4-tricarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C(C(=O)OCC=C)=C1 GRPURDFRFHUDSP-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
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/06—Paper forming aids
- D21H21/10—Retention agents or drainage improvers
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
- D21H17/43—Carboxyl groups or derivatives thereof
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
- D21H17/45—Nitrogen-containing groups
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paper (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【技術分野】
【０００１】
本発明は、製紙用添加剤及び製紙用添加剤の製造方法に関し、詳しくは、酸性、中性、ないしは、アルカリ性領域での抄紙系で、優れた濾水性、歩留まり及び紙力増強効果を発現しうるポリアクリルアミド系共重合体の製紙用添加剤、及び、その製紙用添加剤の製造方法に関する。
【背景技術】
【０００２】
従来より製紙工程において、抄紙機の高速化に伴う生産性の向上、あるいは紙の品質向上を図る為に種々の製紙用添加剤が用いられてきた。とりわけ、紙力増強剤は紙質向上及び生産性向上を図る上で重要な薬品であり、その使用範囲は益々広まると共に、薬品の改良が進んでいる。
【０００３】
紙力増強剤としては、ポリアクリルアミド系共重合体が広く用いられており、そのイオン性の観点から、アニオン性、カチオン性及び、両性の共重合体に分類されている。まず、１９６０年代に、アニオン性ポリアクリルアミド系共重合体が硫酸バンドと併用されるようになった。次いで、１９７０〜８０年代に、濾水や歩留りの改善を目的に、カチオン性を導入したマンニッヒ変性アクリルアミド系ポリマーや、ホフマン変性アクリルアミド系ポリマーが使用されるようになった。しかし、これらの変性アクリルアミド系ポリマーは、製品安定性が悪く、マンニッヒ変性アクリルアミド系ポリマーの場合、製品中にホルマリンを含有するといった問題があった。
【０００４】
次いで、１９８０年代から、アニオン性、及びカチオン性のビニル化合物をアクリルアミドと共重合した両性のポリアクリルアミド系共重合体が使用されるようになった（特開昭６０−９４６９７号公報）。この両性ポリアクリルアミド系共重合体は単独で、又はアニオン性ポリアクリルアミド系共重合体と併用されている。上記のポリアクリルアミド系共重合体は、所定の温度で、モノマー溶液に重合開始剤を添加し、重合を行うことにより製造されてきた。
【０００５】
近年、ポリアクリルアミド系共重合体の紙力向上効果を高めるべく、重合方法の改良が行われている。例えば、予めポリアクリルアミドを合成し、そのポリアクリルアミドの存在下で、アクリルアミド類のモノマー溶液の重合を行う方法（特開平３−２２７４８５号公報）や、ポリアクリルアミドにアクリルアミド等のモノマーを滴下して重合（特開平５−１９５４８５号公報）し、グラフト構造を導入する方法が開示されている。これらの方法は、予めポリアクリルアミドを合成した後で、更にアクリルアミドの重合を行うので生産性が劣るという欠点があった。また、架橋性置換基を側鎖に有するモノマーを含むモノマーを全量滴下重合することで、ポリマー中の分岐・架橋を進め、高分子量化を図り、紙力を向上させる方法が開示されている（特開平７−１３３５９９号公報、特開平７−１８８３５１号公報、特開平１１−２２８６４１号公報、特開平８−６７７１５号公報）。更に、アニオン性ポリアクリルアミド系共重合体、及びカチオン性ポリアクリルアミド系共重合体を２段階の滴下重合で連続的に合成し、いわゆるイオンコンプレックスを形成させることで、性能を向上する方法が開示されている（特開平６−１９９９６５号公報、特開平７−９０７９７号公報）。 しかし、近年、製紙原料の品質の振れに伴う抄紙する際におけるパルプスラリーのｐＨの変動や、古紙の使用量の増加、系のクローズド化の進展に伴う夾雑物の混入、微細繊維の増加等により、従来のポリアクリルアミド系共重合体製紙用添加剤では十分な効果が得られなくなってきている。このような状況下、生産性の向上や紙力の向上を図る為に、更なる製紙用添加剤の改良が求められている。
【発明の開示】
【発明が解決しようとする課題】
【０００６】
本発明は、抄紙する際におけるパルプスラリーのｐＨの変動、製紙原料の悪化に伴う夾雑物の混入、抄紙白水の電導度の増加、及び微細繊維の増加等により紙力増強効果が得られにくい状況においても、優れた紙力増強効果を発揮する製紙用添加剤、及びその製造方法を提供することを目的とする。
【課題を解決するための手段】
【０００７】
本発明者は、上記の課題を解決する為、鋭意研究を重ねた結果、ポリアクリルアミド系共重合体の製紙用添加剤を製造する際において、モノマー類の重合を開始後、特定の反応率に達した時点で残りのモノマー類を添加し、重合することで、紙力増強効果に優れる製紙用添加剤が得られることを見出し、本発明を完成するに至った。
【０００８】
すなわち前記課題を解決するための手段である本発明は、（１）（ａ）（メタ）アクリルアミド、（ｂ）カルボキシル基及び／又はスルホン酸基を有するビニルモノマー及びその塩類、（ｃ）３級アミノ基又は４級アンモニウム塩類を有するビニルモノマー、並びに、（ｄ）多官能性モノマーのみを含有するモノマー類（Ａ）に重合開始剤を加え、重合を開始した後、モノマー類（Ａ）の反応率が２０〜９６．５％に達した時点で、さらに（ａ）（メタ）アクリルアミド、（ｂ）カルボキシル基及び／又はスルホン酸基を有するビニルモノマー及びその塩類、（ｃ）３級アミノ基又は４級アンモニウム塩類を有するビニルモノマー、並びに（ｄ）多官能性モノマーより成る群から選択される少なくとも１種のモノマーのみを含有するモノマー類（Ｂ）を、滴下して重合することを特徴とする製紙用添加剤の製造方法、
（２）前記（１）における滴下するモノマー類（Ｂ）が、（ｂ）カルボキシル基及び／又はスルホン酸基を有するビニルモノマー及びその塩類から成る前記（１）の製紙用添加剤の製造方法、
（３）前記（１）における滴下するモノマー類（Ｂ）が、（ｃ）３級アミノ基又は４級アンモニウム塩類を有するビニルモノマーから成る前記（１）の製紙用添加剤の製造方法、
（４）前記（１）における滴下するモノマー類（Ｂ）が、（ｂ）カルボキシル基及び／又はスルホン酸基を有するビニルモノマー及びその塩類、並びに（ｃ）３級アミノ基又は４級アンモニウム塩類を有するビニルモノマーから成る前記（１）の製紙用添加剤の製造方法、
（５）前記（１）における滴下するモノマー類（Ｂ）が、（ａ）（メタ）アクリルアミド、（ｂ）カルボキシル基及び／又はスルホン酸基を有するビニルモノマー及びその塩類、（ｃ）３級アミノ基又は４級アンモニウム塩類を有するビニルモノマー、並びに（ｄ）架橋性モノマーから成る前記（１）の製紙用添加剤の製造方法、
（６）前記モノマー類（Ａ）の反応率が３０〜９０％に達した時点で、前記モノマー類（Ｂ）を滴下して重合することを特徴とする前記（１）〜（５）のいずれか１項に記載の製紙用添加剤の製造方法、及び
（７）尿素類化合物の存在下で重合することを特徴とする前記（１）〜（６）のいずれか一つに記載の製紙用添加剤の製造方法を提供するものである。
【０００９】
以下、本発明を詳細に説明する。本発明は、（ａ）〜（ｄ）成分のモノマーを含有するモノマー類（Ａ）に重合開始剤を加え、重合を開始した後、モノマー類（Ａ）の反応率が２０〜９６．５％に達した時点で、さらに（ａ）〜（ｄ）成分の少なくとも１種のモノマーを含有するモノマー類（Ｂ）を、滴下することにより重合する製紙用添加剤の製造方法に関する。
【００１０】
本発明で用いることができる（ａ）（メタ）アクリルアミドはアクリルアミド、又はメタクリルアミドであり、これらは、粉体でも、水溶液でも使用することができる。
【００１１】
本発明で用いることができる（ｂ）カルボキシル基を有するビニルモノマーとしては、例えば、アクリル酸、メタクリル酸、及びクロトン酸等の不飽和モノカルボン酸、フマル酸、マレイン酸、イタコン酸、シトラコン酸、及びムコン酸等の不飽和ジカルボン酸、アコニット酸、３−ブテン−１,２,３−トリカルボン酸、４−ペンテン−１,２,４−トリカルボン酸等の不飽和トリカルボン酸が挙げられる。スルホン酸基を有するビニルモノマーとしては、例えば、ビニルスルホン酸、スチレンスルホン酸、（メタ）アリルスルホン酸、２−アクリルアミド−２−メチルプロパンスルホン酸、２−アクリルアミド−２−フェニルプロパンスルホン酸等が挙げられる。また、カルボキシル基を有するビニルモノマー及びスルホン酸基を有するビニルモノマーの塩類としては、前記カルボキシル基を有するビニルモノマー、又は、前記スルホン酸基を有するビニルモノマーのアルカリ金属塩、アルカリ土類金属塩、及びアンモニウム塩等が挙げられる。これらは、１種単独で用いても良いし、２種以上を併用しても良い。
【００１２】
本発明で用いることができる（ｃ）３級アミノ基を有するビニルモノマーとしては、例えばジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、ジメチルアミノプロピル（メタ）アクリレート、及びジエチルアミノプロピル（メタ）アクリレート等のジアルキルアミノアルキル（メタ）アクリレート類、ジメチルアミノプロピル（メタ）アクリルアミド、及びジエチルアミノプロピル（メタ）アクリルアミド等のジアルキルアミノアルキル（メタ）アクリルアミド類、前記３級アミノ基を有するビニルモノマーの塩酸塩、及び硫酸塩等の無機酸塩類、並びに前記３級アミノ基を有するビニルモノマーのギ酸塩、及び酢酸塩等の有機酸塩類が挙げられる。
【００１３】
また、４級アンモニウム塩類を有するビニルモノマーとしては、前記３級アミノ基を有するビニルモノマーと４級化剤との反応によって得られるビニルモノマーが挙げられる。前記４級化剤としては、メチルクロライド、及びメチルブロマイド等のアルキルハライド、ベンジルクロライド、及びベンジルブロマイド等のアラルキルハライド、ジメチル硫酸、ジエチル硫酸、エピクロロヒドリン、３−クロロ−２−ヒドロキシプロピルトリメチルアンモニウムクロライド、並びにグリシジルトリアルキルアンモニウムクロライド等が挙げられる。これらの３級アミノ基、又は４級アンモニウム塩類を有するビニルモノマーは１種単独で用いても良いし、２種以上を併用しても良い。
【００１４】
本発明において（ｄ）架橋性モノマーとしては、例えば、ジ（メタ）アクリレート類、ビス（メタ）アクリルアミド類、ジビニルエステル類等の２官能性モノマー、３官能性モノマー、４官能性モノマー等の多官能性モノマー、等を挙げることができ、これらは１種単独で用いても良いし、２種以上を併用しても良い。前記（ｄ）成分としては、前記の他に水溶性アジリジニル化合物、水溶性多官能エポキシ化合物、シリコン系化合物等も挙げることができ、これらは、１種単独で用いても良いし、２種以上を併用してもよい。
【００１５】
前記ジ（メタ）アクリレート類としては、例えば、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、トリエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、及びグリセリンジ（メタ）アクリレート等を挙げることができ、これらは１種単独で用いても良いし、２種以上を併用しても良い。前記ビス（メタ）アクリルアミド類としては、例えばＮ，Ｎ'−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、ヘキサメチレンビス（メタ）アクリルアミド、Ｎ，Ｎ'−ビスアクリルアミド酢酸、Ｎ，Ｎ'−ビスアクリルアミド酢酸メチル、Ｎ，Ｎ−ベンジリデンビスアクリルアミド、Ｎ，Ｎ'−ビス（アクリルアミドメチレン）尿素等を挙げることができ、これらは１種単独で用いても良いし、２種以上を併用しても良い。前記ジビニルエステル類としては、例えば、アジピン酸ジビニル、セバシン酸ジビニル、ジアリルフタレート、ジアリルマレート、ジアリルサクシネート等を挙げることができ、これらは１種単独で用いても良いし、２種以上を併用しても良い。前記以外の２官能性モノマーとしては、例えば、アリル（メタ）アクリレート、ジビニルベンゼン、ジイソプロペニルベンゼン、Ｎ−メチロールアクリルアミド、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、ジアリルジメチルアンモニウム塩、ジアリルアミン、ジアリルクロレンデート、グリシジル（メタ）アクリレート、シリコン系化合物等を挙げることができ、これらは１種単独で用いても良いし、２種以上を併用しても良い。
【００１６】
前記３官能性モノマーとしては、例えば、トリアクリルホルマール、トリアリルイソシアヌレート、Ｎ，Ｎ−ジアリルアクリルアミド、Ｎ，Ｎ−ジアリルメタクリルアミド、トリアリルアミン、トリアリルトリメリテート等を挙げることができ、これらは１種単独で用いても良いし、２種以上を併用しても良い。
【００１７】
前記４官能性モノマーとしては、例えば、テトラメチロールメタンテトラアクリレート、テトラアリルピロメリテート、Ｎ，Ｎ，Ｎ'，Ｎ'−テトラアリル−１，４−ジアミノブタン、テトラアリルアミン塩、テトラアリルオキシエタン等を挙げることができ、これらは１種単独で用いても良いし、２種以上を併用しても良い。
【００１８】
前記水溶性アジリジニル化合物としては、例えば、テトラメチロールメタン−トリ−β−アジリジニルプロピオネート、トリメチロールプロパン−トリ−β−アジリジニルプロピオネート、４，４'−ビス（エチレンイミンカルボニルアミノ）ジフェニルメタン等を挙げることができ、これらは１種単独で用いても良いし、２種以上を併用しても良い。前記水溶性多官能エポキシ化合物としては、例えば、（ポリ）エチレングリコールジグリシジルエーテル、（ポリ）プロピレングリコールジグリシジルエーテル、（ポリ）グリセリンジグリシジルエーテル、（ポリ）グリセリントリグリシジルエーテル等を挙げることができ、これらは１種単独で用いても良いし、２種以上を併用しても良い。前記シリコン系化合物としては、例えば、３−（メタ）アクリロキシプロピルトリメトキシシラン、３−（メタ）アクリロキシプロピルジメトキシメチルシラン、３−（メタ）アクリロキシプロピルトリメトキシシラン、３−（メタ）アクリロキシプロピルメチルジクロロシラン、３−（メタ）アクリロキシオクタデシルトリアセトキシシラン、３−（メタ）アクリロキシ−２，５−ジメチルヘキシルジアセトキシメチルシラン、ビニルジメチルアセトキシシラン等を挙げることができ、これらは１種単独で用いても良いし、２種以上を併用しても良い。
【００２０】
前記、Ｎ置換（メタ）アクリルアミドとしては、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，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−イソプロピル（メタ）アクリルアミド、及びＮ−ｔ−オクチル（メタ）アクリルアミド等を挙げることができる。
【００２１】
本発明における、尿素類化合物としては例えば、尿素、及びグアニジル尿素のリン酸塩、硫酸塩等が挙げられる。これらは１種単独で用いても良いし、２種以上を併用しても良い。中でも、尿素が好ましい。尿素類化合物はモノマー類（Ａ）、モノマー類（Ｂ）あるいはその両方に加えて、重合を行う。尿素類化合物の一部を重合後、添加しても良い。また、尿素類化合物の全量を重合終了後に添加してもよいが、紙力増強効果の面から見て、モノマー類（Ａ）に加えるのが望ましい。
【００２２】
モノマー類（Ａ）中における上記（ａ）〜（ｄ）の各成分の配合量は、得られるポリアクリルアミド共重合体を含有する製紙用添加剤を使用して紙を製造した場合における、紙の内部結合強度、破裂強度等の紙力や、抄紙時の濾水性や微細繊維、填料等の歩留等の性能を十分に考慮して決定する事ができる。
【００２３】
紙力の面からは、（ａ）〜（ｄ）の総和１００モル％に対し、（ａ）成分が通常９９．７９５〜５５モル％、好ましくは９７．９９〜７９モル％、（ｂ）成分が通常０．１〜２０モル％、好ましくは１〜１０モル％、（ｃ）成分が通常０．１〜２０モル％、好ましくは１〜１０モル％、（ｄ）成分が通常０．００５〜５モル％、好ましくは０．０１〜１モル％である。また、（ａ）〜（ｄ）のモノマーと共重合することができる前記以外の他のモノマー（ｅ）は、５モル％以下で使用する事ができる。
【００２４】
重合途中において、滴下するモノマー類（Ｂ）は、前記（ａ）〜（ｄ）成分の少なくとも一成分を含有するモノマーであればよい。中でも、前記（ｂ）成分を単独で含有するモノマー溶液、前記（ｃ）成分を単独で含有するモノマー溶液、前記（ｂ）及び（ｃ）成分を含有するモノマー溶液、前記（ａ）、（ｂ）、及び（ｃ）成分を含有するモノマー溶液、前記（ａ）〜（ｄ）成分を含有するモノマー溶液が好ましい。
【００２５】
尿素類化合物の添加量は、全モノマーの重量に対して、固形分の３０重量％以下、より好ましくは１０重量％以下が望ましい。尿素類化合物の存在下で、本発明の重合を行うことにより、更に紙力等の効果に優れるポリアクリルアミド共重合体が合成できる。また、本発明は、これらの尿素類化合物を添加することにより、製紙用添加剤の粘度安定性が向上するという特長も併せ持つ。
【００２６】
本発明に用いる重合開始剤としては、従来公知慣用の重合開始剤を用いる事が出来る。具体的には、過硫酸ナトリウム、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩、過酸化ベンゾイル、過酸化水素、ｔｅｒｔ−ブチルハイドロパーオキサイド、ジ−ｔｅｒｔ−ブチルパーオキサイド等の過酸化物、臭素酸ナトリウム、臭素酸カリウム等の臭素酸塩、過ホウ素酸ナトリウム、過ホウ素酸アンモニウム等の過ホウ素酸塩、過炭酸ナトリウム、過炭酸カリウム、過炭酸アンモニウム等の過炭酸塩、過リン酸ナトリウム、過リン酸カリウム、過リン酸アンモニウム等の過リン酸塩を使用することができる。この場合、１種単独でも使用できるが、２種以上組み合わせて使用しても良く、また、還元剤と併用してレドックス系重合剤として使用することが挙げられる。還元剤としては、亜硫酸ナトリウム等の亜硫酸塩、亜硫酸水素ナトリウム等の亜硫酸水素塩、Ｎ,Ｎ,Ｎ’,Ｎ’−テトラメチルエチレンジアミン等の有機アミン、及びアルドース等の還元糖等を挙げることができる。また、これらの還元剤は１種を単独で用いても良いし、２種以上併用しても良い。また、上記以外として、アゾビスイソブチロニトリル、２，２’−アゾビス−２−アミジノプロパン塩酸塩、２，２’−アゾビス−２，４’−ジメチルバレロニトリル、４，４’−アゾビス−４−シアノ吉草酸及びその塩等のアゾ系重合開始剤を用いる事も出来る。通常、重合開始剤を、モノマー溶液であるモノマー類（Ａ）に添加し重合を開始する。但し、残存モノマーの低減を目的として、重合開始剤の一部を重合途中に追添加しても良い。
【００２７】
また、必要に応じて従来公知の連鎖移動剤をモノマー類（Ａ）、モノマー類（Ｂ）に併せて適宜使用できる。従来公知の連鎖移動剤としては、分子内に１個ないし複数個の水酸基を有する化合物、例えばエタノール、イソプロピルアルコール、ブタノール、エチレングリコール、グリセリンアルコール類、ポリエチレンオキサイド、ポリグリセリン等のオリゴマー及びポリマー類、グルコース、アスコルビン酸、ショ糖等の糖類やビタミン類を挙げることができる。また、分子内に１個または複数個のメルカプト基を含む化合物として、例えば、ブチルメルカプタン、メルカプトエタノール、チオグリコール酸及びそのエステル、メルカプトプロピオン酸及びそのエステル、チオグリセリン、システアミン及びその塩等を挙げることができる。また、分子内に１個または複数個の炭素―炭素不飽和結合を有する化合物として、例えば（メタ）アリルアルコール及びそのエステル誘導体、（メタ）アリルアミン、ジアリルアミン、ジメタリルアミン及びそのアミド誘導体、トリアリルアミン、トリメタリルアミン、（メタ）アリルスルホン酸及びその塩、アリルスルフィド類、アリルメルカプタン類を挙げることができる。更に、次亜リン酸を挙げることができる。
【００２８】
本発明におけるポリアクリルアミド系共重合体の合成は、通常、次のように行われる。まず、窒素等の不活性ガス雰囲気下、所定の反応容器にモノマー類（Ａ）と、溶媒である水（有機溶媒を併用することがあっても良い）、必要に応じて上記連鎖移動剤を仕込み、攪拌下、上記重合開始剤を加え重合を開始する。次いで、上記モノマー類（Ａ）の反応率（以下「コンバージョン」と称することがある。）が２０〜９６．５%に達した時、好ましくは３０〜９０%に達した時、モノマー類（Ｂ）を滴下する。滴下後、更に加熱、重合することで、本発明のポリアクリルアミド系共重合体を得る。
【００２９】
コンバージョンは、モノマー類（Ａ）及びモノマー類（Ｂ）における（ａ）〜（ｄ）の各成分の種類、配合量並びに得られたポリアクリルアミド系共重合体を含有する製紙用添加剤を使用して紙を製造した場合における、紙の内部結合強度、破裂強度等の紙力や抄紙時の濾水性や微細繊維、填料等の歩留り等の性能を十分に考慮して上記範囲内で決定することができる。コンバージョンが上記範囲でない場合は、得られたポリアクリルアミド系共重合体を含有する製紙用添加剤を使用して紙を製造した場合における上記の性能が十分でない。
【００３０】
モノマー類（Ａ）とモノマー類（Ｂ）との合計を１００モル％としてモノマー類（Ｂ）の滴下量は、通常、モノマー類（Ｂ）が（ａ）成分を含まない場合は、通常０．１〜４０モル％、好ましくは１〜２０モル％であり、モノマー類（Ｂ）が（ａ）成分を含む場合は、通常１０〜７０モル％、好ましくは２０〜６０モル％である。滴下時間は、通常５〜６０分、好ましくは１０〜３０分である。モノマー類（Ｂ）が複数のモノマー成分からなる場合は複数のモノマーの混合物として滴下しても良いし、あるいは各々のモノマーをそれぞれ滴下しても良い。
【００３１】
重合温度は、通常のラジカル重合が起こる範囲であれば特に制限はないが、通常は５０〜９５℃の範囲で行われる。
【００３２】
コンバージョンを測定する方法としては、例えば「高分子合成の実験法、（大津隆行、木下雅悦 著）に記述されているような、従来公知の技術を用いる事が出来る。本願発明でのコンバージョンの値は、1Ｈ‐ＮＭＲで測定した値である。
【００３３】
重合により合成されるポリアクリルアミド系共重合体の固形分は通常５〜３０重量％であり、ブルックフィールド回転粘度計にて測定した２５℃における粘度は、通常は、２０，０００ｍＰａ・ｓ以下である。
【００３４】
本発明では、モノマー類（Ａ）の重合途中で、モノマー類（Ｂ）を滴下し、重合するので、ポリアクリルアミド系共重合体の存在下で、アクリルアミド類のモノマー溶液の重合をする方法やモノマーの全量を滴下して重合する方法等の従来の方法と比べて、短時間でポリアクリルアミド系共重合体の製造が可能である。
【００３５】
本発明により製造されるポリアクリルアミド系共重合体が従来の方法で製造したポリアクリルアミド系共重合体に比べて、紙力等の効果が優れる理由は、不明であるが、重合途中で滴下する為、最初、比較的低分子量のアクリルアミド系ポリマーが生成し、次いで、重合系に残存する重合開始剤ラジカルによるポリマー中の水素引き抜きによりポリアクリルアミド系共重合体が高分子量化する為、高分岐ポリマーが生成しやすいことや、イオンバランスの最適化が可能であること等が理由ではないかと考えられる。
【００３６】
本発明により製造されるポリアクリルアミド系共重合体を含有する製紙用添加剤は、紙を製造する際に、パルプスラリーに添加することで紙力増強効果を発揮する。パルプ原料として、クラフトパルプ及びサルファイトパルプ等の晒、又は未晒化学パルプ、砕木パルプ、機械パルプ及びサーモメカニカルパルプ等の晒、又は未晒高収率パルプ、並びに新聞古紙、雑誌古紙、段ボール古紙及び脱墨古紙等の古紙パルプのいずれも使用することができる。
【００３７】
本発明により製造されるポリアクリルアミド系共重合体を含有する製紙用添加剤は、パルプスラリーの電導度による影響が従来の製紙用添加剤に比べ少なく、特にパルプスラリーの電導度が８００μＳ／ｃｍ以上の時に従来の製紙用添加剤との性能差が大きい。
【００３８】
また、各々の紙種に要求される物性を発現させるために、本発明により製造される製紙用添加剤に、他の製紙用添加剤を併用させることもできる。併用される他の製紙用添加剤としては、例えば、填料、染料、酸性抄紙用ロジン系サイズ剤、中性抄紙用ロジン系サイズ剤、アルキルケテンダイマー系サイズ剤、アルケニルコハク酸無水物系サイズ剤、特殊変性ロジン系サイズ剤等の弱酸性、中性、及びアルカリ性抄紙用サイズ剤、湿潤紙力向上剤、歩留り向上剤、濾水性向上剤、嵩高剤、並びに消泡剤等が挙げられる。これらは１種単独で用いても良いし、２種以上を併用しても良い。填料としては、クレー、タルク、酸化チタン、重質又は軽質炭酸カルシウム等を挙げることができる。
【００３９】
また、本発明の製紙用添加剤には、本発明により合成された前記ポリアクリルアミド系共重合体を単独で含有しても良いし、アニオン性ポリアクリルアミド系共重合体、マンニッヒ変性アクリルアミド系ポリマー、ホフマン変性アクリルアミド系ポリマー、及び硫酸バンド等も含有していても良い。また、本発明の製紙用添加剤は、単独で使用しても良いし、アニオン性ポリアクリルアミド系共重合体、マンニッヒ変性アクリルアミド系ポリマー、ホフマン変性アクリルアミド系ポリマー、及び硫酸バンド等と併用しても良い。
【００４０】
本発明のポリアクリルアミド系共重合体を含有させた紙は、例えば上述した本発明の製紙用添加剤を用いた抄紙により得られるが、その得られる紙としては、例えば、ＰＰＣ用紙、インクジェット記録用紙、レーザープリンター用紙、フォーム用紙、アート紙、キャスト紙、上質コート紙等の印刷情報用紙、写真用印画紙、クラフト紙、純白ロール紙等の包装用紙、その他のノート用紙、書籍用紙、印刷用紙、新聞用紙等の洋紙、マニラボール、白ボール、チップボール、高級白板等の紙器用板紙、ライナー、中芯原紙、紙管原紙等が挙げられる。
【実施例】
【００４１】
以下、実施例及び比較例を挙げて本発明をより具体的に説明するが、本発明は下記の実施例に限定されるものでは無い。尚、％は特に表示がない限り、重量基準による。また、モル％は特に表示がない限り、モノマー類（Ａ）とモノマー類（Ｂ）との合計を１００モル％としたときの値を示している。
【００４２】
（ポリアクリルアミド系共重合体の合成）
実施例１（モノマーＢが（ｂ）成分よりなる合成法）
攪拌機、温度計、還流冷却管、及び窒素ガス導入管を付した１リットル四つ口フラスコに水４１３．３６ｇ、モノマー類（Ａ）として、５０％アクリルアミド水溶液３０５．３９ｇ（８９．６２モル％）、ジメチルアミノエチルメタクリレート１１．３０ｇ（３．０モル％）、７６％メタクリロイルオキシエチルジメチルベンジルアンモニウムクロライド水溶液２６．８５ｇ（３．０モル％）、イタコン酸１．８７ｇ（０．６モル％）、５％メタリルスルホン酸ナトリウム水溶液２８．０５ｇ（０．３７モル％）、Ｎ，Ｎ’-ジメチルアクリルアミド ２．３８ｇ（１．０モル％）、０．５％トリアクリルホルマール１１．９５ｇ（０．０１モル％）を仕込み、３０％硫酸水溶液でｐＨ２．５に調整した。次いで、窒素ガス雰囲気下、６０℃に昇温し、５％過硫酸アンモニウム水溶液５．７７ｇを加え、２０分で８０℃まで昇温した。これら１段目モノマー（モノマー類（Ａ））のコンバージョンが３３％になった時点で、水１７９．２４ｇ、イタコン酸７．４８ｇ（２．４モル％）から成るモノマー水溶液（Ｂ）を２０分かけて滴下し、８０℃で重合を行った。２５℃における推定粘度が６,０００〜８,０００ｍＰａ・ｓになった時点で、冷却し反応を停止した。固形分２０．３％、ｐＨ３．３、粘度（２５℃、ブルックフィールド回転粘度計使用）７，３００ｍＰａ・ｓのポリマー溶液を得た。
【００４３】
本実施例では、モノマー類（Ｂ）の滴下を行う直前にサンプリングした共重合物について、1Ｈ‐ＮＭＲ測定を行い、モノマーとポリマー由来のピークの強度比よりコンバージョンを算出した。
【００４４】
実施例２〜６（モノマーＢが（ｂ）成分よりなる合成法）
モノマー溶液（Ｂ）を滴下する際の、モノマー類（Ａ）のコンバージョン、及び、イタコン酸の分割添加比（モノマー類（Ａ）中／モノマー類（Ｂ）中）を変更した点を除き、実施例１と同様に行った。コンバージョン、イタコン酸の添加方法（分割添加比）、及び得られたポリアクリルアミド系共重合体の性状を表１に示す。
【００４５】
比較例１
攪拌機、温度計、還流冷却管、及び窒素ガス導入管を付した１リットル四つ口フラスコに水５９２．２６ｇ、５０％アクリルアミド水溶液３０５．３９ｇ（８９．６２モル％）、ジメチルアミノエチルメタクリレート１１．３０ｇ（３．０モル％）、７６％メタクリロイルオキシエチルジメチルベンジルアンモニウムクロライド水溶液２６．８５ｇ（３．０モル％）、イタコン酸９．３５ｇ（３．０モル％）、５％メタリルスルホン酸ナトリウム水溶液２８．０５ｇ（０．３７モル％）、Ｎ，Ｎ’-ジメチルアクリルアミド ２．３８ｇ（１．０モル％）、０．５％トリアクリルホルマール１１．９５ｇ（０．０１モル％）を仕込み、３０％硫酸水溶液でｐＨ２．５に調整した。次いで、窒素ガス雰囲気下、６０℃に昇温し、５％過硫酸アンモニウム水溶液５．７７ｇを加え、２０分で８０℃まで昇温し、そのまま８０℃で重合を行った。２５℃における推定粘度が６,０００〜８,０００ｍＰａ・ｓになった時点で、冷却し反応を停止した。固形分２０．２％、ｐＨ３．４、粘度（２５℃、ブルックフィールド回転粘度計使用）７，１２０ｍＰａ・ｓのポリマー溶液を得た。
表１
【００４６】
【表１】
実施例７
攪拌機、温度計、還流冷却管、及び窒素ガス導入管を付した１リットル四つ口フラスコに水４１３．４０ｇ、イソプロピルアルコール６０．０ｇ、５０％アクリルアミド水溶液３４６．９６ｇ（９１．２９モル％）、７６％メタクリロイルオキシエチルジメチルベンジルアンモニウムクロライド水溶液１３．９８g（１．４モル％）、フマル酸４．０３g（１．３モル％）、０．５％トリアクリルホルマール１３．３３ｇ（０．０１モル％）を仕込んだ。次いで、窒素ガス雰囲気下、６０℃に昇温し、５％過硫酸アンモニウム水溶液４．８８gを加え、２０分で８０℃まで昇温した。これら１段目モノマー（モノマー類（Ａ））のコンバージョンが３５％になった時点で、水１２８．７９ｇ、８０％アクリル酸１４．４５g（６．０mol％）から成るモノマー水溶液を２０分かけて滴下し、８０℃で２時間重合を行った。２５℃における推定粘度が５,０００〜７,０００ｍＰａ・ｓになった時点で、冷却し反応を停止した。固形分２０．３％、ｐＨ３．３、粘度（２５℃、ブルックフィールド回転粘度計使用）６，３６０ｍPa・ｓのポリマー溶液を得た。
【００４８】
実施例８〜１１（モノマー類（Ｂ）が（ｂ）成分よりなる合成法）
モノマー類（Ａ）、及びモノマー類（Ｂ）、連鎖移動剤を表２の様に変えた以外は、実施例７と同様に合成反応を行った。得られたポリアクリルアミド系共重合体の性状を表３に示す。
【００４９】
比較例２、３
モノマー類（Ａ）、連鎖移動剤を表２の様に変えた以外は、比較例１と同様に合成反応を行なった。得られたポリアクリルアミド系共重合体の性状を表３に示す。
表２
【００５０】
【表２】
表３
【００５２】
【表３】
実施例１２（モノマーＢが（ｃ）成分よりなる合成法）
攪拌機、温度計、還流冷却管、及び窒素ガス導入管を付した１リットル四つ口フラスコに水４９４．１５ｇ、モノマー類（Ａ）として、５０％アクリルアミド水溶液３０５．０６ｇ（９０．６２モル％）、７６％アクリロイルオキシエチルジメチルベンジルアンモニウムクロライド水溶液２５．２２ｇ（３．０モル％）、イタコン酸９．２４ｇ（３．０モル％）、５％メタリルスルホン酸ナトリウム水溶液２７．７１ｇ（０．３７モル％）、Ｎ，Ｎ’-ジメチルアクリルアミド ２．３５ｇ（１．０モル％）、０．５％トリアクリルホルマール１１．８１ｇ（０．０１モル％）を仕込んだ。次いで、窒素ガス雰囲気下、６０℃に昇温した。５％過硫酸アンモニウム水溶液１０．８０ｇを加え、重合を開始するとともに８５℃まで昇温した。これら１段目モノマー（モノマー類（Ａ））のコンバージョンが２０．４％になった時点で、水９０．０８ｇ、及び７６％アクリロイルオキシエチルジメチルベンジルアンモニウムクロライド水溶液１６．８１ｇ（２．０モル％）から成るモノマー水溶液（Ｂ）を２０分かけて滴下し、８０℃で保温した。２５℃における推定粘度が６,０００〜９,０００ｍＰａ・ｓになった時点で、冷却し反応を停止した。固形分２０．４％、ｐＨ３．２、粘度（２５℃、ブルックフィールド回転粘度計使用）６，２４０ｍＰａ・ｓのポリマー溶液を得た。
【００５４】
実施例１３〜２０（モノマーＢが（ｃ）成分よりなる合成法）
モノマー溶液（Ｂ）を滴下する際の、モノマー類（Ａ）のコンバージョン、及び、７６％アクリロイルオキシエチルジメチルベンジルアンモニウムクロライドの分割添加比（モノマー類（Ａ）中／モノマー類（Ｂ）中）を変更した点を除き、実施例７と同様に行った。コンバージョン、７６％アクリロイルオキシエチルジメチルベンジルアンモニウムクロライドの分割添加比、及び得られたポリアクリルアミド系共重合体の性状を表４に示す。
【００５５】
比較例４
攪拌機、温度計、還流冷却管、及び窒素ガス導入管を付した１リットル四つ口フラスコに水５３６．８９ｇ、５０％アクリルアミド水溶液３０５．０６ｇ（９０．６２モル％）、７６％アクリロイルオキシエチルジメチルベンジルアンモニウムクロライド水溶液４２．０３ｇ（５．０モル％）、イタコン酸９．２４ｇ（３．０モル％）、５％メタリルスルホン酸ナトリウム水溶液２７．７１ｇ（０．３７モル％）、Ｎ，Ｎ’-ジメチルアクリルアミド ２．３５ｇ（１．０モル％）、０．５％トリアクリルホルマール１１．８１ｇ（０．０１モル％）を仕込んだ。その他は、比較例１と同様に合成反応を行い、固形分２０．２％、ｐＨ３．３、粘度（２５℃、ブルックフィールド回転粘度計使用）８，２００ｍＰａ・ｓのポリマー溶液を得た。
表４
【００５６】
【表４】
実施例２１（モノマーＢが（ｂ）、及び（ｃ）成分よりなる合成法）
攪拌機、温度計、還流冷却管、及び窒素ガス導入管を付した１リットル四つ口フラスコに水６０３．５３ｇ、モノマー類（Ａ）として、５０％アクリルアミド水溶液２６６．４３ｇ（９４．２８モル％）、ジメチルアミノエチルメタクリレート８．４４ｇ（２．７モル％）、イタコン酸４．９７ｇ（１．９２モル％）、５％メタリルスルホン酸ナトリウム水溶液１８．５５ｇ（０．３０モル％）、０．５％トリアクリルホルマール１９．８２ｇ（０．０２モル％）を仕込み、３０％硫酸でｐＨ２．５に調整した。次いで、窒素ガス雰囲気下、６０℃に昇温した。５％過硫酸アンモニウム水溶液４．５４ｇを加え、重合を開始するとともに８５℃まで昇温した。これら１段目モノマー（モノマー類（Ａ））のコンバージョンが３０．２％になった時点で、水７３．７９ｇ、ジメチルアミノエチルメタクリレート０．９４ｇ（０．３０モル％）、イタコン酸１．２４ｇ（０．４８モル％）から成るモノマー水溶液（Ｂ）を２０分かけて滴下し、８０℃で保温した。２５℃における推定粘度が７,０００〜８,０００ｍＰａ・ｓになった時点で、冷却し反応を停止した。固形分１５．４％、ｐＨ３．５、粘度（２５℃、ブルックフィールド回転粘度計使用）７，９００ｍＰａ・ｓのポリマー溶液を得た。
【００５８】
実施例２２〜２３ （モノマーＢが(ｂ)、及び（ｃ）成分よりなる合成法）
モノマー類（Ｂ）を滴下する際の、モノマー類（Ａ）のコンバージョンを変更した点を除き、実施例２１と同様に行った。滴下時のモノマー類（Ａ）のコンバージョン、及び得られたポリアクリルアミド系共重合体の性状を表５に示す。
【００５９】
比較例５
攪拌機、温度計、還流冷却管、及び窒素ガス導入管を付した１リットル四つ口フラスコに水６７５．３２ｇ、５０％アクリルアミド水溶液２６６．４６ｇ（９４．２８モル％）、ジメチルアミノエチルメタクリレート９．３８ｇ（３．０モル％）、イタコン酸６．２１ｇ（２．４モル％）、５％メタリルスルホン酸ナトリウム水溶液１８．５５ｇ（０．３０モル％）、０．５％トリアクリルホルマール１９．８２ｇ（０．０２モル％）を仕込み、３０％硫酸でｐＨ２．５に調整した。その他は、比較例１と同様に合成反応を行った。得られたポリアクリルアミド系共重合体の性状を表５に示す。
表５
【００６０】
【表５】
実施例２４（モノマーＢが（ａ）、（ｂ）、（ｃ）、及び（ｄ）成分よりなる合成法）
攪拌機、温度計、還流冷却管、及び窒素ガス導入管を付した１リットル四つ口フラスコに水３８２．８０ｇ、モノマー類（Ａ）として、５０％アクリルアミド水溶液１９８．６０ｇ（５６．２４モル％）、ジメチルアミノエチルメタクリレート４．６９ｇ（１．２モル％）、イタコン酸７．２７ｇ（２．２５モル％）、５％メタリルスルホン酸ナトリウム水溶液２３．５７ｇ（０．３０モル％）、１％Ｎ，Ｎメチレンビスアクリルアミド３．８３ｇ（０．０１モル％）を仕込み、３０％硫酸でｐＨ３．０に調整した。次いで、窒素ガス雰囲気下、６０℃に昇温した。５％過硫酸アンモニウム水溶液４．５４ｇを加え、重合を開始するとともに８５℃まで昇温した。これら１段目モノマー（モノマー類（Ａ））のコンバージョンが２１．０％になった時点で、水１９６．６３ｇ、５０％アクリルアミド水溶液１３０．２７ｇ（３６．８９モル％）、７６％メタクリロイルオキシエチルジメチルベンジルアンモニウムクロライド水溶液２５．９７ｇ（２．８モル％）、イタコン酸０．８１ｇ（０．２５モル％）、５％メタリルスルホン酸ナトリウム水溶液３．９３ｇ（０．０５モル％）、１％Ｎ，Ｎメチレンビスアクリルアミド３．８３ｇ（０．０１モル％）から成るモノマー水溶液（Ｂ）を２０分かけて滴下し、８０℃で２０分保温した。更に、５％過硫酸アンモニウム水溶液９．０６ｇを加え、そのまま８０℃で保温した。２５℃における推定粘度が６,０００〜９,０００ｍＰａ・ｓになった時点で、冷却し反応を停止した。固形分２０．４％、ｐＨ３．６、粘度（２５℃、ブルックフィールド回転粘度計使用）６，５００ｍＰａ・ｓのポリマー溶液を得た。
【００６２】
実施例２５〜２９（モノマーＢが（ａ）、（ｂ）、（ｃ）、及び（ｄ）成分よりなる合成法）
モノマー類（Ｂ）を滴下する際の、モノマー類（Ａ）のコンバージョンを変更した点を除いて、実施例２４と同様に行った。滴下時のモノマー類（Ａ）のコンバージョン、及び得られたポリアクリルアミド系共重合体の性状を表６に示す。
【００６３】
比較例６
攪拌機、温度計、還流冷却管、及び窒素ガス導入管を付した１リットル四つ口フラスコに水５７９．４３ｇ、５０％アクリルアミド水溶液３２８．８７ｇ（９３．１３モル％）、ジメチルアミノエチルメタクリレート４．６９ｇ（１．２モル％）、７６％メタクリロイルオキシエチルジメチルベンジルアンモニウムクロライド水溶液２５．９７ｇ（２．８モル％）、イタコン酸８．０８ｇ（２．５モル％）、５％メタリルスルホン酸ナトリウム水溶液２７．５０ｇ（０．３５モル％）、１％Ｎ，Ｎメチレンビスアクリルアミド７．６６ｇ（０．０２モル％）を仕込み、３０％硫酸でｐＨ３．０に調整した。その他は、比較例１と同様に合成反応を行った。得られたポリアクリルアミド系共重合体の性状を表６に示す。
【００６４】
比較例７
モノマー類（Ｂ）を滴下する際の、モノマー類（Ａ）のコンバージョンを１５％に変更した点を除いて、実施例２４と同様に行った。滴下時のモノマー類（Ａ）のコンバージョン、及び得られたポリアクリルアミド系共重合体の性状を表６に示す。
【００６５】
実施例３０（尿素を含有する合成法）
攪拌機、温度計、還流冷却管、及び窒素ガス導入管を付した１リットル四つ口フラスコに水３８２．８０ｇ、モノマー類（Ａ）として、尿素９．９６ｇ、５０％アクリルアミド水溶液１８８．６８ｇ（５６．２４モル％）、ジメチルアミノエチルメタクリレート４．６９ｇ（１．２モル％）、イタコン酸７．２７ｇ（２．２５モル％）、５％メタリルスルホン酸ナトリウム水溶液２３．５７ｇ（０．３０モル％）、１％Ｎ，Ｎメチレンビスアクリルアミド３．８３ｇ（０．０１モル％）を仕込み、３０％硫酸でｐＨ３．０に調整した。次いで、窒素ガス雰囲気下、６０℃に昇温した。５％過硫酸アンモニウム水溶液５．３８ｇを加え、重合を開始するとともに８５℃まで昇温した。これら１段目モノマー（モノマー類（Ａ））のコンバージョンが９０．３％になった時点で、水２２７．１２ｇ、５０％アクリルアミド水溶液１２３．７７ｇ（３６．８９モル％）、７６％メタクリロイルオキシエチルジメチルベンジルアンモニウムクロライド水溶液２５．９７ｇ（２．８モル％）、イタコン酸０．８１ｇ（０．２５モル％）、５％メタリルスルホン酸ナトリウム水溶液３．９３ｇ（０．０５モル％）、１％Ｎ，Ｎメチレンビスアクリルアミド３．８３ｇ（０．０１モル％）から成るモノマー水溶液を加えつつ８０℃まで冷却し、８０℃で保温した。２５℃における推定粘度が６,０００〜９,０００ｍＰａ・ｓになった時点で、冷却し反応を停止した。固形分２０．３％、ｐＨ３．６、粘度（２５℃、ブルックフィールド回転粘度計使用）６，４５０ｍＰａ・ｓのポリマー溶液を得た。
【００６６】
実施例３１（尿素を含有する合成法）
モノマー類（Ｂ）を滴下する際の、モノマー類（Ａ）のコンバージョンを変更した点を除いて、実施例３０と同様に行った。滴下時のモノマー類（Ａ）のコンバージョン、及び得られたポリアクリルアミド系共重合体の性状を表６に示す。
【００６７】
比較例８
攪拌機、温度計、還流冷却管、及び窒素ガス導入管を付した１リットル四つ口フラスコに水４１８．３５ｇ、モノマー類（Ａ）として、５０％アクリルアミド水溶液１９７．６４ｇ（５６．２４モル％）、ジメチルアミノエチルメタクリレート４．６６ｇ（１．２モル％）、イタコン酸７．２４ｇ（２．２５モル％）、５％メタリルスルホン酸ナトリウム水溶液２３．５７ｇ（０．３０モル％）、１％Ｎ，Ｎメチレンビスアクリルアミド３．８１ｇ（０．０１モル％）を仕込み、３０％硫酸でｐＨ３．０に調整した。次いで、窒素ガス雰囲気下、４０℃に昇温した。１０％過硫酸アンモニウム水溶液７．９０ｇ、１０％亜硫酸水素ナトリウム水溶液４．６３ｇを加え、重合を開始するとともに８５℃まで昇温した。８５℃で２時間重合後、別途仕込んでおいた水１２７．６０ｇ、５０％アクリルアミド水溶液１２９．６４ｇ（３６．８９モル％）、７６％メタクリロイルオキシエチルジメチルベンジルアンモニウムクロライド水溶液２５．８５ｇ（２．８モル％）、イタコン酸０．８０ｇ（０．２５モル％）、５％メタリルスルホン酸ナトリウム水溶液３．９１ｇ（０．０５モル％）、１％Ｎ，Ｎメチレンビスアクリルアミド３．８１ｇ（０．０１モル％）、３％過硫酸カリウム水溶液４４．５７ｇをそれぞれ１時間かけて滴下した。滴下終了後、更に８５℃で1時間保温し、固形分２０．４％、ｐＨ４．３、粘度（２５℃、ブルックフィールド回転粘度計使用）５，５００ｍＰａ・ｓのポリマー溶液を得た。
【００６８】
比較例９
ビーカーに５０％アクリルアミド水溶液３１０．５５ｇ（９３．１３モル％）、ジメチルアミノエチルメタクリレート４．４２ｇ（１．２モル％）、７６％メタクリロイルオキシエチルジメチルベンジルアンモニウムクロライド水溶液２４．５２ｇ（２．８モル％）、イタコン酸７．６４ｇ（２．５モル％）、５％メタリルスルホン酸ナトリウム水溶液２５．９７ｇ（０．３５モル％）、１％Ｎ，Ｎメチレンビスアクリルアミド７．２４ｇ（０．０２モル％）を仕込みｐＨ４．５に調整、モノマーＡ溶液とした。攪拌機、温度計、還流冷却管、及び窒素ガス導入管を付した１リットル四つ口フラスコに水４９６．８５ｇを仕込み、１％硫酸でｐＨ４．５に調整し、窒素ガス雰囲気下、５０℃に昇温した。次いで、モノマーＡ溶液、１％過硫酸アンモニウム水溶液６１．５５ｇ、０．２％亜硫酸水素ナトリウム水溶液６１．２７ｇを、それぞれ、反応容器に７０分かけて連続滴下した。滴下中は、内温を５０℃に保った。滴下終了後、更に、５０℃で１１０分重合反応を行い、固形分２０．４％、ｐＨ３．８、粘度（２５℃、ブルックフィールド回転粘度計使用）５，０５０ｍＰａ・ｓのポリマー溶液を得た。
【００６９】
比較例１０
ビーカーに水４９．６５ｇ、５０％アクリルアミド水溶液１９．４２ｇ（５．８２モル％）、イタコン酸７．６３ｇ（２．５モル％）、５％メタリルスルホン酸ナトリウム水溶液２５．９９ｇ（０．３５モル％）を仕込み、３０％水酸化ナトリウム水溶液でｐＨ４．５に調整し、１段目モノマー溶液とした。別のビーカーに５０％アクリルアミド水溶液２９１．２５ｇ（８７．２９モル％）、ジメチルアミノエチルメタクリレート４．４３ｇ（１．２モル％）、７６％メタクリロイルオキシエチルジメチルベンジルアンモニウムクロライド水溶液２４．５４ｇ（２．８モル％）、及び１％Ｎ，Ｎメチレンビスアクリルアミド７．２４ｇ（０．０２モル％）を仕込み、３０％硫酸でｐＨ４．５に調整し、第２モノマー溶液とした。攪拌機、温度計、還流冷却管、及び窒素ガス導入管を付した１リットル四つ口フラスコに水４４６．８５ｇ、１％Ｎ，Ｎメチレンビスアクリルアミド５．５５ｇ（０．０２モル％）を仕込み、１％硫酸でｐＨ４．５に調整し、窒素ガス雰囲気下、５０℃に昇温した。次いで、１段目モノマー溶液、０．２％過硫酸アンモニウム水溶液６１．６０ｇ、１％亜硫酸水素ナトリウム水溶液６１．３０ｇを、それぞれ、反応容器に１４分かけて連続滴下した。滴下中は、内温を５０℃に保った。滴下終了後、５０℃で１０分保持した後、モノマー溶液（Ｂ）を５６分かけて滴下した。滴下終了後、５０℃で１００分重合反応を行い、固形分２０．４％、ｐＨ４．６、粘度（２５℃、ブルックフィールド回転粘度計使用）５，７６０ｍＰａ・ｓのポリマー溶液を得た。
表６
【００７０】
【表６】
実施例３２（モノマーＢが（ａ）、（ｂ）、及び（ｃ）成分よりなる合成法）
攪拌機、温度計、還流冷却管、及び窒素ガス導入管を付した１リットル四つ口水４９５．６８ｇ、フラスコにモノマーＡとして、５０％アクリルアミド水溶液２７７．０５ｇ（８１．１０モル％）、７６％アクリロイルオキシエチルジメチルベンジルアンモニウムクロライド水溶液２９．８５ｇ（３．５モル％）、イタコン酸６．２５ｇ（２．０モル％）、５％メタリルスルホン酸ナトリウム水溶液２９．６４ｇ（０．３９モル％）、Ｎ，Ｎ’-ジメチルアクリルアミド ２．３８ｇ（１．０モル％）、０．５％トリアクリルホルマール１１．９８ｇ（０．０１モル％）を仕込み、３０％水酸化ナトリウムでｐＨ３．０に調整した。次いで、窒素ガス雰囲気下、６０℃に昇温した。５％過硫酸アンモニウム水溶液５．４８ｇを加え、重合を開始するとともに８５℃まで昇温した。これら１段目モノマー（モノマー類（Ａ））のコンバージョンが約５０％になった時点で、別途仕込んでおいた水９３．３１ｇ、５０％アクリルアミド水溶液３４．１６ｇ（１０．０モル％）、７６％アクリロイルオキシエチルジメチルベンジルアンモニウムクロライド水溶液１２．７９ｇ（１．５モル％）、イタコン酸１．５６ｇ（０．５０モル％）を２０分かけて滴下し、８０℃で２０分保温した。更に、５％過硫酸アンモニウム水溶液９．０６ｇを加え、そのまま８０℃で保温した。２５℃における推定粘度が６,０００〜９,０００ｍＰａ・ｓになった時点で、冷却し反応を停止した。固形分２０．５％、ｐＨ３．７、粘度（２５℃、ブルックフィールド回転粘度計使用）６，０５０ｍＰａ・ｓのポリマー溶液を得た。
【００７２】
実施例３３〜３４（モノマーＢが（ａ）、（ｂ）、及び（ｃ）成分からなる合成法）
モノマー類（Ｂ）を滴下する際の、モノマー類（Ａ）のコンバージョンを変更した点を除いて、実施例３２と同様に行った。滴下時のモノマー類（Ａ）のコンバージョン、及び得られたポリアクリルアミド系共重合体の性状を表７に示す。
【００７３】
比較例１１〜１２
モノマー類（Ｂ）を滴下する際の、モノマー類（Ａ）のコンバージョンを変更した点を除き、実施例３２と同様に行った。滴下時のモノマー類（Ａ）のコンバージョン、及び得られたポリアクリルアミド系共重合体の性状を表７に示す。
表７
【００７４】
【表７】
実施例３５（尿素を含有する合成法）
攪拌機、温度計、還流冷却管、及び窒素ガス導入管を付した１リットル四つ口フラスコに水４３９．６６ｇ、尿素１０．００ｇ、モノマー類（Ａ）として、５０％アクリルアミド水溶液２３９．３９ｇ（５６．２７５モル％）、ジメチルアミノエチルメタクリレート５．６５ｇ（１．２モル％）、イタコン酸７．７９ｇ（２．０モル％）、５％メタリルスルホン酸ナトリウム水溶液４７．３２ｇ（０．５０モル％）、及び１％Ｎ，Ｎメチレンビスアクリルアミド１１．５３ｇ（０．０２５モル％）を仕込み、３０％硫酸でｐＨ２．５に調整した。次いで、窒素ガス雰囲気下、６０℃に昇温した。５％過硫酸アンモニウム水溶液６．８２ｇを加え、重合を開始するとともに８５℃まで昇温した。これら１段目モノマー（モノマー類（Ａ））のコンバージョンが８９．２％になった時点で、水３３．４６ｇ、５０％アクリルアミド水溶液１５５．６８ｇ（３６．６０モル％）、７６％メタクリロイルオキシエチルジメチルベンジルアンモニウムクロライド水溶液３１．２９ｇ（２．８モル％）、イタコン酸１．９５ｇ（０．５０モル％）、及び５％メタリルスルホン酸ナトリウム水溶液９．４６ｇ（０．１０モル％）から成るモノマー水溶液を加えつつ８０℃まで冷却し、８０℃で保温した。２５℃における推定粘度が６,０００〜９,０００ｍＰａ・ｓになった時点で、冷却し反応を停止した。固形分２５．２％、ｐＨ４．１、粘度（２５℃、ブルックフィールド回転粘度計使用）８，８２０ｍＰａ・ｓのポリマー溶液を得た。
【００７６】
比較例１３（尿素を含有する合成法）
攪拌機、温度計、還流冷却管、及び窒素ガス導入管を付した１リットル四つ口フラスコに水４７３．１２ｇ、尿素１０ｇ、５０％アクリルアミド水溶液３９５．０７ｇ（９２．８７５モル％）、ジメチルアミノエチルメタクリレート５．６５ｇ（１．２モル％）、７６％メタクリロイルオキシエチルジメチルベンジルアンモニウムクロライド水溶液３１．２９ｇ（２．８モル％）、イタコン酸９．７４ｇ（２．５モル％）、５％メタリルスルホン酸ナトリウム水溶液５６．７８ｇ（０．６０モル％）、１％Ｎ，Ｎメチレンビスアクリルアミド１１．５３ｇ（０．０２５モル％）を仕込み、３０％硫酸でｐＨ２．５に調整した。その他は、比較例１と同様に合成反応を行い、固形分２５．５％、ｐＨ４．２、粘度（２５℃、ブルックフィールド回転粘度計使用）８，１１０ｍＰａ・ｓのポリマー溶液を得た。
【００７７】
（紙の作製と物性測定）
応用例１
段ボール古紙を叩解しカナディアン・スタンダード・フリーネス（ＣＳＦ）４１１、電導度１５００μS／ｃｍに調整した濃度２．４％のパルプスラリーに、硫酸バンドをパルプ固形分に対し１．０％添加した。その後、実施例１で製造したポリアクリルアミド系共重合体をパルプ固形分に対し０．５％添加し、更に１分間攪拌した。攪拌の後、このパルプスラリーを電導度３０００μS／ｃｍの水で０．８％に希釈した後、ノーブルアンドウッド製シートマシンにて抄紙して、湿紙を得た。この湿紙を、プレス後、ドラムドライヤーで乾燥して８０ｇ／ｍ2の手抄き紙を得た。得られた手抄き紙を２０℃、ＲＨ６５％の条件下で２４時間調湿した後、各種測定を行った。測定結果を表８に示す。物性の測定は、以下の方法に準じて行った。
【００７８】
比破裂強度 ・・・ＪＩＳ Ｐ−８１１２に準拠した。
内部結合強度 ・・・ＪＡＰＡＮ−ＴＡＰＰＩ紙パルプ試験法Ｎｏ．５４に準拠した。
裂断長 ・・・ＪＩＳ Ｐ−８１１３に準拠した。
ＤＤＴ ・・・Tａｐｐｉ、第５６巻、第１０号（１９７３年）の第４６頁に記載されている「ダイナミック ドライネッジ ジャー（Ｄｙｎａｍｉｃ Ｄｒａｉｎａｇｅ Ｊａｒ）」用と同様な装置を用いて、希釈後のパルプスラリー（濃度０．８％）５００ｍｌを直径７．５ｃｍのジャーに注ぎ、６００ｒｐｍの攪拌をさせながら下部コックを開き、１００メッシュの金網にてろ過させ、一定のろ液量になるまでの時間を測定するものであり、濾水性の評価に用いることができる。ろ液量が２５０ｇに達するまでの時間を測定した。数値が小さいほど、濾水性が良いことを示している。
【００７９】
応用例２〜６、比較応用例１
応用例１において、実施例２〜６、比較例１で製造したポリアクリルアミド系共重合体を用いた点を除いて、応用例１と同様の操作を行った。測定結果を表８に示す。
【００８０】
比較応用例２
応用例１において、ポリアクリルアミド系共重合体を用いない点を除いて、応用例１と同様の操作を行った。測定結果を表８に示す。
表８
【００８１】
【表８】
応用例７〜８、比較応用例３
応用例１において、ダンボール古紙を叩解したＣＳＦ３６０、電導度１５００μＳ／ｃｍに調整したパルプスラリーに実施例７〜８、比較例２で製造したポリアクリルアミド系共重合体を対パルプ固形分で０．６％用いた点を除いて、応用例１と同様の操作を行った。測定結果を表９に示す。
表９
【００８３】
【表９】
応用例９
段ボール古紙を叩解しカナディアン・スタンダード・フリーネス（ＣＳＦ）３６３、電導度１５００μS／cmに調整した濃度２．４％のパルプスラリーに、実施例９で製造したポリアクリルアミド系共重合体を対パルプ固形分０．１５％添加し、更に１分間攪拌した。攪拌の後、このパルプスラリーをｐＨ７．５、電導度１０００μS／cmの水で０．８％に希釈した後、歩留り剤ハイモロックＮＲ−１２ＭＬＳ（ハイモ（株）製）０．０３％を添加し、ノーブルアンドウッド製シートマシンにて抄紙して、湿紙を得た。この湿紙を、プレス後、ドラムドライヤーで乾燥して８０ｇ／ｍ2の手抄き紙を得た。得られた手抄き紙を２０℃、ＲＨ６５％の条件下で２４時間調湿した後、各種測定を行った。測定結果を表１０に示す。
【００８５】
応用例１０〜１１、比較応用例４
応用例９で、実施例１０〜１１、比較例３で製造したポリアクリルアミド系共重合体を用いた点を除いて、応用例９と同様の操作を行った。測定結果を表１０に示す。
表１０
【００８６】
【表１０】
応用例１２〜２０、比較応用例５
段ボール古紙を叩解しカナディアン・スタンダード・フリーネス（ＣＳＦ）３８０、電導度１５００μS／ｃｍ、ｐＨ７．１に調整した濃度２．４％のパルプスラリーに、硫酸バンドをパルプ固形分に対し３．０％添加した。その後、実施例１２〜２０、比較例４で製造したポリアクリルアミド系共重合体をパルプ固形分に対し０．４５％添加し、更に１分間攪拌した。攪拌の後、このパルプスラリーを電導度５０００μS／ｃｍ、ｐＨ６．０の水で０．８％に希釈した後、ノーブルアンドウッド製シートマシンにて抄紙して、湿紙を得た。この湿紙を、プレス後、ドラムドライヤーで乾燥して８０ｇ／ｍ2の手抄き紙を得た。得られた手抄き紙を２０℃、ＲＨ６５％の条件下で２４時間調湿した後、比破裂強度の測定を行った。ＤＤＴの結果と共に測定結果を表１１に示す。
表１１
【００８８】
【表１１】
応用例２１〜２３、比較応用例６
ＢＫＰ（Ｌ／Ｎ＝８／２）をカナディアン・スタンダード・フリーネス（ＣＳＦ）４０２に調整した濃度２．４％のパルプスラリーに、パルプ固形分に対し、炭酸カルシウム（タマパール１２１Ｓ：奥多摩工業（株）製）１０％、実施例２１〜２３、比較例５で製造したポリアクリルアミド系共重合体０．８％、硫酸バンド２．０％を攪拌下、１分間隔で順次添加した。このパルプスラリーをｐＨ７の水で０．８％に希釈し、歩留り剤ハイモロックＮＲ−１２ＭＬＳ（ハイモ（株）製）０．０１５％を添加し、ノーブルアンドウッド製シートマシンにて抄紙して、湿紙を得た。この湿紙を、プレス後、ドラムドライヤーで乾燥して６０ｇ／ｍ2の手抄き紙を得た。得られた手抄き紙を２０℃、ＲＨ６５％の条件下で２４時間調湿した後、比破裂強度、内部結合強度、裂断長を測定した。得られた結果を表１２に示す。
【００９０】
比較応用例７
応用例２１において、ポリアクリルアミド系共重合体を用いない以外は、応用例２１と同様の操作を行った。測定結果を表１２に示す。
表１２
【００９１】
【表１２】
応用例２４〜３１、比較応用例８〜１２
段ボール古紙を叩解しカナディアン・スタンダード・フリーネス（ＣＳＦ）３７８、硫酸カルシウムで電導度１５００μS／ｃｍに調整した濃度２．４％のパルプスラリーに、硫酸バンドをパルプ固形分に対し１．０％添加した。その後、実施例２４〜３１、比較例６〜１０で製造したポリアクリルアミド系共重合体をパルプ固形分に対し０．４％添加し、更に１分間攪拌した。
【００９３】
攪拌後、このパルプスラリーをｐＨ５、硫酸カルシウムで電導度１５００μS／ｃｍに調整した水で０．８％に希釈した後、ノーブルアンドウッド製シートマシンにて抄紙して、湿紙を得た。この湿紙を、プレス後、ドラムドライヤーで乾燥して８０ｇ／ｍ2の手抄き紙を得た。得られた手抄き紙を２３℃、ＲＨ５０％の条件下で２４時間調湿した後、内部結合強度を測定した。測定結果をＤＤＴの結果と共に表１３に示す。
【００９４】
比較応用例１３
応用例２４において、ポリアクリルアミド系共重合体を用いない以外は、応用例２４と同様の操作を行った。測定結果を表１３に示す。
表１３
【００９５】
【表１３】
応用例３２〜３４、比較応用例１４〜１５
応用例１において、実施例３２〜３４、比較例１１〜１２で製造したポリアクリルアミド系共重合体をパルプ固形分に対し０．４％添加し、硫酸バンドを２．０％添加する点を除いて応用例１と同様の操作を行った。比破裂強度の測定結果を表１４に示す。
【００９７】
比較応用例１６
応用例３２において、ポリアクリルアミド系共重合体を用いない点を除いて、応用例３２と同様の操作を行った。測定結果を表１４に示す。
表１４
【００９８】
【表１４】
応用例３５、比較応用例１７
脱墨パルプ（ＤＩＰ）に硫酸バンドをパルプ固形分に対し３．０％添加し、1分間攪拌した。その後、実施例３５、比較例１３で製造したポリアクリルアミド系共重合体をパルプ固形分に対し０．２％添加し、更に１分間攪拌した。
【０１００】
このパルプスラリーをｐＨ４．５、硫酸カルシウムで電導度２０００μS／ｃｍに調整した水で０．８％に希釈した後、ノーブルアンドウッド製シートマシンにて抄紙して、湿紙を得た。この湿紙を、プレス後、ドラムドライヤーで乾燥して４３ｇ／ｍ2の手抄き紙を得た。得られた手抄き紙を２３℃、ＲＨ５０％の条件下で２４時間調湿した後、内部結合強度、裂断長を測定した。測定結果を表１５に示す。
【０１０１】
比較応用例１８
応用例３５において、ポリアクリルアミド系共重合体を用いない以外は、応用例３５と同様の操作を行った。測定結果を表１５に示す。
表１５
【０１０２】
【０１０３】
本発明により製造した製紙用添加剤は、表７〜１５に示すように、従来公知の製造方法で製造したポリアクリルアミド系共重合体と比較して、バランスよく優れた紙力増強効果、及び濾水性を与えることができる。【Technical field】
[0001]
The present invention Papermaking additive and method for producing papermaking additive In particular, in the papermaking system in the acidic, neutral or alkaline region, a polyacrylamide copolymer papermaking additive capable of exhibiting excellent drainage, yield and paper strength enhancing effect, And a method for producing the paper additive About.
[Background]
[0002]
Conventionally, in the papermaking process, various papermaking additives have been used in order to improve productivity accompanying the increase in the speed of a paper machine or improve paper quality. In particular, the paper strength enhancer is an important chemical for improving the paper quality and productivity, and the range of use thereof is further widened and the improvement of the chemical is progressing.
[0003]
Polyacrylamide copolymers are widely used as paper strength enhancers, and are classified into anionic, cationic, and amphoteric copolymers from the viewpoint of ionicity. First, in the 1960s, an anionic polyacrylamide copolymer was used in combination with a sulfuric acid band. Subsequently, in the 1970s and 80s, for the purpose of improving drainage and yield, a Mannich modified acrylamide polymer into which cationic property was introduced and a Hoffman modified acrylamide polymer were used. However, these modified acrylamide polymers have poor product stability, and the Mannich modified acrylamide polymer has a problem that it contains formalin in the product.
[0004]
Subsequently, since the 1980's, amphoteric polyacrylamide copolymers obtained by copolymerizing anionic and cationic vinyl compounds with acrylamide have been used (Japanese Patent Laid-Open No. 60-94697). This amphoteric polyacrylamide copolymer is used alone or in combination with an anionic polyacrylamide copolymer. The polyacrylamide copolymer has been produced by adding a polymerization initiator to a monomer solution at a predetermined temperature and performing polymerization.
[0005]
In recent years, polymerization methods have been improved in order to enhance the paper strength improvement effect of polyacrylamide copolymers. For example, a method in which polyacrylamide is synthesized in advance and a monomer solution of acrylamide is polymerized in the presence of the polyacrylamide (Japanese Patent Laid-Open No. 3-227485), or a monomer such as acrylamide is dropped into polyacrylamide for polymerization. (JP-A-5-195485) and a method for introducing a graft structure is disclosed. These methods have a disadvantage that productivity is inferior because polyacrylamide is further synthesized after previously synthesizing polyacrylamide. In addition, a method is disclosed in which all monomers including a monomer having a crosslinkable substituent in the side chain are dropped and polymerized to advance branching / crosslinking in the polymer, increase the molecular weight, and improve paper strength ( JP-A-7-133599, JP-A-7-188351, JP-A-11-228641, JP-A-8-67715). Furthermore, a method for improving the performance by continuously synthesizing an anionic polyacrylamide copolymer and a cationic polyacrylamide copolymer by two-step dropping polymerization to form a so-called ion complex is disclosed. (JP-A-6-199965, JP-A-7-90797). However, in recent years, due to fluctuations in the pH of the pulp slurry during papermaking due to fluctuations in the quality of papermaking raw materials, increase in the amount of used paper, contamination due to the progress of closed systems, increase in fine fibers, etc. However, sufficient effects cannot be obtained with conventional polyacrylamide copolymer paper additive. Under such circumstances, in order to improve productivity and paper strength, further improvement of papermaking additives is required.
DISCLOSURE OF THE INVENTION
[Problems to be solved by the invention]
[0006]
The present invention is a situation in which it is difficult to obtain a paper strength enhancing effect due to fluctuations in pH of the pulp slurry during papermaking, mixing of impurities due to deterioration of the papermaking raw material, increase in electric conductivity of papermaking white water, increase in fine fibers, etc. The purpose of the present invention is to provide an additive for papermaking that exhibits an excellent effect of enhancing paper strength and a method for producing the same.
[Means for Solving the Problems]
[0007]
As a result of intensive studies to solve the above problems, the present inventor has made a specific reaction rate after starting polymerization of monomers when producing a paper additive for a polyacrylamide copolymer. At that time, the remaining monomers were added and polymerized to find that a paper additive having an excellent paper strength enhancing effect was obtained, and the present invention was completed.
[0008]
That is, the present invention, which is a means for solving the above problems, comprises (1) (a) (meth) acrylamide, (b) a vinyl monomer having a carboxyl group and / or a sulfonic acid group and salts thereof, and (c) tertiary. A vinyl monomer having an amino group or a quaternary ammonium salt, and (d) Multifunctional monomer only The In the monomer (A) contained After the polymerization initiator was added and the polymerization was started, when the reaction rate of the monomers (A) reached 20 to 96.5%, (a) (meth) acrylamide, (b) a carboxyl group and / or Vinyl monomer having sulfonic acid group and salts thereof, (c) vinyl monomer having tertiary amino group or quaternary ammonium salt, and (d) Multifunctional monomer Selected from the group consisting of At least one monomer only Contains Do A method for producing an additive for papermaking, wherein the monomers (B) are dropped and polymerized;
(2) The method for producing a papermaking additive according to (1), wherein the dropped monomer (B) in (1) comprises (b) a vinyl monomer having a carboxyl group and / or a sulfonic acid group and salts thereof,
(3) The method for producing a papermaking additive according to (1), wherein the monomer (B) to be dropped in (1) comprises (c) a vinyl monomer having a tertiary amino group or a quaternary ammonium salt,
(4) The dropped monomers (B) in (1) are (b) a vinyl monomer having a carboxyl group and / or a sulfonic acid group and salts thereof, and (c) a tertiary amino group or a quaternary ammonium salt. (1) a method for producing a papermaking additive comprising a vinyl monomer having
(5) The dropped monomers (B) in (1) are (a) (meth) acrylamide, (b) a vinyl monomer having a carboxyl group and / or a sulfonic acid group, and salts thereof, (c) tertiary amino A method for producing a paper additive of (1), comprising a vinyl monomer having a group or a quaternary ammonium salt, and (d) a crosslinkable monomer,
(6) Any of the above (1) to (5), wherein the monomers (B) are dropped and polymerized when the reaction rate of the monomers (A) reaches 30 to 90% Or a method for producing a paper additive according to claim 1, and
(7) A method for producing an additive for papermaking as described in any one of (1) to (6) above, wherein polymerization is carried out in the presence of a urea compound.
[0009]
Hereinafter, the present invention will be described in detail. In the present invention, after adding a polymerization initiator to the monomers (A) containing the monomers of the components (a) to (d) and starting the polymerization, the reaction rate of the monomers (A) is 20 to 96.5%. Further, the present invention relates to a method for producing a papermaking additive that is polymerized by adding dropwise monomers (B) containing at least one monomer of components (a) to (d).
[0010]
The (a) (meth) acrylamide that can be used in the present invention is acrylamide or methacrylamide, and these can be used in a powder or an aqueous solution.
[0011]
Examples of the vinyl monomer (b) having a carboxyl group that can be used in the present invention include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, And unsaturated dicarboxylic acids such as muconic acid, aconitic acid, 3-butene-1,2,3-tricarboxylic acid, and 4-pentene-1,2,4-tricarboxylic acid. Examples of the vinyl monomer having a sulfonic acid group include vinyl sulfonic acid, styrene sulfonic acid, (meth) allyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and 2-acrylamido-2-phenylpropane sulfonic acid. Can be mentioned. Moreover, as the vinyl monomer having a carboxyl group and the vinyl monomer having a sulfonic acid group, the vinyl monomer having the carboxyl group, or the alkali metal salt, alkaline earth metal salt of the vinyl monomer having the sulfonic acid group, And ammonium salts. These may be used individually by 1 type and may use 2 or more types together.
[0012]
Examples of the vinyl monomer (c) having a tertiary amino group that can be used in the present invention include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and diethylaminopropyl (meta). ) Dialkylaminoalkyl (meth) acrylates such as acrylate, dialkylaminoalkyl (meth) acrylamides such as dimethylaminopropyl (meth) acrylamide, and diethylaminopropyl (meth) acrylamide, hydrochloric acid of vinyl monomer having the tertiary amino group Examples thereof include inorganic acid salts such as salts and sulfates, and organic acid salts such as formates of vinyl monomers having a tertiary amino group and acetates.
[0013]
Moreover, as a vinyl monomer which has quaternary ammonium salt, the vinyl monomer obtained by reaction of the vinyl monomer which has the said tertiary amino group, and a quaternizing agent is mentioned. Examples of the quaternizing agent include alkyl halides such as methyl chloride and methyl bromide, aralkyl halides such as benzyl chloride and benzyl bromide, dimethyl sulfate, diethyl sulfate, epichlorohydrin, 3-chloro-2-hydroxypropyltrimethyl. Ammonium chloride, glycidyl trialkyl ammonium chloride, etc. are mentioned. These vinyl monomers having a tertiary amino group or a quaternary ammonium salt may be used alone or in combination of two or more.
[0014]
In the present invention, the (d) crosslinkable monomer includes, for example, difunctional monomers such as di (meth) acrylates, bis (meth) acrylamides and divinyl esters, trifunctional monomers, tetrafunctional monomers and the like. A functional monomer etc. can be mentioned, These may be used individually by 1 type and may use 2 or more types together. Examples of the component (d) include water-soluble aziridinyl compounds, water-soluble polyfunctional epoxy compounds, silicon compounds and the like in addition to the above, and these may be used alone or in combination of two or more. May be used in combination.
[0015]
Examples of the di (meth) acrylates include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and glycerin di (meth). An acrylate etc. can be mentioned, These may be used individually by 1 type and may use 2 or more types together. Examples of the bis (meth) acrylamides include N, N′-methylenebis (meth) acrylamide, ethylenebis (meth) acrylamide, hexamethylenebis (meth) acrylamide, N, N′-bisacrylamideacetic acid, N, N ′. -Methyl bisacrylamide, N, N-benzylidenebisacrylamide, N, N'-bis (acrylamidomethylene) urea, etc. can be mentioned, and these may be used alone or in combination of two or more. May be. Examples of the divinyl esters include divinyl adipate, divinyl sebacate, diallyl phthalate, diallyl malate, diallyl succinate, and the like. These may be used alone or in combination of two or more. You may use together. Examples of other bifunctional monomers include allyl (meth) acrylate, divinylbenzene, diisopropenylbenzene, N-methylol acrylamide, N, N-dimethyl (meth) acrylamide, and N, N-diethyl (meth) acrylamide. , Diallyldimethylammonium salt, diallylamine, diallylchlorendate, glycidyl (meth) acrylate, silicon compounds, and the like. These may be used alone or in combination of two or more. .
[0016]
Examples of the trifunctional monomer include triacryl formal, triallyl isocyanurate, N, N-diallylacrylamide, N, N-diallylmethacrylamide, triallylamine, triallyl trimellitate, and the like. May be used alone or in combination of two or more.
[0017]
Examples of the tetrafunctional monomer include tetramethylol methane tetraacrylate, tetraallyl pyromellitate, N, N, N ′, N′-tetraallyl-1,4-diaminobutane, tetraallylamine salt, tetraallyloxyethane, and the like. These may be used alone or in combination of two or more.
[0018]
Examples of the water-soluble aziridinyl compound include tetramethylolmethane-tri-β-aziridinylpropionate, trimethylolpropane-tri-β-aziridinylpropionate, 4,4′-bis (ethyleneiminecarbonyl). Amino) diphenylmethane and the like, and these may be used alone or in combination of two or more. Examples of the water-soluble polyfunctional epoxy compound include (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, (poly) glycerin diglycidyl ether, and (poly) glycerin triglycidyl ether. These may be used alone or in combination of two or more. Examples of the silicon compound include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyldimethoxymethylsilane, 3- (meth) acryloxypropyltrimethoxysilane, and 3- (meth). Examples include acryloxypropylmethyldichlorosilane, 3- (meth) acryloxyoctadecyltriacetoxysilane, 3- (meth) acryloxy-2,5-dimethylhexyldiacetoxymethylsilane, vinyldimethylacetoxysilane, and the like. You may use individually by 1 type and may use 2 or more types together.
[0020]
Examples of the N-substituted (meth) acrylamide include N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, and N-isopropyl. (Meth) acrylamide, Nt-octyl (meth) acrylamide, etc. can be mentioned.
[0021]
Examples of the urea compounds in the present invention include urea and guanidylurea phosphates and sulfates. These may be used alone or in combination of two or more. Of these, urea is preferable. The urea compound is polymerized in addition to the monomer (A), the monomer (B), or both. A part of the urea compound may be added after polymerization. Further, the entire amount of the urea compound may be added after the completion of the polymerization, but it is desirable to add it to the monomers (A) from the viewpoint of the paper strength enhancing effect.
[0022]
The amount of each of the components (a) to (d) in the monomers (A) is the same as that of the paper when the paper is produced using the resulting paper additive containing the polyacrylamide copolymer. The paper strength such as the internal bond strength and the burst strength, and the performance such as the drainage at the time of papermaking, the yield of fine fibers, fillers and the like can be determined.
[0023]
From the viewpoint of paper strength, the component (a) is usually 99.795 to 55 mol%, preferably 99.99 to 79 mol%, and the component (b) with respect to 100 mol% of the total of (a) to (d). Is usually 0.1 to 20 mol%, preferably 1 to 10 mol%, component (c) is usually 0.1 to 20 mol%, preferably 1 to 10 mol%, and component (d) is usually 0.005 to 0.005 mol%. 5 mol%, preferably 0.01 to 1 mol%. The other monomer (e) that can be copolymerized with the monomers (a) to (d) can be used at 5 mol% or less.
[0024]
In the middle of the polymerization, the dropped monomers (B) may be any monomer containing at least one of the components (a) to (d). Among them, the monomer solution containing the component (b) alone, the monomer solution containing the component (c) alone, the monomer solution containing the components (b) and (c), (a), (b And a monomer solution containing the component (c) and a monomer solution containing the components (a) to (d) are preferred.
[0025]
The addition amount of the urea compound is preferably 30% by weight or less, more preferably 10% by weight or less, based on the weight of all monomers. By carrying out the polymerization of the present invention in the presence of a urea compound, a polyacrylamide copolymer having further excellent effects such as paper strength can be synthesized. The present invention also has a feature that the viscosity stability of the paper additive is improved by adding these urea compounds.
[0026]
As the polymerization initiator used in the present invention, conventionally known polymerization initiators can be used. Specifically, persulfates such as sodium persulfate, potassium persulfate and ammonium persulfate, peroxides such as benzoyl peroxide, hydrogen peroxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, bromine Bromate such as sodium acid, potassium bromate, perborate such as sodium perborate, ammonium perborate, percarbonate such as sodium percarbonate, potassium percarbonate, ammonium percarbonate, sodium perphosphate, Perphosphates such as potassium perphosphate and ammonium perphosphate can be used. In this case, one kind can be used alone, but two or more kinds may be used in combination, and use as a redox polymerization agent in combination with a reducing agent may be mentioned. Examples of the reducing agent include sulfites such as sodium sulfite, bisulfites such as sodium bisulfite, organic amines such as N, N, N ′, N′-tetramethylethylenediamine, and reducing sugars such as aldose. it can. Moreover, these reducing agents may be used individually by 1 type, and may be used together 2 or more types. Other than the above, azobisisobutyronitrile, 2,2′-azobis-2-amidinopropane hydrochloride, 2,2′-azobis-2,4′-dimethylvaleronitrile, 4,4′-azobis- Azo polymerization initiators such as 4-cyanovaleric acid and its salts can also be used. Usually, a polymerization initiator is added to the monomer (A) which is a monomer solution, and polymerization is started. However, for the purpose of reducing the residual monomer, a part of the polymerization initiator may be additionally added during the polymerization.
[0027]
Moreover, a conventionally well-known chain transfer agent can be suitably used together with monomers (A) and monomers (B) as needed. Conventionally known chain transfer agents include compounds having one or more hydroxyl groups in the molecule, such as oligomers and polymers such as ethanol, isopropyl alcohol, butanol, ethylene glycol, glycerin alcohols, polyethylene oxide, polyglycerin, Examples thereof include sugars such as glucose, ascorbic acid, and sucrose, and vitamins. Examples of the compound containing one or more mercapto groups in the molecule include butyl mercaptan, mercaptoethanol, thioglycolic acid and its ester, mercaptopropionic acid and its ester, thioglycerin, cysteamine and its salt. be able to. Examples of compounds having one or more carbon-carbon unsaturated bonds in the molecule include (meth) allyl alcohol and its ester derivatives, (meth) allylamine, diallylamine, dimethallylamine and its amide derivatives, triallylamine, Examples include methallylamine, (meth) allylsulfonic acid and salts thereof, allyl sulfides, and allyl mercaptans. Furthermore, mention may be made of hypophosphorous acid.
[0028]
The synthesis of the polyacrylamide copolymer in the present invention is usually performed as follows. First, in an inert gas atmosphere such as nitrogen, the monomers (A) and water as a solvent (an organic solvent may be used in combination) in a predetermined reaction vessel, and the chain transfer agent as necessary While charging and stirring, the polymerization initiator is added to start the polymerization. Next, when the reaction rate of the monomers (A) (hereinafter sometimes referred to as “conversion”) reaches 20 to 96.5%, preferably 30 to 90%, the monomers (B ) Is dripped. After dropping, the polyacrylamide copolymer of the present invention is obtained by further heating and polymerization.
[0029]
Conversion uses the types of each component (a) to (d) in the monomers (A) and the monomers (B), the blending amount, and a paper additive containing the obtained polyacrylamide copolymer. When the paper is manufactured, the paper strength such as the internal bond strength and burst strength of the paper and the performance such as the yield of paper making, paper drainage, fine fiber, filler, etc. should be determined within the above range. Can do. When the conversion is not within the above range, the above performance is not sufficient when paper is produced using the paper additive containing the obtained polyacrylamide copolymer.
[0030]
When the total amount of the monomers (A) and the monomers (B) is 100 mol%, the dropping amount of the monomers (B) is usually 0.00 when the monomers (B) do not contain the component (a). 1-40 mol%, Preferably it is 1-20 mol%, and when monomers (B) contain (a) component, it is 10-70 mol% normally, Preferably it is 20-60 mol%. The dropping time is usually 5 to 60 minutes, preferably 10 to 30 minutes. When the monomers (B) are composed of a plurality of monomer components, they may be dropped as a mixture of a plurality of monomers, or each monomer may be dropped.
[0031]
The polymerization temperature is not particularly limited as long as normal radical polymerization occurs. Usually, the polymerization temperature is in the range of 50 to 95 ° C.
[0032]
As a method for measuring the conversion, for example, a conventionally known technique such as described in “Experimental Method of Polymer Synthesis” (written by Takayuki Otsu and Masami Kinoshita) can be used. value is, 1 It is a value measured by 1 H-NMR.
[0033]
The solid content of the polyacrylamide copolymer synthesized by polymerization is usually 5 to 30% by weight, and the viscosity at 25 ° C. measured with a Brookfield rotational viscometer is usually 20,000 mPa · s or less. .
[0034]
In the present invention, since the monomers (B) are dropped and polymerized during the polymerization of the monomers (A), a method or monomer for polymerizing a monomer solution of acrylamides in the presence of a polyacrylamide copolymer is used. Compared with conventional methods such as a method in which the total amount of is dropped and polymerized, a polyacrylamide copolymer can be produced in a short time.
[0035]
The reason why the polyacrylamide copolymer produced according to the present invention is superior in effect such as paper strength compared to the polyacrylamide copolymer produced by the conventional method is unknown, but is dropped during polymerization. First, a relatively low molecular weight acrylamide polymer is formed, and then the polyacrylamide copolymer becomes high molecular weight due to hydrogen abstraction in the polymer by the polymerization initiator radical remaining in the polymerization system. It is thought that the reason is that it is easy to generate and that ion balance can be optimized.
[0036]
The papermaking additive containing the polyacrylamide copolymer produced according to the present invention exhibits a paper strength enhancing effect by being added to the pulp slurry when the paper is produced. As raw materials for pulp, bleached or unbleached chemical pulp, groundwood pulp, bleached or unbleached pulp such as mechanical pulp and thermomechanical pulp, etc. And waste paper pulp such as deinked waste paper can be used.
[0037]
The paper additive containing the polyacrylamide copolymer produced according to the present invention is less affected by the electrical conductivity of the pulp slurry than the conventional paper additive, and in particular, the electrical conductivity of the pulp slurry is 800 μS / cm or more. At that time, the performance difference from the conventional paper additive is large.
[0038]
Moreover, in order to express the physical property requested | required of each paper type, the other papermaking additive can also be used together with the papermaking additive manufactured by this invention. Examples of other papermaking additives used in combination include fillers, dyes, rosin sizing agents for acidic papermaking, rosin sizing agents for neutral papermaking, alkyl ketene dimer sizing agents, and alkenyl succinic anhydride sizing agents. Examples include weakly acidic, neutral and alkaline papermaking sizing agents such as specially modified rosin sizing agents, wet paper strength improvers, yield improvers, freeness improvers, bulkiness agents, and antifoaming agents. These may be used alone or in combination of two or more. Examples of the filler include clay, talc, titanium oxide, heavy or light calcium carbonate, and the like.
[0039]
The paper additive of the present invention may contain the polyacrylamide copolymer synthesized according to the present invention alone, an anionic polyacrylamide copolymer, a Mannich modified acrylamide polymer, A Hoffman-modified acrylamide polymer and a sulfuric acid band may also be contained. The paper additive of the present invention may be used alone or in combination with an anionic polyacrylamide copolymer, a Mannich modified acrylamide polymer, a Hoffman modified acrylamide polymer, and a sulfuric acid band. good.
[0040]
The paper containing the polyacrylamide copolymer of the present invention is obtained, for example, by paper making using the above-mentioned papermaking additive of the present invention. Examples of the paper obtained include PPC paper and inkjet recording paper. Laser printer paper, form paper, art paper, cast paper, high-quality coated paper and other printing information paper, photographic printing paper, kraft paper, pure white roll paper and other packaging paper, other notebook paper, book paper, printing paper, Examples include western paper such as newspaper, manila balls, white balls, chip balls, paperboard boards such as high-grade white boards, liners, core base paper, and paper tube base paper.
【Example】
[0041]
EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following Example. % Is based on weight unless otherwise indicated. Moreover, unless otherwise indicated, mol% has shown the value when the sum total of monomers (A) and monomers (B) is 100 mol%.
[0042]
(Synthesis of polyacrylamide copolymer)
Example 1 (Synthesis method in which monomer B comprises component (b))
In a 1 liter four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube, 413.36 g of water and 305.39 g (89.62 mol%) of a 50% acrylamide aqueous solution as monomers (A) Dimethylaminoethyl methacrylate 11.30 g (3.0 mol%), 76% methacryloyloxyethyldimethylbenzylammonium chloride aqueous solution 26.85 g (3.0 mol%), itaconic acid 1.87 g (0.6 mol%), 5% aqueous sodium methallylsulfonate solution 28.05 g (0.37 mol%), N, N′-dimethylacrylamide 2.38 g (1.0 mol%), 0.5% triacryl formal 11.95 g (0. 01 mol%) and adjusted to pH 2.5 with a 30% aqueous sulfuric acid solution. Next, the temperature was raised to 60 ° C. in a nitrogen gas atmosphere, 5.77 g of 5% ammonium persulfate aqueous solution was added, and the temperature was raised to 80 ° C. in 20 minutes. When the conversion of these first-stage monomers (monomers (A)) reached 33%, an aqueous monomer solution (B) consisting of 179.24 g of water and 7.48 g (2.4 mol%) of itaconic acid was added for 20 minutes. The solution was added dropwise and polymerized at 80 ° C. When the estimated viscosity at 25 ° C. reached 6,000 to 8,000 mPa · s, the reaction was stopped by cooling. A polymer solution having a solid content of 20.3%, pH of 3.3, and a viscosity (25 ° C., using Brookfield rotary viscometer) of 7,300 mPa · s was obtained.
[0043]
In this example, for the copolymer sampled immediately before the dropping of the monomers (B), 1 H-NMR measurement was performed, and conversion was calculated from the intensity ratio of the peak derived from the monomer and the polymer.
[0044]
Examples 2 to 6 (Synthesis method in which monomer B is composed of component (b))
Except that the monomer (A) conversion and the itaconic acid split addition ratio (in monomers (A) / monomers (B)) were changed when the monomer solution (B) was dropped. Performed as in Example 1. Table 1 shows the conversion, the itaconic acid addition method (partition addition ratio), and the properties of the resulting polyacrylamide copolymer.
[0045]
Comparative Example 1
In a 1 liter four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube, water 593.26 g, 50% acrylamide aqueous solution 305.39 g (89.62 mol%), dimethylaminoethyl methacrylate 11. 30 g (3.0 mol%), 76% methacryloyloxyethyldimethylbenzylammonium chloride aqueous solution 26.85 g (3.0 mol%), itaconic acid 9.35 g (3.0 mol%), 5% sodium methallylsulfonate 28.05 g (0.37 mol%) of an aqueous solution, 2.38 g (1.0 mol%) of N, N′-dimethylacrylamide, 11.95 g (0.01 mol%) of 0.5% triacryl formal, The pH was adjusted to 2.5 with a 30% aqueous sulfuric acid solution. Next, the temperature was raised to 60 ° C. in a nitrogen gas atmosphere, 5.77 g of 5% ammonium persulfate aqueous solution was added, the temperature was raised to 80 ° C. in 20 minutes, and polymerization was carried out at 80 ° C. as it was. When the estimated viscosity at 25 ° C. reached 6,000 to 8,000 mPa · s, the reaction was stopped by cooling. A polymer solution having a solid content of 20.2%, a pH of 3.4, and a viscosity (25 ° C., using a Brookfield rotational viscometer) of 7,120 mPa · s was obtained.
Table 1
[0046]
[Table 1]
Example 7
In a 1 liter four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube, water 413.40 g, isopropyl alcohol 60.0 g, 50% acrylamide aqueous solution 346.96 g (91.29 mol%), 76% methacryloyloxyethyldimethylbenzylammonium chloride aqueous solution 13.98 g (1.4 mol%), fumaric acid 4.03 g (1.3 mol%), 0.5% triacryl formal 13.33 g (0.01 mol%) ). Next, the temperature was raised to 60 ° C. in a nitrogen gas atmosphere, 4.88 g of 5% ammonium persulfate aqueous solution was added, and the temperature was raised to 80 ° C. in 20 minutes. When the conversion of these first-stage monomers (monomers (A)) reached 35%, an aqueous monomer solution consisting of 128.79 g of water and 14.45 g (6.0 mol%) of 80% acrylic acid was added over 20 minutes. The solution was added dropwise and polymerization was carried out at 80 ° C. for 2 hours. When the estimated viscosity at 25 ° C. reached 5,000 to 7,000 mPa · s, the reaction was stopped by cooling. A polymer solution having a solid content of 20.3%, a pH of 3.3, and a viscosity (25 ° C., using Brookfield rotary viscometer) of 6,360 mPa · s was obtained.
[0048]
Examples 8 to 11 (Synthesis method in which monomers (B) are composed of component (b))
The synthesis reaction was performed in the same manner as in Example 7 except that the monomers (A), the monomers (B), and the chain transfer agent were changed as shown in Table 2. Table 3 shows the properties of the obtained polyacrylamide copolymer.
[0049]
Comparative Examples 2 and 3
The synthesis reaction was performed in the same manner as in Comparative Example 1 except that the monomers (A) and the chain transfer agent were changed as shown in Table 2. Table 3 shows the properties of the obtained polyacrylamide copolymer.
Table 2
[0050]
[Table 2]
Table 3
[0052]
[Table 3]
Example 12 (Synthesis method in which monomer B comprises component (c))
In a 1-liter four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube, 494.15 g of water and, as monomers (A), 305.06 g (90.62 mol%) of 50% acrylamide aqueous solution , 76% acryloyloxyethyldimethylbenzylammonium chloride aqueous solution 25.22 g (3.0 mol%), itaconic acid 9.24 g (3.0 mol%), 5% sodium methallylsulfonate aqueous solution 27.71 g (0.37 Mol%), 2.35 g (1.0 mol%) of N, N′-dimethylacrylamide, and 11.81 g (0.01 mol%) of 0.5% triacryl formal were charged. Next, the temperature was raised to 60 ° C. in a nitrogen gas atmosphere. 10.80 g of 5% ammonium persulfate aqueous solution was added to initiate polymerization, and the temperature was raised to 85 ° C. When the conversion of these first-stage monomers (monomers (A)) reached 20.4%, 90.08 g of water and 16.81 g of 76% acryloyloxyethyldimethylbenzylammonium chloride aqueous solution (2.0 mol%) The monomer aqueous solution (B) consisting of) was added dropwise over 20 minutes and kept at 80 ° C. When the estimated viscosity at 25 ° C. reached 6,000 to 9,000 mPa · s, the reaction was stopped by cooling. A polymer solution having a solid content of 20.4%, a pH of 3.2, and a viscosity (25 ° C., using Brookfield rotary viscometer) of 6,240 mPa · s was obtained.
[0054]
Examples 13 to 20 (Synthesis method in which monomer B is composed of component (c))
Conversion of monomers (A) when adding monomer solution (B) dropwise, and split addition ratio of 76% acryloyloxyethyldimethylbenzylammonium chloride (in monomers (A) / monomers (B)) The same operation as in Example 7 was performed except for the changed points. Table 4 shows the conversion, the split addition ratio of 76% acryloyloxyethyldimethylbenzylammonium chloride, and the properties of the resulting polyacrylamide copolymer.
[0055]
Comparative Example 4
In a 1-liter four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube, water 536.89 g, 50% aqueous acrylamide solution 305.06 g (90.62 mol%), 76% acryloyloxyethyldimethyl Benzylammonium chloride aqueous solution 42.03 g (5.0 mol%), itaconic acid 9.24 g (3.0 mol%), 5% sodium methallylsulfonate aqueous solution 27.71 g (0.37 mol%), N, N 2.35 g (1.0 mol%) of '-dimethylacrylamide and 11.81 g (0.01 mol%) of 0.5% triacryl formal were charged. Otherwise, the synthesis reaction was performed in the same manner as in Comparative Example 1 to obtain a polymer solution having a solid content of 20.2%, pH 3.3, and viscosity (25 ° C., using Brookfield rotary viscometer) 8,200 mPa · s.
Table 4
[0056]
[Table 4]
Example 21 (Synthesis method in which monomer B comprises components (b) and (c))
In a 1-liter four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube, 603.53 g of water and 266.43 g (94.28 mol%) of 50% acrylamide aqueous solution as monomers (A) Dimethylaminoethyl methacrylate, 8.44 g (2.7 mol%), itaconic acid 4.97 g (1.92 mol%), 5% aqueous sodium methallylsulfonate solution 18.55 g (0.30 mol%), 19.82 g (0.02 mol%) of 5% triacryl formal was charged and adjusted to pH 2.5 with 30% sulfuric acid. Next, the temperature was raised to 60 ° C. in a nitrogen gas atmosphere. 4.54 g of 5% aqueous ammonium persulfate solution was added to initiate polymerization, and the temperature was raised to 85 ° C. When the conversion of these first-stage monomers (monomers (A)) reached 30.2%, water 73.79 g, dimethylaminoethyl methacrylate 0.94 g (0.30 mol%), itaconic acid 1.24 g A monomer aqueous solution (B) composed of (0.48 mol%) was added dropwise over 20 minutes and kept at 80 ° C. When the estimated viscosity at 25 ° C. reached 7,000 to 8,000 mPa · s, the reaction was stopped by cooling. A polymer solution having a solid content of 15.4%, a pH of 3.5, and a viscosity (25 ° C., using Brookfield rotational viscometer) of 7,900 mPa · s was obtained.
[0058]
Examples 22 to 23 (Synthesis method in which monomer B is composed of components (b) and (c))
It carried out like Example 21 except the point which changed conversion of monomers (A) at the time of dropping monomers (B). Table 5 shows the conversion of the monomers (A) at the time of dropping and the properties of the obtained polyacrylamide copolymer.
[0059]
Comparative Example 5
In a 1 liter four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube, 675.32 g of water, 266.46 g (94.28 mol%) of a 50% acrylamide aqueous solution, dimethylaminoethyl methacrylate, 9. 38 g (3.0 mol%), 6.21 g (2.4 mol%) itaconic acid, 18.55 g (0.30 mol%) 5% aqueous sodium methallylsulfonate, 0.5% triacryl formal 19. 82 g (0.02 mol%) was charged and adjusted to pH 2.5 with 30% sulfuric acid. Otherwise, the synthesis reaction was performed in the same manner as in Comparative Example 1. Table 5 shows the properties of the obtained polyacrylamide copolymer.
Table 5
[0060]
[Table 5]
Example 24 (Synthesis method in which monomer B comprises components (a), (b), (c), and (d))
In a 1 liter four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube, 382.80 g of water and 198.60 g (56.24 mol%) of 50% acrylamide aqueous solution as monomers (A) Dimethylaminoethyl methacrylate 4.69 g (1.2 mol%), itaconic acid 7.27 g (2.25 mol%), 5% sodium methallylsulfonate aqueous solution 23.57 g (0.30 mol%), 1% N, N methylenebisacrylamide (3.83 g, 0.01 mol%) was charged, and the pH was adjusted to 3.0 with 30% sulfuric acid. Next, the temperature was raised to 60 ° C. in a nitrogen gas atmosphere. 4.54 g of 5% aqueous ammonium persulfate solution was added to initiate polymerization, and the temperature was raised to 85 ° C. When the conversion of these first-stage monomers (monomers (A)) reached 21.0%, water 196.63 g, 50% aqueous acrylamide solution 130.27 g (36.89 mol%), 76% methacryloyloxyethyl Dimethylbenzylammonium chloride aqueous solution 25.97 g (2.8 mol%), itaconic acid 0.81 g (0.25 mol%), 5% sodium methallylsulfonate aqueous solution 3.93 g (0.05 mol%), 1% An aqueous monomer solution (B) consisting of 3.83 g (0.01 mol%) of N, N methylenebisacrylamide was added dropwise over 20 minutes, and the mixture was kept at 80 ° C. for 20 minutes. Further, 9.06 g of 5% ammonium persulfate aqueous solution was added, and the mixture was kept at 80 ° C. as it was. When the estimated viscosity at 25 ° C. reached 6,000 to 9,000 mPa · s, the reaction was stopped by cooling. A polymer solution having a solid content of 20.4%, a pH of 3.6, and a viscosity (25 ° C., using Brookfield rotary viscometer) of 6,500 mPa · s was obtained.
[0062]
Examples 25 to 29 (Synthesis method in which monomer B is composed of components (a), (b), (c), and (d))
The same procedure as in Example 24 was performed, except that the conversion of the monomers (A) when the monomers (B) were dropped was changed. Table 6 shows the conversion of the monomers (A) at the time of dropping and the properties of the obtained polyacrylamide copolymer.
[0063]
Comparative Example 6
In a 1 liter four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas introduction tube, water 579.43 g, 50% acrylamide aqueous solution 328.87 g (93.13 mol%), dimethylaminoethyl methacrylate 4. 69 g (1.2 mol%), 76% methacryloyloxyethyldimethylbenzylammonium chloride aqueous solution 25.97 g (2.8 mol%), itaconic acid 8.08 g (2.5 mol%), 5% sodium methallylsulfonate 27.50 g (0.35 mol%) of an aqueous solution, 7.66 g (0.02 mol%) of 1% N, N methylenebisacrylamide were charged, and the pH was adjusted to 3.0 with 30% sulfuric acid. Otherwise, the synthesis reaction was performed in the same manner as in Comparative Example 1. Table 6 shows the properties of the obtained polyacrylamide copolymer.
[0064]
Comparative Example 7
The same procedure as in Example 24 was performed except that the conversion of the monomers (A) when the monomers (B) were dropped was changed to 15%. Table 6 shows the conversion of the monomers (A) at the time of dropping and the properties of the obtained polyacrylamide copolymer.
[0065]
Example 30 (Synthesis method containing urea)
In a 1-liter four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube, 382.80 g of water and 9.96 g of urea as a monomer (A), 188.68 g of 50% acrylamide aqueous solution (56 .24 mol%), 4.69 g (1.2 mol%) of dimethylaminoethyl methacrylate, 7.27 g (2.25 mol%) of itaconic acid, 23.57 g (0.30 mol) of 5% aqueous solution of sodium methallylsulfonate %), 1.83 g (0.01 mol%) of 1% N, N methylenebisacrylamide was charged, and the pH was adjusted to 3.0 with 30% sulfuric acid. Next, the temperature was raised to 60 ° C. in a nitrogen gas atmosphere. 5.38 g of 5% ammonium persulfate aqueous solution was added to initiate polymerization, and the temperature was raised to 85 ° C. When the conversion of these first stage monomers (monomers (A)) reached 90.3%, water 227.12 g, 50% acrylamide aqueous solution 123.77 g (36.89 mol%), 76% methacryloyloxyethyl Dimethylbenzylammonium chloride aqueous solution 25.97 g (2.8 mol%), itaconic acid 0.81 g (0.25 mol%), 5% sodium methallylsulfonate aqueous solution 3.93 g (0.05 mol%), 1% While adding an aqueous monomer solution consisting of 3.83 g (0.01 mol%) of N, N methylenebisacrylamide, the mixture was cooled to 80 ° C. and kept at 80 ° C. When the estimated viscosity at 25 ° C. reached 6,000 to 9,000 mPa · s, the reaction was stopped by cooling. A polymer solution having a solid content of 20.3%, pH of 3.6, and a viscosity (25 ° C., using Brookfield rotary viscometer) of 6,450 mPa · s was obtained.
[0066]
Example 31 (Synthesis method containing urea)
It carried out similarly to Example 30 except the point which changed the conversion of the monomers (A) at the time of dripping the monomers (B). Table 6 shows the conversion of the monomers (A) at the time of dropping and the properties of the obtained polyacrylamide copolymer.
[0067]
Comparative Example 8
In a 1-liter four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube, 418.35 g of water and 197.64 g (56.24 mol%) of 50% acrylamide aqueous solution as monomers (A) 4.66 g (1.2 mol%) of dimethylaminoethyl methacrylate, 7.24 g (2.25 mol%) of itaconic acid, 23.57 g (0.30 mol%) of 5% aqueous sodium methallylsulfonate, 1% 3.81 g (0.01 mol%) of N, N methylenebisacrylamide was charged and adjusted to pH 3.0 with 30% sulfuric acid. Next, the temperature was raised to 40 ° C. in a nitrogen gas atmosphere. 7.90 g of 10% aqueous ammonium persulfate solution and 4.63 g of 10% aqueous sodium hydrogen sulfite solution were added to initiate polymerization, and the temperature was raised to 85 ° C. After polymerization at 85 ° C. for 2 hours, 127.60 g of water separately charged, 129.64 g (36.89 mol%) of 50% aqueous acrylamide solution, 25.85 g (2.8%) of 76% methacryloyloxyethyldimethylbenzylammonium chloride aqueous solution Mol%), itaconic acid 0.80 g (0.25 mol%), 5% sodium methallylsulfonate aqueous solution 3.91 g (0.05 mol%), 1% N, N methylenebisacrylamide 3.81 g (0. 01 mol%) 44.57 g of 3% potassium persulfate aqueous solution was added dropwise over 1 hour. After completion of dropping, the mixture was further kept at 85 ° C. for 1 hour to obtain a polymer solution having a solid content of 20.4%, pH 4.3, and viscosity (25 ° C., using Brookfield rotary viscometer) 5,500 mPa · s.
[0068]
Comparative Example 9
In a beaker, 31.55 g (93.13 mol%) of 50% acrylamide aqueous solution, 4.42 g (1.2 mol%) of dimethylaminoethyl methacrylate, 24.52 g (2.8 mol) of 76% methacryloyloxyethyldimethylbenzylammonium chloride aqueous solution. %), 7.64 g (2.5 mol%) itaconic acid, 25.97 g (0.35 mol%) of 5% aqueous sodium methallylsulfonate, 7.24 g (0.02 g) of 1% N, N methylenebisacrylamide Mol%) was adjusted to pH 4.5 to prepare a monomer A solution. A 1 liter four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube was charged with 496.85 g of water, adjusted to pH 4.5 with 1% sulfuric acid, and adjusted to 50 ° C. under a nitrogen gas atmosphere. The temperature rose. Subsequently, the monomer A solution, 61.55 g of 1% ammonium persulfate aqueous solution and 61.27 g of 0.2% sodium hydrogensulfite aqueous solution were continuously added dropwise to the reaction vessel over 70 minutes. During the dropping, the internal temperature was kept at 50 ° C. After completion of the dropping, a polymerization reaction was further performed at 50 ° C. for 110 minutes to obtain a polymer solution having a solid content of 20.4%, pH 3.8, and viscosity (25 ° C., using Brookfield rotary viscometer) 5,050 mPa · s. .
[0069]
Comparative Example 10
In a beaker 49.65 g of water, 19.42 g (5.82 mol%) of 50% aqueous acrylamide solution, 7.63 g (2.5 mol%) itaconic acid, 25.9 g of aqueous 5% sodium methallylsulfonate (0.35 g) Mol%) and adjusted to pH 4.5 with a 30% aqueous sodium hydroxide solution to obtain a first-stage monomer solution. In a separate beaker, 291.25 g (87.29 mol%) of 50% aqueous acrylamide, 4.43 g (1.2 mol%) of dimethylaminoethyl methacrylate, 24.54 g (2.nd) of 76% methacryloyloxyethyldimethylbenzylammonium chloride. 8 mol%) and 7.24 g (0.02 mol%) of 1% N, N methylenebisacrylamide were charged and adjusted to pH 4.5 with 30% sulfuric acid to obtain a second monomer solution. A 1 liter four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube was charged with 446.85 g of water, 5.55 g (0.02 mol%) of 1% N, N methylenebisacrylamide, The pH was adjusted to 4.5 with 1% sulfuric acid, and the temperature was raised to 50 ° C. in a nitrogen gas atmosphere. Next, the first stage monomer solution, 61.60 g of 0.2% ammonium persulfate aqueous solution and 61.30 g of 1% sodium hydrogensulfite aqueous solution were continuously added dropwise to the reaction vessel over 14 minutes. During the dropping, the internal temperature was kept at 50 ° C. After completion of dropping, the mixture was kept at 50 ° C. for 10 minutes, and then the monomer solution (B) was dropped over 56 minutes. After completion of the dropping, a polymerization reaction was carried out at 50 ° C. for 100 minutes to obtain a polymer solution having a solid content of 20.4%, pH 4.6, and viscosity (25 ° C., using Brookfield rotary viscometer) 5,760 mPa · s.
Table 6
[0070]
[Table 6]
Example 32 (Synthesis method in which monomer B comprises components (a), (b), and (c))
495.68 g of 1 liter four-necked water equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube, 277.05 g (81.10 mol%) of 50% acrylamide aqueous solution as monomer A in the flask, 76% acryloyl 29.85 g (3.5 mol%) oxyethyldimethylbenzylammonium chloride aqueous solution, 6.25 g (2.0 mol%) itaconic acid, 29.64 g (0.39 mol%) 5% aqueous sodium methallylsulfonate, 2.38 g (1.0 mol%) of N, N′-dimethylacrylamide and 11.98 g (0.01 mol%) of 0.5% triacryl formal were charged and adjusted to pH 3.0 with 30% sodium hydroxide. . Next, the temperature was raised to 60 ° C. in a nitrogen gas atmosphere. 5.48 g of 5% ammonium persulfate aqueous solution was added to initiate polymerization, and the temperature was raised to 85 ° C. When the conversion of these first-stage monomers (monomers (A)) reached about 50%, 93.31 g of water and 34.16 g (10.0 mol%) of 50% acrylamide aqueous solution were charged separately, 76 % Acryloyloxyethyldimethylbenzylammonium chloride aqueous solution 12.79 g (1.5 mol%) and itaconic acid 1.56 g (0.50 mol%) were added dropwise over 20 minutes, and the mixture was kept at 80 ° C. for 20 minutes. Further, 9.06 g of 5% ammonium persulfate aqueous solution was added, and the mixture was kept at 80 ° C. as it was. When the estimated viscosity at 25 ° C. reached 6,000 to 9,000 mPa · s, the reaction was stopped by cooling. A polymer solution having a solid content of 20.5%, a pH of 3.7, and a viscosity (25 ° C., using Brookfield rotary viscometer) of 6,050 mPa · s was obtained.
[0072]
Examples 33 to 34 (Synthesis method in which monomer B is composed of components (a), (b), and (c))
The same procedure as in Example 32 was performed except that the conversion of the monomers (A) when the monomers (B) were dropped was changed. Table 7 shows the conversion of the monomers (A) at the time of dropping and the properties of the obtained polyacrylamide copolymer.
[0073]
Comparative Examples 11-12
The same operation as in Example 32 was performed except that the conversion of the monomers (A) when the monomers (B) were dropped was changed. Table 7 shows the conversion of the monomers (A) at the time of dropping and the properties of the obtained polyacrylamide copolymer.
Table 7
[0074]
[Table 7]
Example 35 (Synthesis method containing urea)
In a 1 liter four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube, 439.66 g of water, 10.00 g of urea, and 239.39 g of a 50% acrylamide aqueous solution as monomers (A) (56 275 mol%), 5.65 g (1.2 mol%) of dimethylaminoethyl methacrylate, 7.79 g (2.0 mol%) itaconic acid, 47.32 g (0.50 mol) of 5% aqueous solution of sodium methallylsulfonate. %), And 11.53 g (0.025 mol%) of 1% N, N methylenebisacrylamide were charged and adjusted to pH 2.5 with 30% sulfuric acid. Next, the temperature was raised to 60 ° C. in a nitrogen gas atmosphere. 6.82 g of 5% ammonium persulfate aqueous solution was added to initiate polymerization, and the temperature was raised to 85 ° C. When the conversion of these first-stage monomers (monomers (A)) reached 89.2%, water 33.46 g, 50% acrylamide aqueous solution 155.68 g (36.60 mol%), 76% methacryloyloxyethyl Comprising 31.29 g (2.8 mol%) of aqueous dimethylbenzylammonium chloride, 1.95 g (0.50 mol%) of itaconic acid, and 9.46 g (0.10 mol%) of 5% aqueous sodium methallylsulfonate. While adding the monomer aqueous solution, the mixture was cooled to 80 ° C. and kept at 80 ° C. When the estimated viscosity at 25 ° C. reached 6,000 to 9,000 mPa · s, the reaction was stopped by cooling. A polymer solution having a solid content of 25.2%, a pH of 4.1, and a viscosity (25 ° C., using Brookfield rotary viscometer) of 8,820 mPa · s was obtained.
[0076]
Comparative Example 13 (Synthesis method containing urea)
In a 1 liter four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube, water 473.12 g, urea 10 g, 50% acrylamide aqueous solution 395.07 g (92.875 mol%), dimethylaminoethyl 5.65 g (1.2 mol%) of methacrylate, 31.29 g (2.8 mol%) of 76% methacryloyloxyethyldimethylbenzylammonium chloride aqueous solution, 9.74 g (2.5 mol%) itaconic acid, 5% methallyl An aqueous sodium sulfonate solution 56.78 g (0.60 mol%), 11.53 g (0.025 mol%) of 1% N, N methylenebisacrylamide were charged, and the pH was adjusted to 2.5 with 30% sulfuric acid. Otherwise, the synthesis reaction was performed in the same manner as in Comparative Example 1 to obtain a polymer solution having a solid content of 25.5%, pH 4.2, and viscosity (25 ° C., using Brookfield rotary viscometer) 8,110 mPa · s.
[0077]
(Production of paper and measurement of physical properties)
Application example 1
Sulfuric acid band was added to 1.0% of pulp solid content to pulp slurry having a concentration of 2.4% adjusted to Canadian Standard Freeness (CSF) 411 and conductivity of 1500 μS / cm by beating used corrugated paper. Thereafter, 0.5% of the polyacrylamide copolymer produced in Example 1 was added to the pulp solid content, and the mixture was further stirred for 1 minute. After stirring, the pulp slurry was diluted to 0.8% with water having an electric conductivity of 3000 μS / cm, and then paper was made with a sheet machine made by Noble and Wood to obtain a wet paper. The wet paper is pressed and dried with a drum dryer at 80 g / m. 2 Hand-made paper was obtained. The obtained handmade paper was conditioned at 20 ° C. and RH 65% for 24 hours, and then various measurements were performed. Table 8 shows the measurement results. The physical properties were measured according to the following methods.
[0078]
Specific burst strength: Based on JIS P-8112.
Internal bond strength: JAPAN-TAPPI paper pulp test method no. 54.
Breaking length: Based on JIS P-8113.
DDT ・ ・ ・ Tappi, Vol. 56, No. 10 (1973), p. 46, using the same apparatus as that for “Dynamic Drainage Jar”, diluted pulp slurry (Concentration 0.8%) Pour 500 ml into a 7.5 cm diameter jar, open the bottom cock while stirring at 600 rpm, filter through a 100 mesh wire mesh, and measure the time until a constant filtrate volume is reached It can be used to evaluate drainage. The time until the filtrate amount reached 250 g was measured. The smaller the value, the better the drainage.
[0079]
Application examples 2-6, comparative application example 1
In Application Example 1, the same operations as in Application Example 1 were performed except that the polyacrylamide copolymer produced in Examples 2 to 6 and Comparative Example 1 was used. Table 8 shows the measurement results.
[0080]
Comparative application example 2
In Application Example 1, the same operation as in Application Example 1 was performed except that the polyacrylamide copolymer was not used. Table 8 shows the measurement results.
Table 8
[0081]
[Table 8]
Application examples 7-8, comparative application example 3
In Application Example 1, the polyacrylamide copolymer produced in Examples 7 to 8 and Comparative Example 2 was added to a pulp slurry adjusted to a CSF 360 beaten from corrugated cardboard paper and an electric conductivity of 1500 μS / cm to 0.6 pulp solids. The same operation as in Application Example 1 was performed except that% was used. Table 9 shows the measurement results.
Table 9
[0083]
[Table 9]
Application example 9
The polyacrylamide copolymer produced in Example 9 was added to a pulp slurry having a concentration of 2.4% adjusted to Canadian Standard Freeness (CSF) 363 and conductivity of 1500 μS / cm by beating waste corrugated paper. 0.15% was added and the mixture was further stirred for 1 minute. After stirring, the pulp slurry was diluted to 0.8% with water having a pH of 7.5 and an electric conductivity of 1000 μS / cm, and then the yield agent Hymorlock NR-12MLS (manufactured by Hymo Co., Ltd.) 0.03% was added. Papermaking was performed with a Noble and Wood sheet machine to obtain wet paper. The wet paper is pressed and dried with a drum dryer at 80 g / m. 2 Hand-made paper was obtained. The obtained handmade paper was conditioned at 20 ° C. and RH 65% for 24 hours, and then various measurements were performed. Table 10 shows the measurement results.
[0085]
Application examples 10-11, comparative application example 4
The same operations as in Application Example 9 were performed except that the polyacrylamide copolymer produced in Examples 10 to 11 and Comparative Example 3 was used in Application Example 9. Table 10 shows the measurement results.
Table 10
[0086]
[Table 10]
Application examples 12-20, comparative application example 5
Sulfuric acid band is added to pulp solid content by 3.0% to pulp slurry of 2.4% concentration adjusted to Canadian Standard Freeness (CSF) 380, conductivity 1500μS / cm, pH 7.1 by beating used corrugated paper did. Thereafter, 0.45% of the polyacrylamide copolymer produced in Examples 12 to 20 and Comparative Example 4 was added to the pulp solid content, and the mixture was further stirred for 1 minute. After stirring, the pulp slurry was diluted to 0.8% with water having an electric conductivity of 5000 μS / cm and pH 6.0, and then paper was made with a sheet machine made by Noble and Wood to obtain a wet paper. The wet paper is pressed and dried with a drum dryer at 80 g / m. 2 Hand-made paper was obtained. The obtained handmade paper was conditioned at 20 ° C. and RH 65% for 24 hours, and then the specific burst strength was measured. Table 11 shows the measurement results together with the DDT results.
Table 11
[0088]
[Table 11]
Application Examples 21-23, Comparative Application Example 6
To a pulp slurry having a concentration of 2.4% prepared by adjusting BKP (L / N = 8/2) to Canadian Standard Freeness (CSF) 402, calcium carbonate (Tama Pearl 121S: Okutama Industry Co., Ltd.) (Product) 10%, 0.8% of the polyacrylamide copolymer prepared in Examples 21 to 23 and Comparative Example 5 and 2.0% of sulfuric acid band were sequentially added at intervals of 1 minute with stirring. This pulp slurry was diluted to 0.8% with water at pH 7, and 0.015% of the retention agent Hymorlock NR-12MLS (manufactured by Hymo Co., Ltd.) was added. I got paper. This wet paper is pressed and dried with a drum dryer at 60 g / m. 2 Hand-made paper was obtained. The resulting handmade paper was conditioned for 24 hours under the conditions of 20 ° C. and RH 65%, and then the specific burst strength, internal bond strength, and fracture length were measured. The results obtained are shown in Table 12.
[0090]
Comparative application example 7
In Application Example 21, the same operation as in Application Example 21 was performed except that the polyacrylamide copolymer was not used. Table 12 shows the measurement results.
Table 12
[0091]
[Table 12]
Application examples 24-31, comparative application examples 8-12
Sulfuric acid band was added to 1.0% of pulp solids to pulp slurry of 2.4% concentration adjusted to Canadian Standard Freeness (CSF) 378, calcium sulfate and conductivity of 1500μS / cm . Thereafter, 0.4% of the polyacrylamide copolymer produced in Examples 24-31 and Comparative Examples 6-10 was added to the pulp solid content, and the mixture was further stirred for 1 minute.
[0093]
After stirring, this pulp slurry was diluted to 0.8% with water adjusted to have a conductivity of 1500 μS / cm with pH 5 and calcium sulfate, and then paper was made with a Noble and Wood sheet machine to obtain a wet paper. The wet paper is pressed and dried with a drum dryer at 80 g / m. 2 Hand-made paper was obtained. The resulting handmade paper was conditioned for 24 hours under conditions of 23 ° C. and RH 50%, and then the internal bond strength was measured. The measurement results are shown in Table 13 together with the DDT results.
[0094]
Comparative application example 13
In Application Example 24, the same operation as in Application Example 24 was performed, except that the polyacrylamide copolymer was not used. Table 13 shows the measurement results.
Table 13
[0095]
[Table 13]
Application examples 32-34, comparative application examples 14-15
In application example 1, 0.4% of the polyacrylamide copolymer produced in Examples 32-34 and Comparative Examples 11-12 is added to the pulp solid content, except that 2.0% sulfuric acid band is added. The same operation as in Application Example 1 was performed. Table 14 shows the measurement results of the specific burst strength.
[0097]
Comparative application example 16
In Application Example 32, the same operation as in Application Example 32 was performed except that a polyacrylamide copolymer was not used. Table 14 shows the measurement results.
Table 14
[0098]
[Table 14]
Application Example 35, Comparative Application Example 17
A sulfuric acid band was added to deinked pulp (DIP) at 3.0% based on the pulp solid content, and the mixture was stirred for 1 minute. Subsequently, 0.2% of the polyacrylamide copolymer produced in Example 35 and Comparative Example 13 was added to the pulp solid content, and the mixture was further stirred for 1 minute.
[0100]
This pulp slurry was diluted to 0.8% with water adjusted to a conductivity of 2000 μS / cm with pH 4.5 and calcium sulfate, and then papermaking was performed with a Noble and Wood sheet machine to obtain a wet paper. This wet paper is pressed and dried with a drum dryer at 43 g / m 2 Hand-made paper was obtained. The obtained handmade paper was conditioned for 24 hours under the conditions of 23 ° C. and RH 50%, and then the internal bond strength and tear length were measured. Table 15 shows the measurement results.
[0101]
Comparative application example 18
In Application Example 35, the same operation as in Application Example 35 was performed, except that the polyacrylamide copolymer was not used. Table 15 shows the measurement results.
Table 15
[0102]
[0103]
As shown in Tables 7 to 15, the papermaking additive produced according to the present invention has a well balanced paper strength enhancing effect and filtration compared with the polyacrylamide copolymer produced by a conventionally known production method. Aqueous can be given.
Claims (7)
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| CN102272533B (en) * | 2008-12-25 | 2014-11-26 | 三洋电机株式会社 | Air-conditioning control apparatus, cooling system, and air-conditioning control program |
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| US20060249269A1 (en) | 2005-05-03 | 2006-11-09 | Kurian Pious V | High molecular weight compact structured polymers, methods of making and using |
| US8816031B2 (en) | 2006-03-06 | 2014-08-26 | Harima Chemicals, Inc. | Water-soluble polymer and additive for paper manufacture |
| JP5157120B2 (en) * | 2006-10-17 | 2013-03-06 | 栗田工業株式会社 | Method for producing crosslinked polymer and method for producing paper and paperboard |
| JP5640458B2 (en) * | 2010-05-25 | 2014-12-17 | 星光Pmc株式会社 | Method for producing paper-making paper strength enhancer |
| CN103242481B (en) * | 2013-04-26 | 2015-09-09 | 沁阳市制药厂 | A kind of preparation method of high solids content polypropylene-base paper making intensifier |
| JP6376343B2 (en) * | 2014-11-10 | 2018-08-22 | 荒川化学工業株式会社 | Paper additive and paper obtained using the additive |
| ES2930236T3 (en) * | 2017-06-28 | 2022-12-09 | Harima Chemicals Inc | Method for producing a (meth)acrylamide polymer papermaking additive and (meth)acrylamide polymer papermaking additive |
| AU2018291215B2 (en) * | 2017-06-28 | 2020-01-23 | Harima Chemicals, Incorporated | Method for producing (meth) acrylamide polymer papermaking additive and (meth) acrylamide polymer papermaking additive |
| CN112601860B (en) * | 2018-08-31 | 2023-10-03 | 星光Pmc株式会社 | Additive for papermaking, paper and method for producing paper |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3358377B2 (en) * | 1995-03-17 | 2002-12-16 | 日本ピー・エム・シー株式会社 | Surface paper quality improver |
| JP3273534B2 (en) * | 1995-09-14 | 2002-04-08 | 星光化学工業株式会社 | Papermaking additive and papermaking method |
| US6255400B1 (en) * | 1997-11-28 | 2001-07-03 | Mitsui Chemicals, Inc. | Polymer and applications thereof |
| JP2000212229A (en) * | 1999-01-27 | 2000-08-02 | Harima Chem Inc | Additive for paper-making and its preparation |
-
2001
- 2001-12-26 JP JP2002554324A patent/JP4158145B2/en not_active Expired - Lifetime
- 2001-12-26 WO PCT/JP2001/011467 patent/WO2002053835A1/en active Application Filing
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100549545C (en) * | 2005-03-03 | 2009-10-14 | 煜丰科技股份有限公司 | Air conditioner room outdoor heat exchange automatic balancing method |
| CN102272533B (en) * | 2008-12-25 | 2014-11-26 | 三洋电机株式会社 | Air-conditioning control apparatus, cooling system, and air-conditioning control program |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2002053835A1 (en) | 2002-07-11 |
| JPWO2002053835A1 (en) | 2004-05-13 |
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